Linear butadiene-styrene copolymer, production method and composition thereof, and aromatic vinyl re

专利摘要:
This invention discloses a linear butadiene-styrene copolymer wherein the linear butadiene-styrene copolymer has a wide molecular weight distribution range and the aromatic vinyl resin using the linear butadiene-styrene copolymer as a toughening agent has apparently improved impact resistance and gloss. This invention further relates to an aromatic vinyl resin and a production process thereof, wherein the process for producing the aromatic vinyl resin comprises the steps of directly blending a polymer solution with linear butadiene-styrene copolymer and a polymer solution with low cis polybutadiene rubber with the aromatic vinyl Matrix monomers and then carrying out a bulk polymerization, to obtain the aromatic vinyl resin. The process simplifies the process, shortens the process flow and the advantage is the reduction of energy consumption throughout the process. It is more desirable that the aromatic vinyl resin produced by the process of the present invention exhibit markedly improved gloss and impact resistance.
公开号:BE1025614B1
申请号:E2017/5774
申请日:2017-10-27
公开日:2019-05-06
发明作者:Jiancheng Li；Lin Xu；Xue Wang；Jiangwei Zhao
申请人:China Petroleum & Chemical Corporation；Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation；
IPC主号:

专利说明:

Linear butadiene-styrene copolymer, manufacturing method and composition thereof and aromatic vinyl resin and manufacturing method thereof
DESCRIPTION
Field of the Invention
This invention relates to a linear butadiene-styrene copolymer and its production process; this invention further relates to a composition containing the linear butadiene-styrene copolymer, this invention further relates to an aromatic vinyl resin using the composition as a toughening agent and a production method therefor.
Background of the Invention
The traditional aromatic vinyl resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin) and impact-resistant polystyrene (HIPS resin) is obtained from thermal initiation or initiation with radical initiators by adding the dried rubber toughening agent in a certain proportion to polymeric monomers Production of aromatic vinyl resin, as well as a small amount of ethylbenzene as a solvent. The rubber toughening agent used for aromatic vinyl resin may be polybutadiene rubber, solution-polymerized butadiene-styrene rubber (SSBR) or styrene-butadiene-styrene copolymer.
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Low cis polybutadiene rubber and linear butadiene-styrene copolymer are the best toughening agents for the aromatic vinyl resin, which requires high low temperature toughness and high gloss. Compared to other tough rubber, low cis polybutadiene rubber and linear butadiene-styrene copolymer have the following advantages: (1) high cross-linking reactivity and easy grafting with aromatic vinyl resin because their molecular chains contain vinyl side chains; (2) transition metals excluding high purity, thereby obtaining an advantage in improving aging resistance in the aromatic vinyl resin. However, the low cis polybutadiene rubber and the linear butadiene-styrene copolymer are made using anionic polymerization and have the inherent characteristics of the active polymerization products, i.e. generally narrow molecular weight distribution range and single rubber particle size distribution (generally less than 1, 5 and in the range of 1 to 1.2). This easily leads to poorer processability of the rubber and is also contrary to the improvement in the impact resistance of the resin.
The existing aromatic vinyl resin is generally made using the bulk polymerization process. The process is as follows: first preparing solid particles as toughening agent, then dissolving the solid particles of toughening agent in a solvent and mixing with the polymeric monomer of aromatic vinyl resin to obtain a polymerization reaction to obtain aromatic vinyl resin. However, the aromatic vinyl resin made by this method very difficultly meets the requirements of high gloss applications,
BE2017 / 5774 and the causes thereof can be as follows: During extrusion pelletization of the toughener polymer using a twin screw extruder, a crosslinking reaction occurs due to heating and extrusion in the twin screw extruder, resulting in an increased gel content in the solid particles produced leads as a toughening agent with deteriorated coloring, which speaks against an improvement in the gloss and impact resistance of the aromatic vinyl resin.
Content of the invention
An object of this invention is to overcome the deficiencies in the prior art and to provide a linear butadiene-styrene copolymer. The linear butadiene-styrene copolymer has a wide molecular weight distribution range. The aromatic vinyl resin using the low-linear butadiene-styrene copolymer as a toughening agent has an apparently improved impact resistance.
According to the first aspect of this invention, this invention provides a linear butadiene-styrene copolymer having a number average molecular weight of the linear butadiene-styrene copolymer of 70,000 to 160,000 and a molecular weight distribution index of 1.55 to 2 with unimodal distribution, based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit is 10 to 45% by weight and a content of the butadiene structural unit is 55 to 90% by weight.
According to the second aspect of this invention, this invention provides a composition containing a linear butadiene-styrene copolymer and a low cis polybutadiene rubber, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to the
BE2017 / 5774 is the first aspect of this invention and the molecular weight of the low cis polybutadiene rubber has a bimodal distribution, the number average molecular weight of a low molecular weight component in the bimodal distribution is 42,000 to 90,000 with a molecular weight distribution index of 1.55 to 2, wherein the number average molecular weight of a high molecular weight component in the bimodal distribution is 120,000 to 280,000 with a molecular weight distribution index of 1.55 to 2, wherein based on a total content of the polybutadiene rubber having a low cis content, a content of the high molecular weight component is 60 to 95 % Is.
According to the third aspect of this invention, this invention provides a process for producing the linear butadiene-styrene copolymer according to the first aspect of this invention, comprising the following steps:
(1) under an anionic initiation reaction condition, performing an initiation reaction with butadiene and styrene in contact with an organic lithium initiator in alkylbenzene;
(2) adding a blocking agent to a mixture obtained from the initiation reaction of step (1) and performing a polymerization reaction with the mixture containing the blocking agent in a state of an anionic polymerization reaction;
(3) contacting a mixture obtained from the polymerization reaction with a terminating agent to carry out a termination reaction to obtain the polymer solution containing the linear butadiene-styrene copolymer.
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According to the fourth aspect of this invention, this invention provides an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl monomer and a structural unit derived from the toughening agent, wherein the toughening agent is the composition according to the second aspect of this invention.
According to the fifth aspect of this invention, this invention provides a process for producing an aromatic vinyl resin comprising the step of mixing polymeric monomers containing aromatic vinyl monomer with a solution containing a toughening agent to obtain a mixture and polymerizing the mixture wherein the toughening agent solution contains a linear butadiene-styrene copolymer solution and a low cis polybutadiene rubber solution, the linear butadiene-styrene copolymer solution being the polymer solution which is the linear Contains butadiene-styrene copolymer obtained by the process according to the third aspect of this invention; and the solution containing the low cis polybutadiene rubber is a polymer solution containing the low cis polybutadiene rubber prepared by a process comprising the steps of:
(a) performing an initiation reaction with butadiene in contact with an organic lithium initiator in alkylbenzene under an anionic initiation reaction condition;
BE2017 / 5774 (b) adding a blocking agent to a mixture obtained from the initiation reaction of step (a) and performing a polymerization reaction with the mixture containing the blocking agent in a state of the anionic polymerization reaction;
(c) performing a coupling reaction with a mixture obtained from the polymerization reaction by contact with a coupling agent;
(d) contacting a mixture obtained from the coupling reaction with a terminating agent to carry out a terminating reaction to obtain a polymer solution containing low cis polybutadiene rubber.
The linear butadiene-styrene copolymer of this invention has a wide range of molecular weight distribution, which can effectively increase the impact resistance of the aromatic vinyl resin when used as a toughening agent. In contrast to the existing bulk polymerization process for the production of an aromatic vinyl resin in which both low cis polybutadiene rubber and linear butadiene-styrene copolymer are dry granulated and then redissolved, the process of this invention produces both an aromatic vinyl resin the polymer solution of polybutadiene rubber with a low cis content and the polymer solution of linear butadiene-styrene copolymer mixed with the aromatic vinyl matrix monomers to carry out a bulk polymerization to obtain the aromatic vinyl resin. The process of this invention simplifies the process, shortens the process flow, and is advantageous for reducing overall process energy consumption. It is more desirable that
BE2017 / 5774 the aromatic vinyl resin, produced by the process according to the invention, shows a significantly improved gloss and impact resistance.
Detailed description of the exemplary embodiments
Some embodiments of this invention are described in detail below. It is to be understood that the embodiments described herein are given only to describe and explain this invention, but are not intended to be a limitation on this invention.
The endpoints and any value within the ranges disclosed in this invention are not intended to limit the exact ranges or values; these ranges or values should contain those that are closely related to these ranges or values. For numeric ranges, the endpoints of the ranges, the endpoints of the ranges, and the concrete point values and the concrete point values can be combined to obtain one or more new numerical ranges that are considered to be disclosed in this document.
According to the first aspect of this invention, this invention provides a linear butadiene-styrene copolymer.
According to the invention, the molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution, the number average molecular weight (i.e. Mn) of the linear butadiene-styrene copolymer is 70,000 to 160,000 with a molecular weight distribution index (i.e. Mw / Mn, where Mw is the Weight average molecular weight means) from 1.55 to 2 (preferably 1.6 to 2, more preferably 1.8 to 2).
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In this invention, the molecular weight and molecular weight distribution index of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer are measured by gel permeation chromatography analysis using TOSH HLC-8320 gel permeation chromatograph, the chromatographic columns being TSKgel Super NultiporeHZ TSKgel SuperMultiporeHZ standard columns and the solvent is chromatographically pure tetrahydrofuran (THF) using a narrow distribution polystyrene as the standard sample, the polymer sample is made into a 1 mg / ml THF solution, the injection amount of the sample is 10.00 μΐ, the flow rate is 0.3 ml / min and the test temperature is 40.0 ° C.
According to the linear butadiene-styrene copolymer of this invention, based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit may be 10 to 45% by weight, preferably 15 to 43% by weight, a content of the butadiene structural unit may 55 to 90% by weight, preferably 57 to 85% by weight.
According to the invention, the term styrene structural unit relates to the structural unit formed by polymerizing styrene monomers, and the term butadiene structural unit relates to the structural unit formed by polymerizing butadiene monomers. In this invention, the content of the styrene structural unit and the butadiene structural unit is determined by 1H-NMR analysis; during the test the solvent used is deuterated chloroform and tetramethylsilane is used as the internal standard substance.
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According to the linear butadiene-styrene copolymer of this invention, based on the total amount of the linear butadiene-styrene copolymer, the content of the 1,2-structural unit can be 8 to
% By weight, preferably 10 to 13.5% by weight.
In the linear butadiene-styrene copolymer of this invention, the Mooney viscosity of the linear butadiene-styrene copolymer can be 50 to 150, preferably 50 to 140, and more preferably 50 to 135.
According to the invention, the Mooney viscosity is determined using SHIMADZU SMV-201 SK-160 Mooney viscometer according to the method specified in Chinese National Standards GB / T1232-92, the test method containing: ML (1 + 4) and one Test temperature of 100 ° C.
According to the linear butadiene-styrene copolymer of this invention, a gel content of the linear butadiene-styrene copolymer is below 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, by weight.
According to the invention, the gel content is determined using the weight method. The specific procedure is as follows: adding a polymer sample to styrene and oscillating in an oscillator at 25 ° C for 16 hours to completely dissolve soluble substances to obtain a styrene solution with 5% by weight polymer content (the Mass of the rubber sample is denoted by C (in grams); Weigh a 360 mesh pure nickel screen and designate this mass as B (in grams); then filtering the above solution with the nickel screen and washing the nickel screen with styrene after filtering; Drying the nickel screen at 150 ° C and a normal pressure for 30 minutes and then weighing the nickel screen and
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Denote its mass as A (in grams); where the gel content is calculated from the following formula:
Gel content% = [(A-B) / C] x 100%.
According to the linear butadiene-styrene copolymer of this invention, in a preferred embodiment, the number average molecular weight of the linear butadiene-styrene copolymer is 70,000 to 150,000, preferably 75,000 to 140,000, and a molecular weight distribution index of the linear butadiene-styrene copolymer is 1.6 to 2 and preferably 1.8 to 1.95; based on the total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit can be 12 to 40% by weight, preferably 15 to 35% by weight; a content of the butadiene structural unit can be 60 to 88% by weight, preferably 65 to 85% by weight. In the preferred embodiment, a Mooney viscosity of the linear butadiene-styrene copolymer is 50 to 145, preferably 50 to 135. The linear butadiene-styrene copolymer in this embodiment is particularly suitable as a toughening agent of the ABS resin.
According to the linear butadiene-styrene copolymer of this invention, in another preferred embodiment, the number average molecular weight of the linear butadiene-styrene copolymer is 90,000 to 160,000, preferably 10,000 to 160,000; a molecular weight distribution index of the linear butadiene-styrene copolymer is 1.6 to 2, and preferably 1.8 to 2; based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit can be 12 to 45% by weight, preferably 15 to 42% by weight; a content of the butadiene structural unit can be 55 to 88% by weight, preferably 58 to 85% by weight. In the preferred embodiment, the Mooney viscosity of the linear butadiene-styrene copolymer is 80 to 140, preferably 90 to 130 and more preferably 100 to 135. The linear butadiene-styrene copolymer
BE2017 / 5774 according to this exemplary embodiment is particularly suitable as a toughening agent for high-impact polystyrene.
