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    • 专利摘要:
    The invention relates to an improved process for the mass polymerization of solutions comprising monoalkenyl aromatic monomers and optionally monoalkenyl nitrile monomers having a diene rubber dissolved therein wherein the improvement comprises dissolving a minor amount of an aliphatic mono-olefinic compound in said solution and mass polymerizing said solution, said olefinic compound forming free radicals with said monoalkenyl aromatic monomer that are more active than said monoalkenyl aromatic free radicals in grafting said rubber provided a higher grafted rubber phase.
    公开号:SU735172A3
    申请号:SU772498504
    申请日:1977-06-28
    公开日:1980-05-15
    发明作者:Луис Крусе Роберт；Минг-Шенг Пенг Фред
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR GETTING STRESS POLYSTYRENE
    one
    This invention relates to the field of producing high impact polystyrene.
    A known method for producing high impact polystyrene by radical polymerization in the mass of a styrene mixture with 1–20 wt.% Polyb} rubber rubber at 80-180 ° C 1.
    According to this method, mixtures of polymers with dispersed and graft-polymerized rubber phase are obtained. The polymeric | Q mixtures are compacted by the rubber phase directly proportional to the content. The performance of rubber in relation to compaction is greatly increased due to the graft polymerization of rubber with a polymer of the matrix phase with the achievement of inter-jordan compatibility of the rubber and matrix phases.
    In general, rubber is subjected to graft polymerization by matrix monomers in a volume of from about 10 to 100%; moreover, in-y) is sobratom, and graft-monomers form graft-polymers as a coating layer.
    Catalysts based on free residues are used; When the hydrogen is removed from the rubber, the monomers cause a more efficient graft polymerization of the rubber.
    A higher degree of grafting reaches a higher content of catalysis; 1tor,
    however, due to the penetration of catalysts, the molecular weight of the matrix phase is reduced, which leads to a decrease in toughness.
    The purpose of the invention is to improve impact strength and elongation upon stretching of polystyrene.
    The goal is achieved by the fact that high-impact polystyrene is obtained by radical polymerization in the mass of a mixture with 1-20 Eec.% Iolibutadiene at 80-180 ° C in the presence of 0.04-5% by weight of a roaccium mixture of aliphatic monoolefin containing Cs-Cg in the chain or vinyl acetate.
    Monomers used include styrene; o: mono-monovinylidene monoaromatic compounds, e.g., su-motilstirolg o-ethstyrene, O-methyl vinyltoluene; ringed alkylstyrenes in the ring, for example, vinyltoluene, o-ethylstyrene, p-ethylstyrene, 2,4-dimethyl and 11 Liprop; substituted in the ring rajTOi-cHCTiipojK.i, for example, o-chlorostyrene, p-chlorustol, o-6pro.m styrene, 4-dichloro-styrene, cyclic alkyl, halogen-substituted in the ring of styro, 1 example 2-chloro-methylstyrene, 2-dichloro- 4-meta styrene Tak Hcnojibayrot mixtures of monovish todene mono-yoers of the aromatic series.
    Akalogychio carried out the polymerization of a monooric diene rubber solution, where comonomers with monoalic and moomeric aromatic series are used, in particular aliluenitrile monomers, such as acrylonitrile,
    methacrylonitrile and mixtures thereof. In this case, myomeric solutions contain approximately 60-99% by weight of monoalkane and aryl monomer, 1-39% by weight of alkenylnitrile 5 monomer, and approximately 1-20 by weight of 7 diene. YEARS OF A mixture of monoalkyl and aromatic copolymers of the above composition - solution.
    Additionally, catalysts, stabilizers, molecular weight regulators can be added.
    Polymerization can be caused by thermal monr-dimensional free residues or catalysts forming free residues, including actinic rays. Use of the peroxide monomer -butyl hydroperoxide, cubic hydroperoxide, p-Mentat hydrotroxide, cyclopentane hydroperoxide, penagin hydroperoxide, and mixtures thereof.
    Catalysts used in amounts
    0.001-3.0 wt.%, Preferably, 0.005-1.0 wt.% Based on the polymerized product, depending on the polymerization temperature.