According to the second aspect of this invention, this invention provides a composition containing a linear butadiene-styrene copolymer and a low cis polybutadiene rubber, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to the first aspect thereof Invention is.
According to the composition of this invention, the molecular weight of the low cis polybutadiene rubber in bimodal distribution, the number average molecular weight of the low molecular weight component in the bimodal distribution is 42,000 to 90,000 with a molecular weight distribution index of 1.55 to 2 (preferred
1.7 to 2); the number average molecular weight of the high molecular weight component in the bimodal distribution is 120,000 to 280,000 with a molecular weight distribution index of 1.55 to 2 (preferred
1.7 to 2), based on a total amount of the polybutadiene rubber with a low cis content, a content of the high molecular weight component is 65 to 95% by weight.
With respect to the low cis polybutadiene rubber, the low molecular weight component in the bimodal distribution is a linear polymer (i.e., uncoupled polymer) and the high molecular weight component in the bimodal distribution is a coupled polymer (i.e. a star-branched polymer). The coupled polymer includes coupling centers and the linear chains attached to the coupling centers, where the linear chains are from linear polymers. According to the invention, the low cis polybutadiene rubber can be obtained by coupling the linear polymers with
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Coupling agents, and the products obtained contain non-coupled polymers (i.e. low molecular weight
Component) and coupled polymers (i.e. high molecular weight
Component).
With respect to the low cis polybutadiene rubber, the molecular weight distribution index of the low cis polybutadiene rubber is 1.9 to 2.5.
In the present invention, the molecular weight distribution index of the low cis polybutadiene rubber is the total molecular weight distribution index of rubber, that is, the molecular weight distribution index is determined by using the double peaks as a yardstick. The molecular weight distribution index of the high molecular weight component in the bimodal distribution relates to the molecular weight distribution index calculated by using the elution peak of the high molecular weight component as a scale; the molecular weight distribution index of the low molecular weight component in the bimodal distribution relates to the molecular weight distribution index calculated by using the elution peak of the low molecular weight component as a yardstick. The content of the high molecular weight component relates to the percentage of the elution peak area of the high molecular weight component to the total area of the double peaks.
With respect to the low cis polybutadiene rubber, based on the total amount of the low cis polybutadiene rubber, the content of the 1,2-structural unit in the low cis polybutadiene rubber may be 8 to 14% by weight; based on the total amount of the low cis polybutadiene rubber, the content of the cis 1,4-structural unit in the low cis polybutadiene rubber is 30 to 40% by weight.
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According to the invention, the term 1,2-structural unit relates to the structural unit formed in the 1,2-polymerization of butadiene, and the 1,2-structural unit content can also be known as the vinyl content. The term cis-1,4 structural unit relates to the structural unit which is formed in the 1,4-polymerization of butadiene and has a cis configuration, that is to say the structural unit with the formula I:
CH ₂ h ₂ c (I)
According to the invention, the content of the 1,2-structural unit and the cis-1,4-structural unit is determined by using; during the test the solvent is deuterated chloroform and tetramethylsilane is used as the internal standard substance.
In this invention, the Mooney viscosity of the low cis polybutadiene rubber of this invention is 30 to 70, preferably 40 to 70, and more preferably 45 to 70.
According to the invention, a gel content of the polybutadiene rubber with a low cis content is below 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, measured by weight.
According to the invention, in a preferred exemplary embodiment, the number average molecular weight of the low molecular weight component in the bimodal distribution is 45,000 to 75,000 with a molecular weight distribution index of 1.7 to 2
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The number average molecular weight of the high molecular weight component in the bimodal distribution is 140,000 to 190,000 with a molecular weight distribution index of 1.7 to 2. Based on the total amount of the low cis polybutadiene rubber, the content of the high molecular weight component is 70 to 95% by weight. In the preferred embodiment, the Mooney viscosity of the low cis polybutadiene rubber is 40 to 65, preferably 45 to 60. The low cis polybutadiene rubber according to this preferred embodiment is particularly useful as a toughening agent of the acrylonitrile-butadiene-styrene copolymer (that is, ABS resin).
According to the invention, in another preferred exemplary embodiment, the molecular weight is in the number average of the low molecular weight component in the bimodal distribution
000 to 90,000 with a molecular weight distribution index of 1.7 to 2, the number average molecular weight of the high molecular weight component in the bimodal distribution is 150,000 to 270,000, preferably 160,000 to 260,000 with a molecular weight distribution index of 1.7 to 2 (preferred
1.8 to 2). Based on a total amount of the polybutadiene rubber with a low cis content, the content of the high molecular weight component is 60 to 95% by weight, preferably 65 to 95% by weight. According to this preferred embodiment, the Mooney viscosity of the low cis polybutadiene rubber is 45 to 70, preferably 50 to 70. The low cis polybutadiene rubber according to this preferred embodiment is particularly suitable as a toughening agent of high impact polystyrene (i.e. is called HIPS resin).
According to the composition of this invention, the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer can be 0.3 to 6: 1
BE2017 / 5774. If the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer is within the above range, the composition is particularly suitable as a toughening agent of the aromatic vinyl resin. The weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer is preferably 0.3-6: 1, preferably 0.4-4: 1, more preferably 0.45-3: 1 and more preferred 0.5-2: 1st
In a preferred embodiment, the weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer is 0.63: 1, preferably 0.8-2: 1, and more preferably 1-1.5: 1. The composition according to this preferred embodiment is particularly suitable as a toughening agent for ABS resin.
In another preferred embodiment, the weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer is 0.43: 1, preferably 0.45-2: 1, and more preferably 0.5-1.5: 1. The composition according to this preferred embodiment is particularly suitable as a toughening agent for high-impact polystyrene.
According to the third aspect of this invention, this invention provides a process for producing the linear butadiene-styrene copolymer according to the first aspect of this invention, comprising the following steps:
(1) On condition of an anionic
Initiation reaction there is an initiation reaction of butadiene and styrene in contact with an organic lithium initiator in alkylbenzene;
BE2017 / 5774 (2) adding a blocking agent to a mixture obtained from the initiation reaction of step (1) and performing a polymerization reaction with the mixture containing the blocking agent in a state of an anionic polymerization reaction, (3) contacting a mixture from the polymerization reaction with a terminating agent to carry out a termination reaction to obtain the polymer solution containing linear butadiene-styrene copolymer.
The alkylbenzene is used as the polymerization solvent in step (1). The alkylbenzene can be one or more of monoalkylbenzene, dialkylbenzene and trialkylbenzene. Specifically, the alkylbenzene can be selected from compounds with the formula II.
wherein Rj_ and Rg are the same or different and are independently selected from hydrogen atom or Cj__5-alkyl, for example hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl or neoamyl; in addition, Rj_ and Rg are not hydrogen atom at the same time.
The alkylbenzene is preferably one or more selected from the group consisting of toluene, ethylbenzene and dimethylbenzene. The alkylbenzene is more preferably ethylbenzene.
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In step (1), the alkylbenzene is used as the polymerization solvent, and an amount may allow the total concentration of butadiene and styrene in the alkylbenzene to be 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, more preferably 20% by weight or more, more preferably 25% by weight or more, particularly preferably 30% by weight or more. The amount of the alkylbenzene can allow the total concentration of butadiene and styrene in the alkylbenzene to be 70% by weight or less, preferably 65% by weight or less, more preferably 60% by weight or less. The total concentration of butadiene and styrene in alkylbenzene is preferably 30 to 60% by weight, more preferably 35 to 55% by weight and more preferably 40 to 55% by weight. The obtained polymer solution with the linear butadiene-styrene copolymer by polymerization at the above monomer concentration can be mixed directly with the polymeric monomers from the aromatic vinyl resin for bulk polymerization without solvent removal to produce aromatic vinyl resin such as ABS resin and HIPS resin.
In step (I), the amount of styrene and butadiene corresponding to the intended linear butadiene-styrene copolymer can be selected on the basis of the total amount of styrene and butadiene, a content of styrene can be 10 to 45% by weight, preferably 15 to 43% by weight his; the content of butadiene can be 55 to 90% by weight, preferably 57 to 85% by weight.
In a preferred embodiment, based on the total amount of styrene and butadiene, a styrene content can be 12 to 40% by weight, preferably 15 to 35% by weight; a content of butadiene can be 60 to 88% by weight, preferably 65 to 85% by weight, and the polymer solution obtained with linear butadiene-styrene copolymer according to this exemplary embodiment is particularly suitable as toughening agent of the ABS resin.
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In another preferred exemplary embodiment, based on the total amount of styrene and butadiene, a styrene content can be 12 to 45% by weight, preferably 15 to 42% by weight; a content of butadiene can be 55 to 88% by weight, is preferably 58 to 85% by weight, and the polymer solution obtained with linear butadiene-styrene copolymer according to this exemplary embodiment is particularly suitable as toughening agent of impact-resistant polystyrene.
In step (1), the initiation reaction is used to enable a contact reaction of styrene and butadiene with an organic lithium initiator and to carry out the oligomerization to obtain an oligomer with an active end group, for example an oligomer with an active end group and a molecular weight of 100 to 200. In general, the initiation reaction can be carried out at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C. A time of the initiation reaction may be 1 to 8 minutes, preferably 1 to 5 minutes, preferably 2 to 4.5 minutes and more preferably 3 to
Minutes.
In step (1), the organic lithium initiator can be any typical organic lithium initiator that can initiate the polymerization of styrene and butadiene in the anionic polymerization field. The organic lithium initiator is preferably an organic mono-lithium compound and more preferred is the compound of formula III.
RgLi formula III, wherein R3 is Cj __] _ Q-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
BE2017 / 5774 n-amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the different isomers), heptyl (including the different isomers), octyl (including the different isomers), nonyl (including the different isomers) or decyl (including the different isomers
The specific examples of the organic lithium initiator may include, but are not limited to: one or more selected from the group consisting of lithium ethide, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium and isobutyllithium.
The organic lithium initiator is preferably one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium. The organic lithium initiator is more preferably n-butyllithium.
The amount of the organic lithium initiator can be selected according to the molecular weight of the intended polymer. Preferably, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (2) to be 70,000 to 160,000. In a preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (2) to be 70,000 to 150,000 (preferably 75,000 to 140,000) and the polymer solution with the linear butadiene -Styrene copolymer in this embodiment is particularly suitable as a toughening agent of ABS resin. In another preferred embodiment, the amount of organic allows
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Lithium initiator that the number average molecular weight of the polymer obtained from the polymerization reaction in the
Step (2), 90,000 to 160,000 (preferably 100,000 to
160,000) and the polymer solution containing the linear butadiene-styrene copolymer in this preferred embodiment is particularly suitable as a toughening agent for a high-impact polystyrene.
The method for determining the amount of initiator according to the molecular weight of the intended polymer is known to the person skilled in the art and is therefore not described in detail in this disclosure.
In step (1), the organic lithium initiator is added to a polymerization system in the form of a solution.
For example, a solvent in a solution of the organic lithium initiator may be one or more of hexane, cyclohexane and heptane, and a concentration of this solution is preferably 0.5 to 2 mol / 1 and preferably 0.8 to
1.5 mol / 1.
In step (2), the blocking agent is added to the mixture obtained from the initiation reaction to carry out the polymerization reaction. The blocking agent is selected from one or more metal alkyl compounds and preferably one or more is selected from the group consisting of organic aluminum compound, organic magnesium compound and organic zinc compound.
The organic aluminum compound can be one or more of the compounds of formula IV.
Γ
R ₆ AI R ₅
Formula IV,
BE2017 / 5774 wherein R4, R5 and Rg are identical or different from one another and are selected independently from Cj__g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl , tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).
The specific examples of the organic aluminum compounds may include, but are not limited to: one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum and triisobutyl aluminum, and preferably selected from triethyl aluminum and / or triisobutyl aluminum.
The organic magnesium compound can be one or more of the compounds having the formula V.
Rs Mg R7
Formula V wherein R7 and Rg are identical or different and are independently selected from Cj__g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl , tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers) or octyl (including the various isomers).
The specific examples of the organic magnesium compound may include, but are not limited to: one or more selected from the group consisting of di-n-butyl magnesium, di-sec-butyl magnesium, diisobutyl magnesium,
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Di-tert-butylmagnesium and n-butyl-sec-butylmagnesium and preferred is n-butyl-sec-butylmagnesium.
The organic zinc compound can be the compound of formula VI.
^ ¹⁰ Z ⁿ Formula VI wherein Rg and Rj_q are identical or different and are independently selected from Cj__g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n -Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).
The specific examples of the organic zinc compound may include, but are not limited to: one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-sec-butyl zinc,
Diisobutyl zinc and di-tert-butyl zinc and preferably selected from diethyl zinc and / or di-n-butyl zinc.
The blocking agent is preferably an organic aluminum compound and / or organic magnesium compound. More preferably, the blocking agent is one or more selected from the group consisting of triethyl aluminum, triisobutyl aluminum and n-butyl-sec-butyl magnesium.
The amount of the blocking agent can be selected according to the type.
In one embodiment, the blocking agent is the organic aluminum compound, and a molar ratio of the organic aluminum compound and the organic lithium initiator may be 0.6-0.95: 1, preferably 0.7
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0.9: 1, the organic aluminum compound is calculated by the aluminum element and the organic lithium initiator is calculated by the lithium element.
In another embodiment, the blocking agent is the organic magnesium compound, and a molar ratio of the organic magnesium compound and the organic lithium initiator may be 1-6: 1, preferably 2-4: 1, the organic magnesium compound calculated by magnesium element, and the organic lithium initiator is calculated by lithium element.
In another embodiment, the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound, a molar ratio of the organic aluminum compound to the organic magnesium compound to the organic lithium initiator can be 0.5-2: 1 -5: 1, is preferably 0.8-1: 1.5-3: 1, the organic aluminum compound by aluminum element, the organic magnesium compound by magnesium element and the organic lithium initiator by lithium -Element to be calculated.
In another embodiment, the blocking agent is an organic zinc compound, a molar ratio of the organic zinc compound to the organic lithium initiator can be 1-6: 1, preferably it is 2-4: 1, the organic zinc compound is replaced by zinc Element is calculated and the organic lithium initiator is calculated by lithium element.
In step (2), the polymerization reaction can be carried out under a conventional condition of the anionic polymerization reaction. In general, the condition of the polymerization reaction may include:
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Temperature of 50 to 140 ° C, preferably 70 to 130 ° C and more preferably 80 to 120 ° C; a time of 60 to 150 min, preferably 70 to 120 min.
In step (3), the terminating agent is added to the mixture obtained from the polymerization reaction to inactivate active chains. The terminating agent may be one or more of Cj__4 alcohol, organic acid and carbon dioxide and is preferably one or more of isopropanol, geoceric acid, citric acid and carbon dioxide, and more preferred is carbon dioxide.
In a preferred embodiment, step (3) includes: performing a contact reaction with the mixture obtained from the polymerization reaction in step (2) with carbon dioxide. Carbon dioxide is used to carry out the termination reaction. Carbon dioxide can form carbonates with metal ions (Li, Mg, Al, Zn and Fe) in the polymerization system, so that the chromogenic reaction of metal ions is avoided and the polymer product produced has a low color. The carbon dioxide can be injected into the reaction system in the form of a gas, for example carbon dioxide gas at 0.2 to 1 MPa (gauge pressure), preferably 0.3 to 0.6 MPa (gauge pressure) is injected into the mixture by the polymerization reaction is obtained. The carbon dioxide can also be introduced into the mixture obtained by the polymerization reaction in the form of a water solution of dry ice; for example, 0.5 to 2 mol / 1 of dry ice in water is introduced into the mixture obtained from the polymerization reaction.
In this embodiment, a termination reaction condition may include: temperature from 50 to 80 ° C, time from 10 to 40 min.
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According to the method for producing the linear butadiene-styrene copolymer in this invention, the polymer solution obtained from the termination reaction in step (3) can be directly discharged, or used in the subsequent operations without solvent removal treatment; for example, the polymer solution can be used directly to prepare the toughening agent of the aromatic vinyl resin, produced by a bulk polymerization process. Under a specific condition, the polymer solution obtained from the termination reaction in step (3) can also be treated for solvent removal; for example, the evaporation process is used to remove parts of the solvents so as to meet the requirements of the subsequent process operations. The polymer solution obtained from the termination reaction in step (3) can also be treated for solvent removal using conventional methods (e.g. coagulation) and is extruded and pelletized through an extruder (e.g. twin screw extruder) to give the corresponding polymer granules.
According to the method for producing the linear butadiene-styrene copolymer of this invention, the use of alkylbenzene as a polymerization solvent while introducing a blocking agent during the polymerization reaction can effectively broaden the molecular weight distribution range of the linear butadiene-styrene copolymer produced. The linear butadiene-styrene copolymer obtained by the production method of this invention generally has a molecular weight distribution index of 1.55 to 2, preferably 1.6 to 2 and more preferably 1.8 to 2. In addition, the method for producing the polybutadiene rubber can with low cis content strong according to the invention
BE2017 / 5774 reduce the gel content of the polymer produced; for example, the gel content of the linear butadiene-styrene copolymer is less than 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, by weight. The linear butadiene-styrene copolymer produced by the process of the invention is particularly suitable as a toughening agent of the acrylonitrile-butadiene-styrene copolymer (i.e. ABS resin) and the impact-resistant polystyrene (i.e. HIPS resin).
According to the fourth aspect of this invention, this invention provides an aromatic vinyl resin containing a structural unit derived from aromatic vinyl monomer and a structural unit derived from the toughening agent, wherein the toughening agent is the composition according to the second aspect of this invention.
In this invention, the term structure derived from aromatic vinyl monomer refers to the structural unit formed by aromatic vinyl monomers, and the structural unit and aromatic vinyl monomers have the same atom types and atomic numbers except for the electron structure with some modification; the term structural unit derived from the toughening agent refers to the structural unit formed by the toughening agent, and the structural unit and the toughening agent have the same atom types and the same atomic number except for the electron structure with some modification.
The aromatic vinyl monomer refers to the monomer containing both aryl (e.g. vinyl) and vinyl in the molecular structure. The specific examples of the aromatic vinyl monomer may include, but are not limited to: one or more selected from the group consisting of
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Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, oethylstyrene, p-ethylstyrene and vinyl naphthalene. The aromatic vinyl monomer is preferably styrene.
The aromatic vinyl resin may contain only the structural unit derived from the aromatic vinyl monomers and the structural unit derived from the toughening agent, or may further contain another structural unit derived from other vinyl monomers. The specific examples of the other vinyl monomers may include, but are not limited to: one or more selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and maleic acid.
In a preferred embodiment, the aromatic vinyl resin contains only the structural unit derived from the aromatic vinyl monomers and the structural unit derived from the toughening agent, and a preferred aromatic vinyl resin is a high impact polystyrene. Based on the total amount of the high impact polystyrene, a content of the styrene structural unit may be 80 to 95% by weight, is preferably 85 to 93% by weight and more preferably 88 to 92% by weight; a content of the butadiene structural unit can be 5 to 20% by weight, preferably 7 to 15% by weight and more preferably 8 to 12% by weight. The weight average molecular weight of the high impact polystyrene can be 150,000 to 350,000, is preferably 160,000 to 220,000 and more preferably is 170,000 to 300,000, and the molecular weight distribution index can be 1.8 to 3.8, preferably 2 to 3 , 5 and more preferably 2.5 to 3.3.
In another embodiment, the aromatic vinyl matrix resin contains the structural unit derived from the aromatic vinyl monomers, the structural unit derived from the
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Toughening agent, and the structural unit derived from acrylonitrile, and a preferred aromatic vinyl resin is acrylonitrile-butadiene-styrene copolymer. The composition of the acrylonitrile-butadiene-styrene copolymer can be routinely selected. In general, based on a total amount of the acrylonitrile-butadiene-styrene copolymer, a content of the butadiene structural unit can be 5 to 20% by weight, 8 to 15% by weight being preferred; a content of the styrene structural unit can be 55 to 75%, preferably 60 to 72% by weight; a content of the acrylonitrile structural unit (ie the structural unit formed by acrylonitrile) can be 10 to 35% by weight, preferably 15 to 30% by weight. The weight average molecular weight of the acrylonitrile-butadiene-styrene copolymer can be 100,000 to 400,000, preferably 150,000 to 350,000 and more preferably 180,000 to 300,000, and the molecular weight distribution index can be 2 to 4, preferably 2.2 to 3.5 and more is preferred from 2.3 to 3.
The total amount of toughening agent can be routinely selected. With regard to the total content of the aromatic vinyl resin, the content of the toughening agent may be 2 to 25% by weight, 5 to 20% by weight being preferred. The amount of toughening agent can be optimized according to the type of aromatic vinyl resin.
In a preferred embodiment, the aromatic vinyl resin is acrylonitrile-butadiene-styrene resin; based on a total content of the aromatic vinyl resin, a preferable content of the toughening agent is 5 to 20% by weight, more preferably 6 to 15% by weight, and more preferably 8 to 13% by weight.
In another preferred embodiment, the aromatic vinyl matrix resin is high impact polystyrene; based on a total amount of the aromatic vinyl resin
BE2017 / 5774 a preferred content of the toughening agent 5 to 15% and more preferred are 6 to 12% by weight.
According to the fifth aspect of this invention, this invention provides a process for producing an aromatic vinyl resin comprising the steps of mixing the polymeric monomers containing the aromatic vinyl monomer with a solution containing a toughening agent to obtain a mixture and polymerizing the A mixture in which the solution containing the toughening agent contains a solution containing linear butadiene-styrene copolymer and a solution with polybutadiene rubber having a low cis content, the solution containing the linear butadiene-styrene copolymer is the polymer solution containing the linear butadiene-styrene copolymer obtained by the method according to the third aspect of this invention; and the solution containing the low cis polybutadiene rubber is a polymer solution containing low cis polybutadiene rubber made by a method comprising the steps of:
(a) under an anionic initiation reaction condition, butadiene in contact with an organic lithium initiator in alkylbenzene is subjected to an initiation reaction;
(b) a blocking agent is placed in a solution obtained from the initiation reaction of step (a), and polymerization reaction is carried out with the mixture that the
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Contains blocking agent, carried out in a condition of an anionic polymerization reaction;
(c) a mixture obtained from the polymerization reaction is subjected to a coupling reaction by contacting with a coupling agent;
(d) A mixture obtained from the coupling reaction is contacted with a terminating agent to carry out a terminating reaction to obtain a polymer solution containing low cis polybutadiene rubber.
The alkylbenzene is used as the polymerization solvent in step (a). The alkylbenzene can be one or more selected from the group consisting of monoalkylbenzene, dialkylbenzene and trialkylbenzene. Specifically, the alkylbenzene can be selected from the compounds of formula II.
wherein Rj_ and R2 are the same or different and are each independently selected from hydrogen or Cj__5alkyl, for example hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl , Isoamyl, tert-amyl or neoamyl; in addition, Rj_ and R2 are not simultaneously a hydrogen atom.
The alkylbenzene is preferably one or more selected from the group consisting of toluene, ethylbenzene and
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Dimethylbenzene. The alkylbenzene is more preferably ethylbenzene.
In step (a), the alkylbenzene is used as a polymerization solvent and its amount enables the concentration of butadiene in the alkylbenzene to be 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, more preferably 20 % By weight or more, more preferably 25% by weight or more, particularly preferably 30% by weight or more. The amount of the alkylbenzene may allow the concentration of butadiene in the alkylbenzene to be 70% by weight or less, preferably 65% by weight or less, more preferred
% By weight or less. The concentration of butadiene in the alkylbenzene is preferably 30 to 60% by weight, more preferably up to 55% by weight and more preferably 40 to 55% by weight. The obtained polymer solution containing low cis polybutadiene rubber obtained by polymerization at the above monomer concentration can be directly mixed with the polymeric monomers of aromatic vinyl resin for bulk polymerization without solvent removal to prepare an aromatic vinyl resin such as ABS resin and HIPS resin.
In step (a), the initiation reaction is used to allow butadiene to contact an organic lithium initiator and carry out the oligomerization to give an oligomer with active end groups, for example an oligomer with active end groups and a molecular weight of 100 to 200. In general, the initiation reaction can be carried out at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C. A time of the initiation reaction can be 1 to 8 minutes, preferably 1 to 5 minutes, preferably 2 to
4.5 minutes and more preferably 3 to 4 minutes.
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In step (a), the organic lithium initiator can be any typical organic lithium initiator that can initiate the polymerization of butadiene in the anionic polymerization field. The organic lithium initiator is preferably an organic mono-lithium compound and more preferred is the compound of formula III.
R ₃ Li
Formula III, wherein R _{3 is} C] __] _ Q-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert-amyl, neoamyl , Hexyl (including the various isomers), heptyl (including the various isomers), octyl (including the various isomers), nonyl including the various isomers) or decyl (including the various isomers)
The specific examples of the organic lithium initiator may include, but are not limited to: one or more selected from the group consisting of lithium ethide, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium and isobutyllithium.
The organic lithium initiator is preferably one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium. The organic lithium initiator is more preferably n-butyllithium.
The amount of the organic lithium initiator can be selected according to the molecular weight of the expected polymer. Preferably, the amount of the organic lithium initiator enables the molecular weight in
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The number average of the polymer obtained from the polymerization reaction in step (b) is 42,000 to 90,000. In a preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (b) to be 45,000 to 75,000 and the polymer solution containing low cis polybutadiene rubber This preferred embodiment is particularly suitable as a toughening agent for ABS resin. In another preferred embodiment, the amount of the lithium organic initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (b) to be 50,000 to 90,000 and the polymer solution containing low cis polybutadiene rubber In this preferred embodiment, it is particularly suitable as a toughening agent of high-impact polystyrene.
The method for determining the amount of initiator according to the molecular weight of the expected polymer is known to the person skilled in the art and is therefore not described in detail.