    Regulatory molecular weight regulators, such as mercaptans, halides, and tertiary, are also added in an amount of 0.001-1.0% by weight, calculated on the polymerizing material. In order to adjust the viscosity at a high conversion and for the purpose of a specific molecular weight adjustment, it is also possible to add 2-20% by weight of diluents to the monomer composition, such as methyl benzene, ethyl toluene, ethyl xylene, diethyl benzene or benzene. Additionally, small amounts of atoxide or stabilizers, such as common alkylated phenols, can be introduced during or after polymerization. The composition may also contain other additives, such as plasticizers, lubricants, dyes, and non-reactive, preformed polymeric material that is soluble or dispersible in the composition.
    The diene rubbers used are soluble in the monomers described. The transformation temperature of rubber is not higher than 0 ° C, preferably.
    no higher than (-) 20C (test ASTMD-746-52T) on one or several conjugated 13-Dienzx, for example, butadiene, isophen, cyclonentadine-13; 3- and 2-chloro-13-butadiene, pipsrilene. Such rubbers include copolymers and block copolymers of conjugated 1,3-dienes with a content to an equivalent amount and weight of one or more copolymerizing monomers with unsaturated monoethylene bonds, such as monovinyldienic aromatic hydrocarbons, for example styrene; aralkylstyrene, such as o-, m-, and p-methy1styrene1, 2,4-; himethylstyrene, aroethylstyrene, p-tert-butylstyrene; o: -methylstyrene, O-methylstyrene, 0 -methyl-methylmethyl styrene; vinylnaphthalene: arhalogenmonovshliden aromatic hydrocarbons, for example o-, m- and p-chlorostyrene, 2,4-dibromostyrene, 2-methyl-4-chlorostyrene; acrylonitrile, methacrylonitrile; alkyl acrylates, for example. mer methyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate; the corresponding alkyl methacrylates; acrylamides, eg, acrplamide, methacrylamide, N-butyl acrylamide; unsaturated ketones, such as vinyl methyl ketone, methyl isopropenyl ketone; but. α-olefins, for example ethylene, propylene; pyridines; vinyl ester complex, for example, vishat acetate, vinyl stearate; vinyl and vinylidene halides, such as vinyl and vinylidene chlorides and bromides, and the like.
    The rubber may contain up to 2.0% of a binding agent, based on the weight of the monomer or monomers forming the rubber, it may be difficult for the rubber to dissolve in the graft polymerization dp monomers, and excessive crosslinking may impair the rubber characteristics.
    A preferred group of rubbers are stereospecific polybutadiene cows produced by the polymerization of 1,3-butadiene. These rubbers differ in the content of cis-isomers and 70-2% of trans-isomers, usually contain 85% of polybutadiene, obtained by 1,4-addition, with 1,2-adhesives - 15%. Mooney viscosity (100 ° C) 20-70 at a second-order conversion temperature of about (-) 50 to (-) 105 ° C according to ASTM TestD..746-52T standard test.
    Monoolefinic compounds of the aliphatic series.
    A smaller amount of mono-olefin compound is used in combination with matrix monomers. Such monoolefin compounds can be substituted or unsubstituted and chosen so that when added to the growing alkenyl aromatic chain, they form a more reactive residue than the alkenyl zromati. cical residue, and alkyl hydrogen are more easily extracted from dissolved rubber molecules for easier and easier graft polymerization of rubber. Monoalkeyuslnye monomers aromatics tsa are more reactive monomers due to their conjugated structures, however alkenyl aromatic monomer1 {th free residue at the end of the growing chain is stabilized by resonance and okazgoaets from 1osntelno unreactive not cleaved easily allilny hydrogen from the rubber molecule for the purpose of initiating graft -polymerization. Mono-olefin compounds are not conjugated and are less active than monomers even when added to a growing chain. Not stabilized by resonance, they form highly active free residues that can form bonds with the pebble chains, split off hydrogen, so they cause the formation of more graft polymerization sites, increasing the grafting rate. Since such olefinic compounds do not easily polymerize with other compounds, but easily polymerize with the stretch chains of alkenyl aromatic compounds, there are plenty of free residues (small amounts of reactivity require small amounts to facilitate grafting, about 0.04–5 wt.% in terms of m solution.
    The mechanics of the reaction, in which inert olefinic compounds form ochega active free residues, have not been fully studied. One of the factors is stabilization. account of resonance, but it does not always occur in this spatial difficulty; another factor is the polarity of the unsaturated double bond.