In step (a), the organic lithium initiator is added to a polymerization system in the form of a solution.
For example, a solvent in a solution of the organic lithium initiator may be one or more of hexane, cyclohexane and heptane, and a concentration of this solution is preferably 0.5 to 2 mol / 1 and more preferably 0.8 to 1.5 mol / 1.
In step (b), the blocking agent is added to the mixture obtained from the initiation reaction to carry out the polymerization reaction. The blocking agent is selected from one or more metal alkyl compounds and preferably one or more is selected
BE2017 / 5774 from the group consisting of an organic aluminum compound, organic magnesium compound and organic
Zinc compound.
The organic aluminum compound can be one or more of the compounds of formula IV.
6 ^R 6 ^{Al Rs} formula IV, in which R4, R5 and Rg are identical or different from one another and are selected independently from Cj__g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).
The specific examples of the organic aluminum compounds may include, but are not limited to: one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum and triisobutyl aluminum, and preferably selected from triethyl aluminum and / or triisobutyl aluminum.
The organic magnesium compound can be one or more of the compounds having the formula V.
Rs Mg R7
Formula V wherein R7 and Rg are identical or different and are independently selected from Cj__g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl , tert-amyl, neoamyl,
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Hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).
The specific ones of the organic magnesium compound can include, but are not limited to: one or more selected from the group consisting of di-n-butyl magnesium, di-sec-butyl magnesium, diisobutyl magnesium, di-tert-butyl magnesium and n-butyl-sec-butyl magnesium and n-butyl-sec-butyl magnesium is preferred.
The organic zinc compound can be the compound of formula VI.
^ ¹⁰ Z ⁿ Formula VI wherein Rg and Rj_q are identical or different and are independently selected from C] __ g-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl , n-amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).
The specific examples of the organic zinc compound may include, but are not limited to: one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-sec-butyl zinc,
Diisobutyl zinc and di-tert-butyl zinc and preferably selected from diethyl zinc and / or di-n-butyl zinc.
The blocking agent is preferably an organic aluminum compound and / or organic magnesium compound. More preferably, the blocking agent is one or more selected from the group consisting of triethyl aluminum, triisobutyl aluminum and n-butyl-sec-butyl magnesium.
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The amount of the blocking agent can be selected according to the type.
In one embodiment, the blocking agent is the organic aluminum compound, and a molar ratio of the organic aluminum compound and the organic lithium initiator may be 0.6-0.95: 1, preferably 0.70.9: 1, that organic aluminum compound is calculated by the aluminum element and the organic lithium initiator is calculated by the lithium element.
In another embodiment, the blocking agent is the organic magnesium compound, and a molar ratio of the organic magnesium compound and the organic lithium initiator may be 1-6: 1, preferably 2-4: 1, the organic magnesium compound calculated by magnesium element, and the organic lithium initiator is calculated by lithium element.
In another embodiment, the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound, a molar ratio of the organic aluminum compound to the organic magnesium compound to the organic lithium initiator can be 0.5-2: 1 -5: 1, is preferably 0.8-1: 1.5-3: 1, the organic aluminum compound by aluminum element, the organic magnesium compound by magnesium element and the organic lithium initiator by lithium -Element to be calculated.
In another embodiment, the blocking agent is an organic zinc compound, a molar ratio of the organic zinc compound to the organic lithium initiator can be 1-6: 1, preferably it is 2-4: 1, the
BE2017 / 5774 organic zinc compound is calculated by zinc element and the organic lithium initiator is calculated by lithium element.
In step (b), the polymerization reaction can be carried out under a conventional condition of the anionic polymerization reaction. In general, the condition of the polymerization reaction may include: temperature of 50 to 140 ° C, preferably 70 to 130 ° C and more preferably 80 to 120 ° C; a time of 60 to 150 min, preferably 70 to 120 min.
In step (c), a coupling agent is used to carry out the coupling of the mixture obtained from the polymerization reaction in step (b), and part of the polymer chains are bonded to form multi-arm star polymers so that the molecular weight of the one produced Low cis polybutadiene rubber shows a bimodal distribution. The specific examples of the coupling agent may include, but are not limited to, one or more selected from the group consisting of tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-octamethylene bromide, γ-aminopropyltriethoxysilane, γGlycidoxypropyltrimethoxysilane, and γ (methylacrylyl), γ (methylacrylyl) ß-aminoethyl) -γaminopropyltrimethoxysilan. The coupling agent is preferably tetrachlorosilane and / or methyltrichlorosilane.
The amount of the coupling agent can be selected according to an introduction amount of the intended multi-arm star polymer of the low cis polybutadiene rubber. Preferably, the amount of the coupling agent enables the molecular weight of the finally obtained low cis polybutadiene rubber to be in a bimodal distribution, the molecular weight in
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Number average of the high molecular weight component (i.e.
Polymer components formed by the coupling) in the bimodal distribution is 120,000 to 280,000 and the content (also known as coupling efficiency) of the high molecular weight component is 65 to 95% by weight.
In a preferred embodiment, the amount of the coupling agent enables the molecular weight of the low cis polybutadiene rubber finally produced to be in a bimodal distribution, the number average molecular weight of the high molecular weight component in the bimodal distribution is 140,000 to 190,000 and the content the high molecular weight component is 70 to 95% by weight. The polymer solution containing the low cis polybutadiene rubber according to this embodiment is particularly suitable as a toughening agent for ABS resin.
In another preferred embodiment, the amount of coupling agent allows the molecular weight of the low cis polybutadiene rubber ultimately produced to be in the bimodal distribution, the number average molecular weight of the high molecular weight component in the bimodal distribution, 150,000 to 270,000, preferably 160 000 to 260,000 and the content of the high molecular weight component is 60 to 95% by weight, preferably 65 to 95% by weight. The polymer solution containing polybutadiene rubber with a low cis content according to this exemplary embodiment is particularly suitable as a toughening agent for high-impact polystyrene.
The amount of coupling agent expected coupling efficiency. Ratio of the coupling agent initiator 0.1-0.5: 1, can preferably be determined according to the In general, the molar to organic lithium is 0.15-0.4: 1. The organic
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Lithium initiator refers to the organic lithium initiator used in the initiation reaction in step (a) and does not contain the organic lithium initiator that is added to remove the contaminants in the reaction system before adding the polymeric monomers. The coupling agent can be added to the polymerization system in the form of a solution. For example, the solvent for dissolving the coupling agent may be one or more of hexane, cyclohexane and heptane, and the concentration of the coupling agent is preferably 0.05 to 1 mol / 1, preferably 0.1 to 0.5 mol / 1 and more preferably 0 , 1 to 0.2 mol / 1.
The coupling reaction can be carried out under conventional conditions in step (c). In general, a condition of the coupling reaction may include: a temperature of 50 to 100 ° C, preferably 60 to 80 ° C, and a time of 20 to 150 min, preferably 30 to 120 min.
In step (d) the terminating agent is added to the mixture obtained from the coupling reaction to inactivate the active chains. The terminating agent may be one or more selected from the group consisting of C] _- 4 ^_ alcohol, organic acid and carbon dioxide, and preferably one or more selected from the group consisting of isopropanol, geoceric acid, citric acid and carbon dioxide, and more preferred carbon dioxide.
In a preferred embodiment, step (d) includes: performing a contact reaction with the mixture obtained from the coupling reaction in step (c) with carbon dioxide. Carbon dioxide is used to carry out the termination reaction. Carbon dioxide can form carbonates with metal ions (Li, Mg, Al, Zn and Fe) in the polymerization system, so that the chromogenic reaction of the metal ions
BE2017 / 5774 avoided and the polymer product produced has a lower color. The carbon dioxide can be injected into the reaction system in the form of a gas; for example, the carbon dioxide gas of 0.2 to 1 MPa (gauge pressure), preferably 0.32 to 0.6 MPa (gauge pressure) is injected into the mixture obtained from the coupling reaction. The carbon dioxide can also be introduced into the mixture in the form of a water solution of dry ice obtained from the coupling reaction; for example, 0.5 to mol / 1 dry ice in water is introduced into the mixture obtained from the coupling reaction.
In this embodiment, a termination reaction condition may include: a temperature of 50 to 80 ° C, a time of 10 to 40 minutes.
The polymer solution obtained from the termination reaction in step (d) can be used directly to prepare the toughening agent of the aromatic vinyl resin produced by the bulk polymerization process.
The use of alkylbenzene as the polymerization solvent while the blocking agent is introduced during the polymerization reaction can effectively broaden the molecular weight distribution range of the low cis polybutadiene rubber produced and the molecular weight of the low cis polybutadiene rubber in the polymer solution, the polybutadiene rubber containing low cis, obtained from the invention, is in bimodal distribution. The molecular weight distribution range of the low molecular weight component in the bimodal distribution can be 1.55 to 2, is preferably 1.7 to 2, the molecular weight distribution range of the high molecular weight component in the bimodal distribution can be 1.55 to 2,
BE2017 / 5774 is preferred 1.7 to 2. In addition, the polymer solution containing the low cis polybutadiene rubber obtained by this invention has a low gel content; for example, the gel content is below 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, measured by weight.
According to the process for producing the aromatic vinyl resin according to this invention, the polymer solution containing the toughening agent can be used directly for producing the aromatic vinyl resin without solvent removal treatment, thereby shortening the process route and reducing the operating power consumption. This can also effectively prevent the gel content from increasing and the deterioration of the color of the polymer, which can be caused by the solvent removal process, so as to influence the impact resistance and the gloss of the aromatic vinyl resin finally obtained.
According to the process for producing the aromatic vinyl resin of this invention, the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer can be 0.3-6: 1. If the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer falls within the above range, the composition is particularly suitable as a toughening agent of the aromatic vinyl resin. The weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer is preferably 0.3-6: 1, preferably 0.4-4: 1, preferably 0.45-3: 1 and more preferred 0.5-2: 1st
According to the process for producing the aromatic vinyl resin of this invention, the specific ones
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Examples of the aromatic vinyl monomer include, but are not limited to: one or more of styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, n-ethyl styrene and vinyl naphthalene. The aromatic vinyl monomer is preferably styrene.
The polymeric monomer may contain other vinyl monomers in addition to aromatic vinyl monomers. The specific examples of other vinyl monomers may include, but are not limited to: one or more selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and maleic acid.
According to the process for producing the aromatic vinyl resin of this invention, the polymerization reaction can be carried out by free radical polymerization. The free Radikai initiator type used in free radical polymerization is not particularly limited and can be selected routinely; for example, the free radical initiator can be one or more of the free radical initiators for thermal decomposition. The free radical initiator is preferably one or more of peroxide initiator and azodinitrile initiator. The specific examples of the free radical initiator may include, but are not limited to: one or more selected from the group consisting of dibenzoyl peroxide, tert-butylperoxy-2ethylhexyl carbonate, peroxydicarbonate, percarboxy ester, alkyl peroxide and azodinitrile compound (e.g. azodiisobutyl nitrile and azo-bis -isoheptonitril). The free radical initiator is preferably one or more selected from the group consisting of dibenzoyl peroxide,
Di (o-methylbenzoyl) peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexyl carbonate.
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The amount of the free radical initiator can be routinely selected so that the aromatic vinyl resin having the expected molecular weight can be obtained. The method for determining the amount of initiator according to the expected polymer molecular weight is known to the person skilled in the art and is therefore not described in detail.
According to the process for producing the aromatic vinyl resin of this invention, the polymerization reaction can be carried out under routine conditions. More preferably, a condition of the polymerization reaction includes: temperature from 100 to 155 ° C (e.g. 100 to 150 ° C) and time from 4 to 12 hours (e.g. 7 to 9 hours).
In a preferred example, one condition of the polymerization reaction includes: first reaction at 100 to 110 ° C. for 1 to 3 h, optionally reaction at 115 to 125 ° C. for 1 to 3 h (eg 1.5 to 2.5 h), then Reaction at 130 to 140 ° C for 1 to 3 h (eg 1.5 to 2.5 h) and finally reaction at 145 to 155 ° C for 1 to 3 h (for example 1.5 to 2.5 h). A condition of the polymerization reaction preferably contains: first reaction at 105 to 110 ° C. for 1 to 2 hours, subsequent reaction at 120 to 125 ° C. for 1 to 2 hours, subsequent reaction at 130 to 135 ° C. for 1 to 2 hours and finally Reaction at 150 to 155 ° C for 1 to 2 h.
Hereinafter, this invention will be described in detail in some embodiments, but the scope of this invention is not limited.
In the following examples, the pressure of CO2 is pressure gauge.
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The following test procedures are used in the following examples:
(1) molecular weight and
Molecular weight distribution index
The molecular weight and the molecular weight distribution index are determined using TOSOH HLC-8320 gel permeation chromatograph. The gel permeation chromatograph is equipped with TSKgel SuperMultiporeHZ-N and TSKgel SuperMultiporeHZ standard columns; the solvent is chromatographically pure THF and narrow distribution polystyrene is used as the standard sample.
The test procedure for the molecular weight and molecular weight distribution index of low cis polybutadiene rubber and linear butadiene-styrene copolymer is as follows: the solvent is chromatographically pure THF and narrow distribution polystyrene is used as a standard sample; the polymer sample is made into a 1 mg / ml THF solution; an injection amount of the sample is 10.00 μΐ; a flow rate is 0.35 ml / min and the test temperature is 40.0 ° C.
The molecular weight distribution index of the low cis polybutadiene rubber is the total molecular weight distribution index of rubber, that is, the molecular weight distribution index is determined by using double peaks as the standard. The molecular weight distribution index of the high molecular weight component in the bimodal distribution relates to the molecular weight distribution index calculated by using the elution peak of the high molecular weight component as a yardstick.
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The molecular weight distribution index of the low molecular weight component in the bimodal distribution relates to the molecular weight distribution index calculated by using the elution peak of the low molecular weight component as a yardstick. The content of the high molecular component relates to the percentage of the area of the elution peak of the high molecular component to the total area of the double peaks.
The test procedure for the molecular weight and the molecular weight distribution index of ABS resin and HIPS resin is as follows: dissolving ABS resin and HIPS resin with toluene and performing centrifugal separation; after agglomeration of the upper clear solution with ethanol, the clear solution is dissolved with THF and then made into a 1 mg / l solution. THF is used as the mobile phase and the test temperature is 40 ° C.
(2) Microscopic structure of the polymer containing: content of each structural unit, content of the 1.2 structural unit and content of the cis-1,4 structural unit.
The content is determined using the AVANCEDRX40OMHz nuclear magnetic resonance system, produced by BRUKER. During the test, the solvent used is deuterated chloroform and tetramethylsilane is used as the internal standard substance.
(3) Mooney viscosity
Mooney viscosity is determined using SHIMADZU SMV-201 SK-160 Mooney Viscometer according to the procedure given in GB / T1232-92, the test procedure is ML (1 + 4) and the test temperature is 100 ° C.
BE2017 / 5774 (4) gel content
The gel content is determined using the weight method. The specific procedure is as follows: adding a polymer sample in styrene and oscillating in an oscillator at 25 ° C for 16 hours so as to completely dissolve soluble substances to obtain a styrene solution with 5% by weight polymer content (the mass of the Rubber sample is referred to as C (in grams); weighing a 360 mesh pure nickel sieve and denoting the mass as B (in grams); then filtering the above solution with the nickel sieve and washing the nickel sieve with styrene after filtering; drying the nickel sieve at 150 ° C and normal pressure for 30 minutes and then weighing the nickel sieve and denoting the mass as A (in grams); the gel content is calculated using the following formula:
Gel content% = [(A-B) / 0] x 100% (5) impact resistance
The impact resistance of the ABS resin is determined using a specific test method for impact resistance with a cantilever beam (J / m) according to ASTMD256 and the dimension of the sample tape used is 63.5 mm x 12.7 mm x 6.4 mm.
The impact strength of HIPS resin is determined using a specific test method for the impact strength (in kJ / m ^) of the cantilever beam in GB / T1843-1996, and the dimension of the sample tape used is 80 mm x 10 mm x 4 mm.
BE2017 / 5774 (6) 60 ° gloss is determined using a
Procedure according to ASTM D526 (60 °)
example 1
This method is provided to describe this invention.
(1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 5 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C. for 3 min is reacted to; then 4 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solvents is raised to 90 ° C. and the mixture is reacted at this temperature for 120 min; 6.5 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 40 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution Al with polybutadiene rubber with low cis content (the concentration of the polymers is
Wt.%). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
(2) 275 g of ethylbenzene, 67.5 g of styrene and 157.5 g of butadiene are mixed and 1.8 ml of n-hexane solution from n
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Butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C for a reaction for 3 min; 1.5 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 120 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B1 of the linear butadiene-styrene copolymer (concentration of the polymers is 45% by weight). The
Molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
(3) The solution Al and the solution Bl are at one
Weight ratio of 1: 1 mixed, to obtain a mixed solution as toughening agent CI. 40 g of toughening agent CI, 140 g of styrene, 40 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C and then the mixture is polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain ABS resin PI, and the properties thereof are shown in Table 3.
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Reference example 1
According to step (3) of the procedure of Example 1, that is, the toughening agent CI is not used during the production of ABS resin, and the amount of the polymerized monomers and the solvent is adjusted as follows: 140 g styrene, 40 g acrylonitrile, 16 g of butadiene and 22 g of ethylbenzene to give ABS resin Rl, and the properties are shown in Table 3.
Example 2
This method is provided to describe this invention.
(1) 275 g of ethylbenzene is mixed with 275 g of butadiene, and 5.2 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 3 min; then 4.4 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is at this temperature
Reacted for 120 min; 5.8 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 70 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.5 MPa while being held at this temperature for 20 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution
BE2017 / 5774 as a polymeric ethylbenzene solution A2 with polybutadiene rubber with a low cis content (the concentration of the polymers is 55% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
(2) 225 g of ethylbenzene, 69 g of styrene and 206 g of butadiene are mixed and 2.3 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C added for a reaction for 3 min;
1.9 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 120 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B2 of the linear butadiene-styrene copolymer (concentration of the polymers is 55% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
(3) Solution A2 and solution B2 are mixed at a weight ratio of 1: 0.8 to obtain a mixed solution as toughening agent C2. 50 g of toughening agent C2, 130 g of styrene, 50 g of acrylonitrile and 0.03 g of di-o-methylbenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C and then the mixture at this temperature for 2 h
BE2017 / 5774 polymerized, the temperature of the reaction solution is increased to 135 ° C and then the mixture is polymerized at this temperature for 2 h. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, vacuum flashing is performed on the reaction product to remove unreacted monomers and the solvent to obtain ABS resin P2, and the properties thereof are shown in Table 3.
Example 3
This method is provided to describe this invention.
(1) 250 g of ethylbenzene is mixed with 250 g of butadiene, and 4.2 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 30 ° C while Is reacted for 4 min; then 3.6 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solution is raised to 80 ° C. and the mixture is reacted at this temperature for 100 min; 3.8 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while being held at this temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A3 with polybutadiene rubber with low cis content (the concentration of the polymers is
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Wt.%). The molecular weight of the low cis polybutadiene rubber in the solution is bimodal
Distribution, and the specific properties are in
Table 1 given.
(2) 250 g of ethylbenzene, 50 g of styrene and 200 g of butadiene are mixed and 1.8 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 35 ° C added for a reaction for 5 min;
1.5 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / 1) is added and the temperature of the reaction solution is raised to 80 ° C. and the mixture reacts at this temperature for 110 min. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B3 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
(3) Solution A3 and solution B3 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as toughening agent C3. 40 g of toughening agent C3, 120 g of styrene, 50 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 1.5 h; the temperature of the reaction solution is raised to 125 ° C and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C and then the mixture is kept at this temperature for 2 hours
BE2017 / 5774 polymerized. Finally the temperature of the reaction solution is raised to 155 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to give ABS resin P3, and the properties thereof are shown in Table 3.
Example 4
This method is provided to describe this invention.
(1) 250 g of ethylbenzene is mixed with 250 g of butadiene, and 3.7 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 3 min; then 3 ml of methylbenzene solution of triethylaluminum (the concentration of triethylaluminum is 1 mol / l) are added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 120 min; 7 ml of n-hexane solution of methyltrichlorosilane (the concentration of methyltrichlorosilane is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while being held at this temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer A4 ethylbenzene solution with low cis polybutadiene rubber (the concentration of the polymers is
Wt.%). The molecular weight of the low cis polybutadiene rubber in the solution is bimodal
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Distribution, and the specific properties are given in Table 1.
(2) 250 g of ethylbenzene, 40 g of styrene and 210 g of butadiene are mixed and 3.4 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C added for a reaction for 5 min;
2.7 ml of methylbenzene solution of triethylaluminum (concentration of triethylaluminum is 1 mol / 1) is added and the temperature of the reaction solution is raised to 80 ° C. and the mixture reacts at this temperature for 120 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B4 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
(3) Solution A4 and solution B4 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as toughening agent C4. 40 g of toughening agent C4, 130 g of styrene, 50 g of acrylonitrile and 0.03 g of tert-butyl peroxybenzoate are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C and then the mixture is polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C and then the mixture
BE2017 / 5774 polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to give ABS resin P4, and the properties thereof are shown in Table 3.
Example 5
This method is provided to describe this invention.
(1) 250 g of ethylbenzene is mixed with 250 g of butadiene and 4.4 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 3 min; then 3.5 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solvents is raised to 90 ° C. and the mixture is reacted at this temperature for 120 min; 4.4 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A5 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is bimodal
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Distribution, and the specific properties are given in Table 1.
(2) 250 g of ethylbenzene, 87.5 g of styrene and 162.5 g of butadiene are mixed, and 2 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C added for a reaction for 3 min; 1.6 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / 1) is added and the temperature of the reaction solution is raised to 80 ° C. and the mixture is reacted at this temperature for 120 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B5 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The
Molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
(3) Solution A5 and solution B5 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as toughening agent C5. 40 g of toughening agent C5, 150 g of styrene, 40 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is raised to 150 ° C and then the mixture at that temperature for
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Reaction product carried out a vacuum flashing
Removal of unreacted monomers and the
Solvent, to obtain ABS resin P5, and the
Properties thereof are shown in Table 3.
Example 6
This example is provided to describe this invention.
According to the procedure of Example 1, the difference being that in steps (1) and (2) carbon dioxide is replaced with isopropanol as a terminating agent, i.e. 0.2 g of isopropanol is added to the reaction system and held for 15 minutes ,
A polymeric ethylbenzene solution A6 made of polybutadiene rubber with a low cis content (concentration of the polymer is 45% by weight) is obtained in step (1); and the molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution and the properties are shown in Table 1.
A polymeric ethylbenzene solution B6 of the linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight) is obtained in step (2); and the molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution and the properties are shown in Table 2.
ABS resin P6 is obtained in step (3) and the properties are shown in Table 3.
Comparative Example 1
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According to the procedure of Example 1, the difference being that in step (3) the toughening agent is only 40 g of solution Al and that the amount of styrene in step (3) is increased to 145 ° g and after vacuum flashing ABS resin DPI is obtained to remove the unreacted monomer and solvent. The properties are given in Table 3.
Comparative Example 2
According to the procedure of Example 1, the difference being that in step (3) the toughening agent is only 40 g of solution B1 and that the amount of styrene in step (3) is increased to 135 g, and after vacuum flashing Removal of the unreacted monomer and solvent will result in ABS resin DPI. The properties are given in Table 3.
Comparative Example 3
According to the procedure of Example 1, the difference being that silicon tetrachloride is not added, to carry out a coupling reaction in step (1), whereby a polymeric ethylbenzene solution is DAI of low cis polybutadiene rubber (concentration of the polymer 45% by weight) is obtained, and the molecular weight of the polybutadiene rubber having a low cis content in the solution is in a unimodal distribution. The specific properties are given in Table 1.
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In step (3), Al in the toughening agent is replaced by DAI, and thereby ABS resin DP3 is obtained; whose
Properties are given in Table 3.
Comparative Example 4
According to the procedure of Example 1, the difference being that in step (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 7.5 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) added to the mixture at 35 ° C while reacting for 3 minutes; 6.4 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are then added, and the temperature of the reaction solution is raised to 80 ° C. and the mixture is reacted at this temperature for 120 min; 9.2 ml of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / 1) are added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution DA2 made of polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
In step (3), Al is replaced by DA2, and thereby ABS resin DP4 is obtained. Its properties are given in Table 3.
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Comparative Example 5
According to the procedure of Example 1, the difference being that in step (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 2.7 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) added to the mixture at 40 ° C while reacting for 4 min; 2.2 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are then added, and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 80 min; 3.3 ml of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / 1) are added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution DA3 made of polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
In step (3), Al is replaced by DA3, and ABS resin DP5 is thereby obtained. Its properties are given in Table 3.