    Mono-olefin compounds, when dissolved in a rubber-monomer solution, in which the bulk of the monomer consists of an alkenyl aromatic monomer, cause a higher degree of grafting. Mono-olefin compounds of this kind are selected from a cadaver consisting of monoolefruvs that form free residues with monoalkenyl aromatic monomer p3, more active than monoalkenyl aromatic ip 1y residue when transferred with a rubber chain.
    Preferred mono olefin-1 compounds of the aliphatic series are compounds that have low resonance stabilization and preferably attached to the monoalkenyl monomer of the aromatic series of high stability due to resonance and therefore produce a very reactive residue that induces a chain transfer in which the rubber removes hydrogen, forming a free residue on a rubber molecule, and the graftpolymerization of the styrene monomer is easy. These compounds, for example, include ethyl, propylene, butene-1, hexene-1, vinyl acetate, ethyl lyshex ether allyl acetate, and compounds of low resonance stability and low polarity of an unsaturated double bond.
    According to the proposed method, rubber particles should be obtained and dispersed in the first reactor and then graft-polymerized and stabilized to withstand dimensions and structure. The KonniecTBO absorbed monomer-half-dimensional phase described above is held at the above-described predetermined level by uniform polymerization, in which the monomer is converted to a polymer, and at least one part is grafted to rubber, the particle size is stabilized. With an increase in the number of absorbed hours, stabilized inside the rubber cup-shch, the effectiveness of the auxiliary effect of the rubber phase on the mixture increases. Rubber particles act in a large step in the form of pure rubber particles, if the absorption is controlled in the volume described above, during their stabilization on the initial steps and during the whole polymerization process. Rubber graft-polymer particles are also externally with their structure stabilized with respect to size and dispersibility in the monomer-half-dimensional phase. -H
    The first reactor forms the polymerization mixture of the monomer polymer phase, with the rubber phase dispersed therein. The mixture is then polymerized by a gradual multistage, generally linearly proceeding after imimerization, with the conversion of the polymer in the first stage within a range of from about 10-50 to 50-90% in the last stage of the isobaric transferable reactor. This ensures a gradual increase in the polymer content in the monomer polymer phase.
    The amounts of the total absorbed polymer phase and the graft polymerized polymers are measured. The target polymerizable mixed product (1g) is dispersed in 10 ml of a solvent mixture of acetone and methyl ethyl ketosh (50/50), which dissolves the polymer matrix phase, but leaves the rubbery phase in a dispersed state. The rubber phase is separated from the dispersion by centrifuging in the form of a gel and dried in a vacuum oven at 50 ° C for 12 hours, then the weight of the dry gel is determined. Dry gel, hard gel j QQ in a mixture of polymers,% by weight of a mixture nbjiHNiepog Graft-polymer dry gel -KayivK:, shg and absorbed pro- ... k jJ rubber tsukty in Kluchukb,% Graft-polymer and the percentage of rubber absorbed by the dry gel rubber polymer per unit of rubber is determined by the IR spectrochemical analysis of the dry gel; According to the proposed invention, preferably about 0.5-5 g of absorbed and graft-polymer per 1 g of diene rubber. The swelling index of the graft particles is determined by dispersing the dry gel for 12 hours in toluene. The gel is separated by a centrifuge, leaving the product (toluene) drained. The wet gel is weighed and then dried in a vacuum oven for 12 hours at, then syooweast IOT weight. the weight of the wet gel swelling index ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– rubber The percentage of dry gel is the percentage of gel in the polymer mixture and is dispersed in the rubber phase containing absorbed polymers and graft polymers. The percentage of gel varies depending on pro-. cent amount of rubber added to the monomer composition and the total amount of graft-polymer and absorbed polymer in the rubber phase. The properties of the target product are determined by rubber swelling index. A low swelling index indicates that the rubber was subjected to blending with a number during the polymerization process into the polymer phase in rubber-based particles. Typically, npeiBpawHHe monomer into a polymer in the absorbed phase depends on the rate of monomer conversion to the polymer in the monomer-polymeric phase. If rektsi in the second reactor gives ripe Bipaiijejffle in the amount of about 70-90% instead of 99-100%, the polymerization mixture can be made non-volatile separation of residual monomers from the mixture. The temperature of the polymerization mixture rises to about 185-250 ° C; pyr monomer otdeat nig, 1yluch.a target the Compound ymerov. K10 particles often mix ignreM heating the mixture to approximately 150-250 ° C for a period of