Comparative Example 6
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According to the procedure of Example 1, the difference being that in step (2) 275 g of ethylbenzene, 67.5 g of styrene and 157.5 g of butadiene are mixed and 4.7 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while reacting for 3 min; then 4 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are added, and the temperature of the reaction solution is raised to 60 ° C. and the mixture is reacted at this temperature for 80 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution DB1 made of linear butadiene-styrene copolymer (the concentration of the polymer is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in unimodal distribution and the specific properties are shown in Table 2.
In step (3), B1 is replaced by DB1, and thereby ABS resin DP6 is obtained. Its properties are given in Table 3.
Comparative Example 7
According to the procedures of Example 1, the difference being that in step (2) 275 g of ethylbenzene with
67.5 g of styrene and 157.5 g of butadiene are mixed and
1.3 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C. while reacting for 4 min; then 1 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added, and the
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The temperature of the reaction solution is raised to 90 ° C. and the mixture reacts at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution DB2 made of linear butadiene-styrene copolymer (the concentration of the polymer is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
In step (3), B1 is replaced by DB2, and thereby ABS resin DP6 is obtained. Its properties are given in Table 3.
Comparative Example 8
According to the procedure of Example 1, with the difference that in step (1) triisobutylaluminium is not used during the polymerization and the polymerization rate and polymerization temperature cannot be controlled in the polymerization process; explosive polymerization occurs while generating a large amount of gel. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DA4 from the low cis polybutadiene rubber (concentration of the polymer is 45% by weight) and the molecular weight of the low cis polybutadiene rubber in the Solution is in trimodal distribution and the properties are given in Table 1.
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In step (3), Al is replaced by DA4 and thereby
Obtained ABS resin DP8. The property parameters are in
Table 3 indicated.
Comparative Example 9
According to the procedure of Example 1 with the difference that in step (1) ethylbenzene is replaced by the same amount of nhexane. The reaction solution obtained is polymeric n-hexane solution DA5 made of polybutadiene rubber with a low cis content (concentration of the polymer is
Wt.%). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
In step (3) the solvent of DA5 is over
Steam coagulation removed, the rest is dried in a plasticizer and dissolved in ethylbenzene to give 45% by weight of ethylbenzene solution, to replace Al and ABS resin DP9 is obtained. The properties are given in Table 3.
Comparative Example 10
According to the procedure of Example 1 with the difference that in step (2) during the polymerization
Triisobutyl aluminum is not used, and the polymerization rate and polymerization temperature cannot be controlled in the polymerization process; explosive polymerization occurs while generating a large amount of gel. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DB3 made of linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight).
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The linear butadiene-styrene copolymer in the solution is in a bimodal distribution and the properties are given in Table 2.
In step (3), B1 is replaced by DB3, and ABS resin DP10 is thereby obtained. The property parameters are given in Table 3.
Comparative Example 11
According to the procedure of Example 1 with the difference that in step (2) ethylbenzene is replaced by the same amount of nhexane. The reaction solution obtained is polymeric n-hexane solution DB4 made of linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 2.
In step (3) the solvent of DB4 is over
Steam coagulation is removed, the rest is dried in a plasticizer and dissolved in ethylbenzene to give 45% by weight of ethylbenzene solution, to replace B1 and ABS resin DP11 is obtained. The properties are given in Table 3.
Comparative Example 12
According to the procedure of Example 1, except that in step (3) Al is replaced by DA4 made in Comparative Example 8, B1 is replaced by DB3 made in Comparative Example 10, and thereby ABS resin DP12 is obtained; the properties are given in Table 3.
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Comparative Example 13
According to the procedure of Example 1 with the difference that in step (3) the solvent of DA5 and DB4 passes through
Steam coagulation is removed, the rest of it is dried in the plasticator and dissolved in ethylbenzene to give 45% ethylbenzene solution to replace Al and Bl and ABS resin DP13 is obtained. The properties are given in Table 3.
Comparative Example 9 Comparative Example 8 Comparative Example 5 Comparative Example 4 Comparative Example 3 Example 6 Example 5 Example 4 Example 3 Example 2 example 1 No. 165000 102000 + 155000 291000 102000 - 147000 182000 185000 188000 173000 147000High molecular component 1.37 1.69 + 1.72 2.03 1.76 - 1.76 1.89 1.93 1.90 1.96 1.76 s:3 92 37 + 59 93^1-1 - 92 <1 d ^ d ^ <1 CO ^1-1 92 Content (wt.%) 51000 49000 91000 32000 46000 46000 57000 71000 59000 54000 46000Low molecular weight component 1.32 1.64 1, 96 1.67 1.71 1.71 1.85 1.89 1.86 1.92 1.71 s:3 <1<1100 CO 26CO^1-1 CO Content (wt.%)
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Comparative Example 9 Comparative Example 8 Comparative Example 5 Comparative Example 4 Comparative Example 3 Example 6 Example 5 Example 4 Example 3 Example 2 example 1 No. COσ> 18.2 10.6 10.4 I— ¹ o co I— ¹ o co I— ¹ I— ¹ 10.9 10.7 I— ¹ I— ¹ ΓΌ I— ¹ o co Content of the 1.2 structural unit (% by weight) Low cis polybutadiene rubber 35.2 32.8 33.8 33.8 33.6 33.6 34.6 34.8 33.8 34.1 33.6 Content of cis-1,4-Structural unit (% by weight) CO σ> -xj ΓΌ CO I- ¹ I- ¹ -xj -xj CT (JI (£> (JI co (JI ΓΌ -xj Mooneyviscosity649CO co O coΓΌΓΌ Gel content(Ppm) 1.56 2.94 2.21 1, 91 I— ¹ -xj I— ¹ I - ¹ (£> CO 2.33 2.08 2.36 2.23 I - ¹ (£> CO s:3
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comparison Comparative Example 10 Comparative Example 7 Comparative Example 6 Example 6 Example 5 Example 4 Example 3 Example 2 example 1 No. 147000 136000 (84% by weight) +273000 (16% by weight) 184000 52000 134000 132000 77000 138000 122000 1340001.36 ο ω ,, s ^1-1 O CO c V fr I— ¹ Ό c + c + LS σ> O fu + S CO OHH t S + O><O H- C ^u 1- ^ - 3 Μ Φ g. > Φ 1 b 3 5 ^ 1 b 1 3 ° H- 1.99 1.82 1.84 1.92 1.87 1.93 1.94 1.84 s:3 Μ 29, 8 30.2 30, 1 29, 9 34.9 16, 1 20.2 25, 1 29, 9 Styrene structural unit content (% by weight) 70.1 <1 o 69, 870, 1st 65, 1st 83, 9 <1CO <1 year 70, 1st Butadiene structural unit content (% by weight)17.4 10, 8 10.2 10.2 10.7 10.3 10, 1 10, 9 10.2 Content of1.2 structural unit (% by weight) 133 127 162 Jù. 131 126 en I— ¹ 108 117 131 Mooneyviscosity 27 577jù. Μ Μ co Ο Ο CO Gel content(Ppm)
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ΒΕ2017 / 5774 σ φ
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Η · (D στ
ΒΕ2017 / 5774
σ < σ < σ < σ < ro ro ro ro ro σ ö W Φ Φ (D (D φ Φ Φ Φ Φ Φ Φ Φ Φ Φ φ φ Hi · hi Hi Hi Hi H· H· H· H· H· Η · hh Η · en kQ en kQ en kQ en kQ s s s s s en φ s Ή I— ¹ Ή I— ¹ U I- ¹ U I- ¹ Ό Ό Ό Ό Ό Ό Β Ό Ι-χ * Η · φ H · (D H · Φ H · Φ H· H· H· H· H· Η · φ Η · Ζ-κ Φ Η · (D H Φ H Φ H Φ Φ Φ Φ Φ Φ 3 Φ Ν I- ¹ Ω I- ¹ Ω I- ¹ Ω I- ¹ Ω I— ¹ I— ¹ I— ¹ I— ¹ I— ¹ I— ¹ Ν I— ¹ Β * B * B * B *1 jù. s1 co en1 ho en1 i— ¹ and 1 ΟΊ s Jù. 00 Μ^1-11-1 ω co Get Φ et £ co CO LO lo LO 1 - ^{1 1} - ¹ 1 - ^{1 1} - ¹ 1 - ^{1 1} - ^{1 1} - ¹ year. C0 <Ο weight Β · Β γ + B B Β B * £ L ρ> I— ¹ LO O^1-1 σ> Jù. O ΟΊ s^1-1 σ> Jù. ο ο Φ c + Η · Η · £ φ CL Φ γ + Β Β 1 1 Hi ω Φ γ + ω Gel· σ> O> σ> σ><1σ><1 σ> weight Β · Β γ + Β ΒΒ Β Β pJ LO CO LO lo LO O 00^1-1 Μ ο <Ο I— ¹ <1 jù. 00 Μ Μ <O s ΟΊ 00 Μ ο ο Φ (- + ο η · α i— CL Φ c + hi 1Hi Μ M Μ Μ Μ^1-1 Μ ho Μ Μ Μ ο φ < ω œ η- h Β · Β Λ Q φ er pJ^1-1 M^1-11-11-1 CO Jù. <1 00^1-11-1 l-J i-l Ι-ί I— ¹ <1 CO s^1-1 Jù. CO s O 00^1-1 Jù. ο ο Φ r + V Η · B gU B ϋ c +CL Φ ^{1 1} - ¹ 1 Hi Μ M I— ¹ Μ Μ^1-1 Μ Μ Μ Μ Μ σ> CO σ> CO <1 CO^1-1 s Μ Jù. C0 ο O CO <1Jù. Jù. <o σ> σ> Μ s ο O O O O O O O O ο Ο s; ο O O O O O O O O ο ο ο O O O O O O O O ο ο Μ M M Μ Μ Μ Μ Μ Μ 00 Μ s s:ΟΊ cnJù. σ> s Jù. Jù. 00^1-1 00^1-1 o>^1-1 co jù.^1-1 σ> <o Μ 00 y I— ^{1 1-11-1} Μ Μ Μ Μ co 00 <Ο ΜQ I zod σ> M O^1-1 s^1-1 Jù. co CO C0 O00 jù. CO CO jù. 00σ>3, ΟLO CO CO <1 <o CO CO <o <o <Ο <ΟI— ¹ ρ> ΟΊ^1-1 M CO Jù.^1-1 <o CO 00^1-1 Μ coO Ν
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ΒΕ2017 / 5774
Comparative Example 13 Comparative Example 12 Comparative Example 11 Comparative Example 10 Comparative Example 9 Comparative Example 8 Comparative Example 7 Comparative Example 6 Comparative Example 5 No.<1bO 9, 0 9, 0^1-1 COCO 00 9, 6 9, 6 Butadiene structural unit content (% by weight) 69, 7 71.2 69, 5 kOJù. 69, 7 <1 o 69, 6 68.3 69, 1 Styrene structural unit content (% by weight) 21.1 21.6 21.5 21.6 21.2 21.3 21.1 22.1 21.3 Content of the acrylonitrile structural unit (% by weight) 236000 178000 267000 223000 251000 197000 238000 265000 194000 s: 2, 91 3.44 2.86 3, 17 2, 92 2, 92 2.72 2.64 2.48 S s:S3 151 COCO^1-1 173 193 114 156 139 214 I zod (J / m) 72 73 <1<1 <1 82 82 CO bO CO CO <1 CO (60 °) gloss
Table 3 (continued)
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Comparing Example 1 with Comparative Examples 1 through 7 and 12 through 13 and Reference Example 1, it can be seen that ABS resin, using a combination of low cis polybutadiene rubber and linear butadiene-styrene copolymer as toughening agent, has improved impact resistance and has shine.
Comparing Example 1 with Comparative Examples 8-11, it can be seen that the processes for making the low cis polybutadiene rubber and the linear butadiene-styrene copolymer of this invention show a well-controlled polymerization process and the polymer produced has a low gel Has salary. The ABS resin using a combination of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer as a toughening agent has improved high impact strength and gloss. The polymer solution produced from the low cis polybutadiene rubber and the polymer solution produced from the linear butadiene-styrene copolymer can be used directly as a toughening agent for mixing with the polymeric monomers to produce the ABS resin by a free-radical polymerization reaction without solvent removal and renewed Dissolution can be used before performing the free radical polymerization reaction, obtaining in situ formation of the ABS resin.
Example 7
This method is provided to describe this invention.
(1) 300 g of ethylbenzene are mixed with 200 g of butadiene and 3.7 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) becomes that
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Mixture given at 40 ° C while reacting for 3 min; then 3.1 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solvents is raised to 100 ° C. and the mixture is reacted at this temperature for 90 min; 4.6 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A7 with polybutadiene rubber with a low cis content (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
(2) 300 g of ethylbenzene, 60 g of styrene and 140 g of butadiene are mixed and 1.6 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C added for a reaction for 3 min;
1.3 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 90 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the
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Reaction solution as a polymeric ethylbenzene solution B7 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 5.
(3) Solution A7 and solution B7 are at one
Weight ratio of 1: 1 mixed to obtain a mixed solution as toughening agent C7. 35 g of toughening agent C7, 150 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, vacuum flashing is carried out on the reaction product to remove unreacted monomers and the solvent to obtain HIPS resin P7, and the properties thereof are shown in Table 6.
Reference example 2
According to step (3) of the procedure of Example 7, that is, toughening agent C7 is not used during the production of HIPS resin, and the amount of the polymerized monomers and the solvent is adjusted as follows: 150 g of styrene, 14 g of butadiene and 18 g of ethylbenzene to obtain HIPS resin R2, and the properties are shown in Table 6.
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Example 8
This method is provided to describe this invention.
(1) 275 g of ethylbenzene is mixed with 225 g of butadiene, and 2.9 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 3 min; then 2.4 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solvents is raised to 100 ° C. and the mixture is reacted at this temperature for 90 min; 2.4 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 70 ° C. and the mixture is reacted at this temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.5 MPa while being held at this temperature for 20 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A8 with polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
(2) 275 g of ethylbenzene, 56.2 g of styrene and 168.8 g of butadiene are mixed and 2.6 ml of n-hexane solution of n
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Butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C for a reaction for 3 min; 2.2 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 100 ° C. and the mixture is reacted at this temperature for 90 min. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B8 of the linear butadiene-styrene copolymer (concentration of the polymers is 45% by weight). The
Molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are shown in Table 5.
(3) Solution A8 and solution B8 are at one
Weight ratio of 1: 2 mixed, to obtain a mixed solution as toughening agent C8. 40 g of toughening agent C8, 170 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted
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Monomers and the solvent to obtain HIPS resin P8 and the properties thereof are shown in Table 6.
Example 9
This method is provided to describe this invention.
(1) 250 g of ethylbenzene is mixed with 250 g of butadiene, and 5.0 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 30 ° C while Is reacted for 4 min; then 10 ml of methylbenzene solution of n-butyl-secbutylmagnesium (the concentration of n-butyl-secbutylmagnesium is 1 mol / 1) are added and the temperature of the reaction solution is raised to 80 ° C. and the mixture is reacted at this temperature for 120 min ; 6 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while being held at this temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A9 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
BE2017 / 5774 (2) 250 g of ethylbenzene, 50 g of styrene and 200 g of butadiene are mixed and 1.5 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture 40 ° C added for a reaction for 3 min; 3 ml of methylbenzene solution of n-butyl-sec-butylmagnesium (concentration of n-butyl-sec-butylmagnesium is 1 mol / 1) is added and the temperature of the reaction solution is raised to 100 ° C. and the mixture is reacted at this temperature for min , Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B9 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 5.
(3) The solution A9 and the solution B9 are mixed at a weight ratio of 1: 0.8 to obtain a mixed solution as a toughening agent C9. 40 g of toughening agent C9, 170 g of styrene and 0.02 g of dibenzoyl peroxide are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, a vacuum is applied to the reaction product
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Flashing was carried out to remove unreacted monomers and the solvent to obtain HIPS resin P9, and the properties thereof are shown in Table 6.
Example 10
This method is provided to describe this invention.
(1) 300 g of ethylbenzene is mixed with 200 g of butadiene and 2.4 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 4 min; then 2 ml of methylbenzene solution of triethyl aluminum (the concentration of triethyl aluminum is 1 mol / l) are added and the temperature of the reaction solution is raised to 100 ° C. and the mixture is reacted at this temperature for 90 min;