time sufficient to remove the rubber particles so that their Nebuchani index is approximately 7-20, preferably 8-16. The polymer of the matrix phase of polymer blends preferably has a dispersion index (Myy / Mf), where Muu is a weight average molecular weight, and M is a digital average molecular weight of about 2.0-4.0, preferably 2.2-3.5 . The average molecular weight of the polymer of the matrix phase preferably ranges from 170,000 to 500,000 with an average molecular weight of about 50,000,200,000. Polymerization of steps. Polymerization after prepolymerization is preferably carried out in a cylindrical, generally horizontal, through, stepwise, isobaric, stirred reaction zone, maintaining the conditions necessary for the polymerization of the first prepolymerized mixture by gradual, multi-step, mostly linear, through polymerization. At all stages, shear is inverted and cooled by evaporation of the vapor phase under isobaric conditions in the above reaction zone. At each stage: uniform polymerization is carried out) with temperature control and interfacial contact. Step by step, hydraulic pressure is created, starting from the first step downstream to the last, providing mostly linear flow, of the medium through the reactive zone. At all the stages, the preset transformation is maintained, obtaining in the reaction zone a polymer of a predetermined molecular weight distribution and a predetermined average molecular weight while maintaining the integrity of the structure of dispersed rubber particles. In this reaction, a polymerization mixture is obtained in the reaction zone with a total polymer content determined by a multi-stage equilibrium polymerization and evaporation of the monomers. The reactor operates under regulated isobaric conditions. For alkenyl aromatic monomers, for example styrene polymerization, the working pressure is 0.42, 0 kg / cm. Styrene reacts exothermically, cooling is cooled to the first O41, by evaporation of a portion of the monomer of the reaction mass. Additional cooling may be jacketed. Cooling is also carried out using a condensed recycle monomer entering the reaction zone. The mass is in a state of boiling, the temperature is determined by the natural ratio between the vapor pressure and the boiling point. This ratio is also a function of the relative amounts of polymer, monomer a and other substances (for example, soluble rubber, solvents and (additives). BECAUSE the quantity of polymer continuously increases during the passage of the polymer through the reactor, and the amount of monomer decreases accordingly Additionally, due to losses during the cooking, the temperature gradually rises from the inlet to the outlet. Taking into account the natural swelling of the boiling mass and the necessary space for the removal of steam, the reactor works t with a load of 10-90%, preferably 40-80% of the volume. Steam leaves the reactor to a condenser located outside the reactor, where it condenses with and can be supercooled. This condensate can then be fed back to the entrance to the reactor, where the fractions of previously removed vapors are heated by condensation and mixed with other incoming free substances. In a multistage reactor at each stage, they are thoroughly mixed, so that the reaction mass is homogeneous. Disks separating individual areas from each other do not allow the medium to flow in the opposite direction. The gap between the disk and the housing although allows for some return flow of the medium, but mainly regulates the translational motion of the medium through the sections from the inlet of the reactor to the exit from it. The flow of the medium is linear. In a staged reactor divided into regions, a relatively low conversion level is always observed in the first stage, since the monomer solution is continuously fed there. The conversion rate at this stage is relatively high due to the high monomer concentration. In each subsequent stage, the level of transformation than in the previous one, which causes a decrease in the rate of conversion. However, this phenomenon is compensated for by the fact that the temperature is higher and the monomer is evaporated from the mass. Thus the general degree of conversion. Polymer per unit of loaded material of a step reactor is higher than the degree of conversion in a single-stage reactor with the same conversion levels and temperature. The gap between the rotating diaphragm partitions and the cylindrical wall may be 1-10% of the radius of the shell, with higher values being at the end of the reactor, where a high level of conversion is observed and the viscosity reaches its maximum. The flow of the medium passes through these gaps from one step to another, in the opposite direction the steam passes from the full-sized mixture, above the level of the latter. The monomer-polymer solution flows through the reaction zone mainly with a pinhole, with minimal back mixing, from the first stage to the last under hydraulic pressure. The temperature regime in the reaction zone is carried out by pressure, npHiieM, so that the polymerization solution of the melt under the action of the heat of its own polymerization. The monomer-gas phase is removed at a rate sufficient to maintain the temperature of the polymerization solution 100-180 ° C and the isobaric conditions of 0.4-2.0 kg / cm. Monomer, such as styrene, is polymerized, giving 233 calories per g of polymerizate. The heat energy of styrene residue is equal to 83 calories per 1 g of evaporated product, thus the reactor, such as P1) avsh1o, removes 2 kg of monomer from the polymerisation mass per 1 kg of converted polystyrene, which returns back to the first polymerization stage at a rate sufficient to maintain uniform polymerization at a controlled temperature: - :: under isobaric conditions. The reaction zone can be charged to 1590% of its volume with a polymerizing solution, the remaining space being filled with the exhausted monomer. From the last zone of the system unload the mixture, the degree of conversion of which is 10-90%. The last steps of the reaction zone are usually maintained at a temperature of 130180 ° C, i.e. higher than in the first reactor of the system, with the formation of polymers having an average molecular weight of low order of 170000-250000. The blended polymer may have a molecular weight in the order of 170000-350000. This range makes it possible to obtain a wide range of polymers with different molecular weight distributions and different levels of reaction load. In a step reaction zone, it is advisable to use a step isobaric stirring, a continuous LYO reactor, which is controlled by the liquid level, maintained to adjust the temperature in the second zone. The output stream of vaporous monomer is condensed in a condenser and collected in a collection box. It can be returned to the first step of the reaction zone. The preferred way to recuperate conditions in the reaction zone is to control temperature. At the final stage of the reactor. The system includes the determination of the temperature in the liquid phase of the last stage of the reactor using the signal obtained in this way to check the thermostat modified with the overshoot coming from the setpoint generator at the setpoint temperature. Received signal modified by signal obtained by reading pressure 1173517212
    nor in the solid phase of the reactor, is used to add to the usual added in the reaction zone,
    adjusting the pressure regulator, regulating, preferably, at the last stage from the priest, in turn, the discharge valve, is not enough for multi-staged dosing pumps with a discharge channel from the collection of consoles. danated monomer, entering about - s. Corresponding adjustment of reactors per cycle. By setting the pressure above such a condensed monomer in the collector, the temperature of the final stage of the reactor can be very accurately and quickly monitored and controlled to achieve a given value of the desired order. The temperature of each stage. it quickly reaches an equilibrium value based on the pressure of the reactor and the content of the polymer solids of the polymerization solution of each stage. The application of the proposed method makes it possible to obtain polyalkeshny polymer mixtures of an aromatic range of high toughness. The polymer mixture of polymer, dispersed rubber and monomer mixture includes a liquid phase leaving the reactor. This mixture contains solid polymer particles in an amount of about 50-90 wt.%, Is extracted from the reactor with a caster pump and is sent to 30in.i heating or processing. that leads to loss of volatility. One zone of volatility loss can be loaded with pressure below atmospheric pressure or certain vacuum values. It is possible to use shuhs or several zones of volatility loss. According to the process described above, after having extracted the alkyne monomers of the paiBKo aromatic series, like their / lower oligomers, they can be lost from the first soHSi, they can be condensed and sent to the receiver, the flow of condensed monomers and oligomers can be condensed and sent to the receiver. re-injected into the first stage of the reactor. Analogs, monomers and oligomers, evaporated in the second zone, usually loaded with a slightly lower pressure but compared to the first, are removed,. is condensed and sent to a receiver, from which a stream of condensed monomers and oligomers can also be introduced back into the reactor. Preferably, the oligomers, by evaporating the sheaves in any of the volatility loss zones, can be separated from the evaporating monomer by distillation and separately introduced back into the reactive zone or removed from the process itself. In preparing certain polymers, it is preferable to add high boiling point organic compounds to the polymers obtained, preferably during the polymerization process. These additives include internal lubricants, such as mineral oils or other heavy oil agents, or mold separators, such as fatty acids, their complex salts and waxes. These various types of loading provide for the preparation of polymers with special physical properties and molecular weight distribution from 30 to 100%. Example 1. Rubber solutions were manufactured