3.2 ml of n-hexane solution of methyltrichlorosilane (the concentration of trichlorosilane is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 90 min. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution A10 with polybutadiene rubber with a low cis content (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
BE2017 / 5774 (2) 300 g of ethylbenzene, 30 g of styrene and 170 g of butadiene are mixed and 1.3 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture 40 ° C added for a reaction for 3 min; 1 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / 1) is added and the temperature of the reaction solution is raised to 90 ° C. and the mixture is reacted at this temperature for 100 min. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B10 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 5.
(3) Solution A10 and Solution B10 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as toughening agent C10. 35 g of toughening agent C10, 170 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted
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Monomers and the solvent to obtain HIPS resin P10, and the properties thereof are shown in Table 6.
Example 11
This method is provided to describe this invention.
(1) 300 g of ethylbenzene are mixed with 200 g of butadiene, and 3.9 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while Is reacted for 3 min; then 3.1 ml of methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solvents is raised to 120 ° C. and the mixture is reacted at this temperature for 70 min; 4.3 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at this temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as a polymer Ethylbenzene solution All with low cis polybutadiene rubber (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
(2) 300 g of ethylbenzene, 80 g of styrene and 120 g of butadiene are mixed and 2.0 ml of n-hexane solution of n-butyllithium
BE2017 / 5774 (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C for a reaction for 3 min;
1.7 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 100 ° C. and the mixture is reacted at this temperature for 90 min. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution B1 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the specific properties are given in Table 5.
(3) The solution All and the solution B1 are in one
Weight ratio of 1: 1 mixed, to obtain a mixed solution as toughening agent Cll. 40 g of toughening agent Cll, 170 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is raised to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is raised to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally the temperature of the reaction solution is raised to 150 ° C. and then the mixture is polymerized at this temperature for 2 h. After the polymerization, the reaction product is vacuum flashed to remove unreacted
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Monomers and the solvent to obtain HIPS resin Pli, and the properties thereof are shown in Table 6.
Comparative Example 14
Following the procedure of Example 7 with the difference that in step (3) the toughening agent is only solution A7 and the amount of styrene in step (3) is increased to 160 g and after vacuum flashing to remove the unreacted monomer and the solvent, HIPS resin DP14 is obtained. The properties are given in Table 6.
Comparative Example 15
According to the procedure of Example 7 with the difference that in step (3) the toughening agent is only solution B7 and the amount of styrene in step (3) is reduced to 145 g and after vacuum flashing to remove the unreacted monomer and the Solvent HIPS resin DP15 is obtained. The properties are given in Table 6.
Comparative Example 16
Following the procedure of Example 7, except that silicon tetrachloride is not added, to carry out a coupling reaction at step (1), whereby a polymeric ethylbenzene solution DA6 with low cis polybutadiene rubber (the concentration of the polymer is 40 % By weight) is obtained, and the molecular weight of the low cis polybutadiene rubber is in unimodal distribution and the properties are shown in Table 4.
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In step (3), A7 is replaced by DA7 and thereby
Obtained HIPS resin DP16. The property parameters are in
Table 6 given.
Comparative Example 17
According to the procedure of Example 7, with the difference that in step (1) 5.0 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is added to the mixture at 40 ° C while reacting for 5 min; then 4.2 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solution is raised to 100.degree. and the mixture is reacted at this temperature for 80 min; 5.5 ml of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / 1) is added to the reaction system, then the temperature of the reaction solution is reduced to 70 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at this temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric ethylbenzene solution DA7 made of polybutadiene rubber with a low cis content (concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution in bimodal distribution and the specific properties are shown in Table 4.
In step (3), A7 is replaced by DA7, and HIPS resin DP17 is thereby obtained. The property parameters are given in Table 6.
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Comparative Example 18
According to the procedure of Example 7 with the difference that in step (1) the amount of the n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1)
2.2 ml, the amount of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / 1) is 1.9 ml, the amount of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / 1) is 2.2 ml and the reaction solution obtained is polymeric ethylbenzene solution DA8 made of polybutadiene rubber with a low cis content (concentration of the polymer is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is bimodally distributed in the solution and the properties are shown in Table 4.
In step (3), A7 is replaced by DA8, and HIPS resin DP18 is thereby obtained. The property parameters are given in Table 6.
Comparative Example 19
According to the procedure of Example 7 with the difference that in step (2) the amount of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1) is 4 ml, the amount of methylbenzene solution of triisobutylaluminum (Concentration of triisobutylaluminum is 1 mol / 1) is 3.5 ml and the reaction solution obtained is polymeric ethylbenzene solution DB5 made of linear butadiene-styrene copolymer (concentration of the butadiene-styrene copolymer in the solution is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution in the solution and the properties are given in Table 5.
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In step (3), B7 is replaced by DB5 and thereby
Obtained HIPS resin DP19. The property parameters are in
Table 6 given.
Comparative Example 20
According to the procedure of Example 7 with the difference that in step (2) the amount of the n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / 1)
Is 1.1 ml, the amount of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / 1) is 0.85 ml and the reaction solution obtained is polymeric ethylbenzene solution DB6 from linear butadiene-styrene copolymer (concentration of butadiene-styrene Copolymer in the solution is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution in the solution and the properties are given in Table 5.
In step (3), Bl is replaced by DB6 and HIPS resin DP20 is obtained. The property parameters are given in Table 6.
Comparative Example 21
According to the procedure of Example 7, with the difference that in step (1) triisobutylaluminum is not used during the polymerization and in the polymerization process the polymerization rate and the polymerization temperature cannot be controlled; explosive polymerization occurs while generating a large amount of gel. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DA9 made of polybutadiene rubber
BE2017 / 5774 low cis content (concentration of the polymer is
Wt.%). The molecular weight of the low cis polybutadiene rubber in the solution is trimodal
Distribution and properties are given in Table 4.
In step (3), A7 is replaced by DA9 and HIPS resin DP21 is obtained. The property parameters are given in Table 6.
Comparative Example 22
According to the procedure of Example 7 with the difference that in step (1) ethylbenzene is replaced by the same amount of nhexane. The reaction solution obtained is polymeric n-hexane solution DA10 made of polybutadiene rubber with a low cis content (the concentration of the polymer is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is bimodal distribution and the properties are shown in Table 4.
In step (3) the solvent of DA10 is over
Steam coagulation is removed, the rest is dried in a plasticator and dissolved in ethylbenzene to give 40% by weight of ethylbenzene solution to replace A7, and HIPS resin DP22 is obtained. The property parameters are given in Table 6.
Comparative Example 23
According to the procedure of Example 7, with the difference that in step (2) triisobutylaluminum is not used during the polymerization and in the polymerization process the polymerization rate and the polymerization temperature cannot be controlled; an explosive polymerization occurs during a large amount
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Gel is generated. The supernatant is separated from the polymerization reaction system to give a polymeric ethylbenzene solution DB7 of linear butadiene-styrene copolymer (concentration of the polymer is 40% by weight). The
Molecular weight of the linear butadiene-styrene copolymer in the solution is in bimodal distribution and the properties are shown in Table 5.
In step (3), B7 is replaced by DB7 and HIPS resin DP23 is obtained. The property parameters are given in Table 6.
Comparative Example 24
According to the procedure of Example 7 with the difference that in step (2) ethylbenzene is replaced by the same amount of nhexane. The reaction solution obtained is polymeric n-hexane solution DB8 made of linear butadiene-styrene copolymer (the concentration of the polymer is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution and the properties are given in Table 5.
In step (3) the solvent of DB8 is over
Steam coagulation is removed, the rest of it is dried in a plasticator and dissolved in ethylbenzene to give 40% by weight of ethylbenzene solution to replace B7, and HIPS resin DP24 is obtained. The property parameters are given in Table 6.
Comparative Example 25
According to the procedure of Example 7, except that in step (3) A7 is replaced by DA9 made in Comparative Example 21, B7 is replaced by DB7
BE2017 / 5774 is produced in Comparative Example 23, and thereby HIPS resin DP25 is obtained. The properties are given in Table 6.
Comparative Example 26
According to the procedure of Example 7 with the difference that in step (3) the solvent of DA10, prepared in Comparative Example 22, and DB8, prepared in
Comparative Example 24, which is removed by steam coagulation, dried in a plasticator and dissolved in ethylbenzene, to obtain a 40% by weight benzene solution to replace A7 and B7, and HIPS resin DP26 is obtained. The properties are given in Table 6.
Comparative Example 22 Comparative Example 21 Comparative Example 18 Comparative Example 17 Comparative Example 16 Example 11 Example 10 Example 9 Example 8 Example 7 No. 197000 187000+155000 Ca)Ο σι ΟΟ Ο 128000 - 169000 229000 234000 259000 182000 S3 High molecular component 1.33 1.79 + 1.72 1, 97 1.73 - 1.86 1.94 1.97 1.95 1.82 S s:s3 94 34 + 58 72 CO Μ - CO Μ <1 co CO Jù. 66 93 Content (wt.%) 62000 σι co ο ο ο CO σι ο ο ο 40000 57000 53000 co co o o o 73000 81000 57000 S3 Low molecular weight component 1.27 1.74 1, 92 1.68 1.74 1.81 1.89 1.92 1.91 1.74 S s:S3CO 28 I - ¹ co 100 I - ¹ co 22 I— ¹ Ca) Jù. <1 Content (wt.%)
C £) ο
ΒΕ2017 / 5774
Comparative Example 22 Comparative Example 21 Comparative Example 18 Comparative Example 17 Comparative Example 16 Example 11 Example 10 Example 9 Example 8 Example 7 No. Μ 17.8 13.3 12.8 12.1 13.7 12.7 xj 12.3 12.1 Content of 1,2-structural unit(% Wt.) Low cis polybutadiene rubber 35.4 34.1 35.4 35, 6 36, 4 34.8 35, 9 35.3 35, 8 36, 4 Content of cis-1,4-Structural unit (% by weight) 43 72 <1 co 31 29 en jù. 66 59 62 59 Mooneyviscosityσι co coΜΜ Ο στ xj 4 ^ Gel content(Ppm) 1.59 2, 91 2.34 1, 97 1.74 2.21 2.26 2.23 2.39 2.03 s:3
ΟΊ -xl -xl
Comparative Example 24 Comparative Example 23 Comparative Example 20 Comparative Example 19 Example 11 Example 10 Example 9 Example 8 Example 7 No. 144000 136000 (82% by weight) +273000 (18% by weight) 214000 53000 106000 158000 147000 124000 1360001.31 1.69 + 1.71 < ^M w ^{/ M} n ^of linear butadiene-styrene copolymer 2.19) 1, 95 1, 67 1.83 1.84 1.96 1.91 1.87 s:3 30, 1 30.2 30.1 30.1 40.3 15, 1 20, 1 25, 0 30, 1 Styrene structural unit content (% by weight)69, 8 6 9.9 6 9.9 59, 7 CO 4ù. <1 75, 0Butadiene structural unit content (% by weight) 4U. 17.4 13.5 11.2 13, 1 11.2 13, 1 12.7 11.8 Content of1.2 structural unit (% by weight) 121 148 178 57 114 101 127 119 129 Mooneyviscosity 25 613O 4 ^ O CO 4U. CO Gel content(Ppm)
H σ φ
I— ¹
I - ¹ φ
ΟΊ co Μ
ΒΕ2017 / 5774
Comparative Example 18 Comparative Example 17 Comparative Example 16 Comparative Example 15 Comparative Example 14 Example 11 Example 10 Example 9 Example 8 Reference example 2 Example 7 No. uo COuo uoO <1CO8, 6 CO<1 11.8 10, 1 CO<1 9.1 Butadiene structural unit content (% by weight) 90.8 91.1 91.0 92.2 90, 1 91.4 91.3 CO CO COkO 91.3 90, 9 Styrene structural unit content (% by weight) 273000 261000 252000 245000 196000 218000 238000 265000 247000 174000 286000 s: 2.73 2.56 2, 64 2.48 2.72 2.57 2.61 2.66 2.48 3.21 2.56 S s:S3 11.8 uoO CO ^1-1 O 10.2 11.3 12.2 16, 7 15.4 CO ^1-1 14.6 Impact resistance (kJ / m ² ) 58 77 79 82 cn CO CO <1 1 - ¹ CO CO Jù. 66 CO (60 °) gloss
UC
CO
BE2017 / 5774
Comparative Example 26 Comparative Example 25 Comparative Example 24 Comparative Example 23 Comparative Example 22 Comparative Example 21 Comparative Example 20 Comparative Example 19 No. 8, 6 <1 1 - ¹ CO CO <1 kO kO COkO Butadiene structural unit content (% by weight) 91.4 92.9 co 91, 6 91.1 92.1 knockoutCO 91.1 Styrene structural unit content (% by weight) 215000 164000 271000 244000 243000 208000 294000 221000 s: 2, 91 3.47 2.73 2, 94 2.84 3, 04 2.69 2.49 S s:S3 10.3 cnd ^ 12.1 CO<1 11.8 <1 I— ¹ kO ^1-1 <1 kO Impact resistance (kJ / m ² ) 58 d ^CO ΜKjo Μ <1 <1<1 (60 °) gloss
Table 6 (continued)
ΟΊ -xl -xl
BE2017 / 5774
Comparing Example 7 with Comparative Examples 15 to 20 and 25 to 26 and Reference Example 2, it can be seen that HIPS resin using a combination of low cis polybutadiene rubber and linear butadiene-styrene copolymer as a toughening agent apparently improved impact resistance and Has shine.
Comparing Example 7 with Comparative Examples 21 through 24, it can be seen that the processes for making the low cis polybutadiene rubber and the linear butadiene-styrene copolymer of the invention show a well-controlled polymerization process and the polymer produced shows a low gel Content. The HIPS resin using a combination of low cis polybutadiene rubber and the linear butadiene-styrene copolymer as a toughening agent has improved impact resistance and gloss. The polymer solution prepared from the low cis polybutadiene rubber and the polymer solution prepared from the linear butadiene-styrene copolymer can be used directly as a toughening agent for mixing with the polymeric monomers for the production of the HIPS resin by free radical polymerization reaction without solvent removal and redissolution before the free radical polymerization reaction is carried out, with in situ formation of the HIPS resin.
While this invention has been described in detail in some preferred embodiments, this invention is not limited to this. Various simple variations, including combinations of the technical features in any appropriate manner, can be made in the technical scheme of this invention within the scope of the technical concept of this invention, and these simple variations and combinations are intended to be disclosure of these
BE2017 / 5774
Invention to be viewed, what is the scope of
Invention belongs.

权利要求:
Claims (25)
[1]
1. Linear butadiene-styrene copolymer, wherein the molecular weight of the linear butadiene-styrene copolymer has a number average molecular weight of 70,000 to 160,000 and one
Molecular weight distribution index of 1.55 to 2 in unimodal distribution, with respect to the total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit 10 to 45 wt .-% and a content of the butadiene-styrene unit 55 to 90 wt .% and wherein, based on the total amount of the linear butadiene-styrene copolymer, a content of the 1,2-structural unit is 10 to 13.5% by weight.
[2]
2. The linear butadiene-styrene copolymer according to claim 1, wherein a Mooney viscosity of the linear butadiene-styrene copolymer is 50 to 150.
[3]
3. Linear butadiene-styrene copolymer according to one of claims 1 or 2, wherein a gel content of the linear butadiene-styrene copolymer below 20 ppm, preferably not more than 15 ppm and preferably not more than
Is 10 ppm measured as weight.
[4]
4. A composition containing a linear butadiene-styrene copolymer and a polybutadiene rubber with a low cis content, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to one of claims 1 to 3 and the molecular weight of the polybutadiene rubber
BE2017 / 5774 is low cis in the bimodal distribution, the number average molecular weight of a low molecular weight component in the bimodal distribution is 42,000 to 90,000, the molecular weight distribution index is 1.55 to 2, the number average molecular weight of a high molecular weight component in the bimodal distribution 120,000 to 280,000 with a molecular weight distribution index of
1.55 to 2, wherein based on the total amount of the polybutadiene rubber with a low cis content, a content of the high molecular weight component is 60 to 95% by weight.
[5]
5. The composition of claim 4, wherein, based on the total amount of the low cis polybutadiene rubber, the content of the cis 1,4-structural unit in the low cis polybutadiene rubber is 30 to 40% by weight.
[6]
The composition of claim 4 or 5, wherein a molecular weight distribution index of the low cis polybutadiene rubber is 1.9 to 2.5.
[7]
A composition according to any one of claims 4 to 6, wherein, based on the total amount of the low cis polybutadiene rubber, a content of the 1,2 structural unit in the low cis polybutadiene rubber is 8 to 14% by weight.
[8]
8. A composition according to any one of claims 4 to 7, wherein a gel content of the low cis polybutadiene rubber is less than 20 ppm, preferably not higher than 15 ppm and more preferably not higher than
Is 10 ppm measured as weight.
BE2017 / 5774
[9]
9. A composition according to any one of claims 4 to 8, wherein a Mooney viscosity of the low cis polybutadiene rubber is 30 to 70, preferably 40 to 70 and more preferably 45 to 70.
[10]
10. The composition according to any one of claims 4 to 9, wherein the low molecular weight component in the bimodal distribution is a linear polymer and the high molecular weight component in the bimodal distribution is a coupled polymer.
[11]
11. The composition according to any one of claims 4 to 10, wherein a weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer 0.3-6: 1, preferably 0.4-5: 1 and more preferably 0, 5-2: 1 is.
[12]
12. A process for the preparation of the linear butadiene-styrene copolymer according to claim 1, comprising the following steps:
(1) under an anionic initiation reaction condition, butadiene and styrene in contact with an organic lithium initiator in alkylbenzene are subjected to an initiation reaction, (2) adding a blocking agent to a mixture obtained from the initiation reaction of step (1), and performing one Polymerization reaction with the mixture containing the blocking agent in a condition of an anionic polymerization reaction, (3) contacting a mixture obtained from the polymerization reaction with a terminating agent,
100
BE2017 / 5774 for performing a termination reaction, under
Obtaining the polymer solution containing linear butadiene-styrene copolymer.
[13]
13. The method of claim 12, wherein the total concentration of butadiene and styrene in alkylbenzene is 30 to 60% by weight, preferably 35 to 55% by weight and more preferably 40 to 55% by weight.
[14]
14. The method of claim 12 or 13, wherein the alkylbenzene is one or more selected from the group consisting of methylbenzene, ethylbenzene and xylene.
[15]
15. The method according to any one of claims 12 to 14, wherein the blocking agent selected from one or more selected from the group consisting of an organic aluminum compound, organic magnesium compound and organic zinc compound, preferably the organic aluminum compound one or is several of compounds of formula IV
Γ ^r 6 AI R ₅ Formula IV wherein R4, R5 and Rg are independently selected from C] __ g-alkyl;
more preferably the organic aluminum compound is one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum and triisobutyl aluminum and preferred
101
BE2017 / 5774 is selected from triethylaluminium and / or triisobutylaluminum, in which the organic magnesium compound is preferably one or more compounds of the formula V,
Re Mg R7
Formula V wherein R7 and Rg are independently selected from Cj__galkyl, more preferably the organic magnesium compound is one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-tert-butylmagnesium and nButyl-sec-butylmagnesium and preferably n-butyl-secbutylmagnesium, in which the organic zinc compound is preferably one or more of compounds having the formula VI, ^Rl ° ^{Zn Rg} formula VI in which Rg and Rj_q are independently selected from Cj__gAlkyl, more preferred the organic zinc compound is one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-secbutyl zinc, diisobutyl zinc and di-tert-butyl zinc and is preferably selected from diethyl zinc and / or di-nbutyl zinc, wherein preferably the blocking agent is the organic aluminum compound and the amount of the organic
102
BE2017 / 5774
Aluminum compound and the organic lithium initiator enables a molar ratio of Al element to Li element of 0.6-0.95: 1, preferably 0.7: 0.9: 1, preferably the blocking agent is the organic magnesium compound and the amount of organic magnesium compound and the organic lithium initiator enables a molar ratio of Mg element to Li element of 16: 1, preferably 2-4: 1, wherein preferably the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound and the amount of the organic aluminum compound, the organic magnesium compound and the organic lithium initiator is a molar ratio of Al element to Mg element to Li element of 0.5-2: 1-5: 1, preferably 0.81: 1.5-3: 1, in which the blocking agent is preferably the organic zinc compound and the amount of the organic zinc compound and the organic lithium initiator is a molar ratio of the Zn element to the Li element from 1-6: 1, preferably 2-4: 1.
[16]
16. The method according to any one of claims 12 to 15, wherein in step (1) the initiation reaction at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C, at a time of the initiation reaction from 1 to 8 min, preferably 1 to 5 min, preferably 2 to 4.5 min and more preferably 3 to 4 min, in step (2) a temperature of the polymerization reaction is 50 to 140 ° C., preferably 70 to 130 ° C. and more preferably 80 up to 120 ° C, a time of
103
BE2017 / 5774
Polymerization reaction is 60 to 150 min and preferably 70 to 120 min, in step (3) the terminating agent is carbon dioxide.
[17]
17. Aromatic vinyl resin containing a structural unit derived from aromatic vinyl monomer and a structural unit derived from toughening agent, wherein the toughening agent is the composition according to any one of claims 4 to 11.
[18]
The aromatic vinyl resin according to claim 17, wherein the aromatic vinyl resin is acrylonitrile-butadiene-styrene resin or high impact styrene resin.
[19]
19. A process for producing an aromatic vinyl resin containing steps for mixing polymeric monomers containing aromatic vinyl monomer with a solution containing toughening agent to obtain a mixture and polymerizing the mixture, wherein the solution with the toughening agent is a solution with linear butadiene-styrene Copolymer and a solution containing low cis polybutadiene rubber, the linear butadiene-styrene copolymer solution being the linear butadiene-styrene copolymer polymer solution obtained by the process of any one of claims 12 to 16; and the low cis polybutadiene rubber solution is a low cis polybutadiene rubber polymer solution prepared by a method comprising the steps of:
(a) under an anionic condition
Initiation reaction performing a
104
BE2017 / 5774
Initiation reaction of butadiene in contact with an organic lithium initiator in alkylbenzene, (b) adding a blocking agent to a mixture obtained from the initiation reaction of step (a) and performing a polymerization reaction with the mixture containing the blocking agent in an anionic state Polymerization reaction, (c) performing a coupling reaction with a mixture obtained from the polymerization reaction by contacting with a coupling agent, (d) contacting a mixture obtained from the coupling reaction with a terminating agent to carry out a terminating reaction to obtain a polymer solution containing polybutadiene - Low cis rubber.
[20]
20. The method of claim 19, wherein in step (a) the concentration of butadiene in the alkylbenzene 30 to
60% by weight, preferably 35 to 55% by weight and more preferably 40 to 55% by weight.
[21]
21. The method of claim 19 or 20, wherein in step (a) the alkylbenzene is one or more selected from the group consisting of methylbenzene, ethylbenzene and xylene.
[22]
22. The method according to any one of claims 19 to 21, wherein in step (2) the blocking agent is one or more selected from the group consisting of organic aluminum compound, organic magnesium compound and organic zinc compound,
105
BE2017 / 5774 wherein the organic aluminum compound is preferably one or more compounds with the formula IV,
Γ ^r 6 AI R ₅ Formula IV wherein R4, R5 and Rg are independently selected from C] __ g-alkyl;
more preferably the organic aluminum compound is one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum and triisobutyl aluminum and is preferably selected from triethyl aluminum and / or triisobutyl aluminum, wherein preferably the organic magnesium Compound is one or more compounds of formula V,
Re Mg R7
Formula V wherein R7 and Rg are independently selected from Cj__galkyl, more preferably the organic magnesium compound is one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-tert-butylmagnesium and n-butyl-sec-butyl magnesium and preferably n-butyl-sec-butyl magnesium,
106
BE2017 / 5774 in which preferably the organic zinc compound is one or more of compounds having the formula VI, ^Rl ° ^{Zn Rg} formula VI in which Rg and Rj_q are selected independently from Cj__galkyl, more preferably the organic zinc compound is one or more is selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-secbutyl zinc, diisobutyl zinc and di-tert-butyl zinc and is preferably selected from diethyl zinc and / or di-n-butyl zinc, wherein the blocking agent is preferably the organic aluminum compound and the amount of the organic aluminum compound and the organic lithium initiator enables a molar ratio of Al element to Li element of 0.6-0.95: 1, preferably 0.7: 0.9: 1, preferably the blocking agent is the organic magnesium compound and the amount of the organic magnesium compound and the organic lithium initiator enables a molar ratio of Mg element to Li element of 16: 1, preferably 2-4: 1, wherein be preferably the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound and the amount of the organic aluminum compound, the organic magnesium compound and the organic lithium initiator is a molar ratio of Al element to Mg element to Li element from 0.5-2: 1-5: 1, preferably 0.81: 1.5-3: 1 enables
107
BE2017 / 5774 wherein the blocking agent is preferably the organic zinc compound and the amount of the organic zinc compound and the organic lithium initiator is a molar ratio of the Zn element to the Li element of
1-6: 1, preferably 2-4: 1.
[23]
23. The method according to any one of claims 19 to 22, wherein in step (a) the initiation reaction at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C, at a time of the initiation reaction from 1 to
8 min, preferably 1 to 5 min, preferably 2 to 4.5 min and more preferably 3 to 4 min, in step (2) a temperature of the polymerization reaction is 50 to 140 ° C., preferably 70 to 130 ° C. and more preferably 80 to 120 ° C, a time of the polymerization reaction is 60 to 150 min and preferably 70 to 120 min, in step (c) the coupling agent is tetrachlorosilane and / or methyltrichlorosilane, a temperature of the coupling reaction is 50 to 100 ° C and preferably 60 to 80 ° C, a coupling reaction time is 20 to 150 min and preferably 30 to 120 min in step (d) the terminating agent is carbon dioxide.
[24]
24. The method according to any one of claims 19 to 23, wherein a weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer is 0.3-6: 1, preferably 0.4-5: 1 and more preferably 0, 5-2: 1 is.
108
BE2017 / 5774
[25]
25. The method according to any one of claims 19 to 24, wherein the aromatic vinyl resin is acrylonitrile butadiene styrene resin or high impact styrene resin.

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同族专利:

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公开号 | 公开日

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DE102017219342A1|2019-03-14|

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JP6665145B2|2020-03-13|

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BE1025614A1|2019-04-29|

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CN109485791B|2021-10-19|

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CN109485791A|2019-03-19|

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KR20190030136A|2019-03-21|

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JP2019052283A|2019-04-04|

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DE102017219342B4|2021-01-21|

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KR101976551B1|2019-05-09|

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法律状态:
2019-06-05| FG| Patent granted|Effective date: 20190506 |

优先权:

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申请号 | 申请日 | 专利标题

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CN201710822652.7A|CN109485791B|2017-09-13|2017-09-13|Linear styrene-butadiene copolymer, process for producing the same, composition thereof, aromatic vinyl resin and process for producing the same|

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CN201710822652.7|2017-09-13|

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