comprising 95 parts by weight. styrene and 5 weight.h. polybutadiene rubber. The solutions are cleaned with nitrogen for 2 hours in order to remove the dissolved oxygen. At a conversion rate of styrene monomer of 10-40%, kinetic studies are carried out in which the main percentage of vaccination takes place (about 65%). In this case, the speed of the grafting process is investigated more accurately, since a high degree of viscosity and gelatinization phenomena do not affect the rate of polymerization and grafting. Experiments show that with bulk polymerization with a degree of 10-50% graft, 65% is 65%, while with a conversion degree of 50-100%, grafting is 35%. Therefore, the grafting efficiency turns out to be critical in the first stages of bulk polymerization, which is the purest system for investigating the effectiveness of grafting in the bulk polymerization process. The solutions are subjected to harsh polymerization in bulk, moving them in tubes 2.5 x 20 cm in size. They are displaced with a glass rod equipped with disks with a size of 1.5 and 0.3 cm fixed to it at a distance. When the rods pass through pressure-tight gaskets load at 4 rpm with a shear rate of less than 100. The transmutation is measured by precipitating the polymerized polymer in methanol and water solutions, followed by filtration, and essentially precipitated polymer in vacuo. The molecular weights of the polymer are measured by the intrinsic viscosity in toluene at 25 ° C. The graft level is determined according to the experiment described above, using a mixture of acetone and methyl ethyl ketone to separate into the grafted coffer and polymer phase. The solution, purged with nitrogen, is polymerized at 130 ° C for 1 hour and rapidly cooled in order to determine the molecular weight of the polymer and the degree of grafting, including grafting in the form of occlusion or internal grafting inside the particles. The analysis shows that the degree of conversion is about 20%, and the rubber phase contains about 70% by weight of graft copolymer13 pa in terms of rubber Gtrn molecules rkGg mass of matrix peehyrroles (Pfada about 82000. From the average, the degree of grafting is relative to tyg, and the molecular weight of the polymer (high carrier, indicating a low cTcrieim of chain transfer with rubber / uw due to grafting. Example 2. Repeat the process of measure 1 with heptamethylated ethylene Ha; and as a mono-olefin aliphatic compound and in order to purify the rubber solution. The solubility of ethylene in the styrene-rubber solution is about 0.04 wt.% based on the solution at and 3 atm, on polymerization. The analysis shows that the degree of conversion is about 20%, and the rubber phase contains about 220 wt.% of a graft copolymer in terms of rubber with a molecular weight of 345,000 matrix polystyrene. From the data it follows that the ethylene monoolefin compound of the aliphatic series when dissolved in smaller quantities of rubber-monomer solution causes a highly intense process with inoculation with bulk polymerization solutions containing monoalkyl aromatic monomer row and dissolved diene rubber. The olefinic compound forms, with the aforementioned alkenyl monomer of the aromatic series, free radicals that are more active during chain transfer with this rubber than the purely aromatic aromatic monomer, increasing the graft polymerization of the polymer molecules to obtain the above rubber phase. Example 3. The processes of example 2 are repeated using propylene and butene-1 as olefinic compounds. The solubility of propylene is equal to 03% by weight in terms of solution; moreover, the content of butene-1 is 1.0 wt.% at 130 ° C and at 3 atm. The analysis shows that propylene causes a graft polymerization degree of about 220 wt.% In terms of rubber and PM molecules, the mass of polystyrene is 338,000. Butene-1 determines a graft polymerization degree of 140% and a molecular weight of 288,000. Example 4. It is carried out similarly to the example 1, purged with nitrogen in order to remove oxygen, the solution is then 5 wt.% Based on the solution of liquid hexene-1 in this solution as an olefinic compound. The analysis shows that the degree of graft polymerization is 90%, and mol. mass i 35600 Obviously, higher molecular weight olefinic compounds are not as effective when producing graft copolymers than olefinic compounds with a lower 7214 molecular weight, they give more graft copolymer than styrene monomer in pure in (e. Example 5. Example 4 is repeated, a solution of 5% by weight of vinyl acetate in a rubber solution. The analysis shows that the degree of graft-popmertape is about 1809 "in terms of rubber; the molecular weight of the polystyrene ethereal phase is 330000, Knead These olfint-, difficult to polymerizable with each other, have the ability to polymerize with styrene free radicals, forming extremely active (e free frameshields that cause effective chain transfer with rubber. Example 6. By mixing the mixture for Hh at 40 ° C, a monomer is obtained A no-rubber solution consisting of 8 wt .h stereospecific polybutagen rubber in 92 parts of styrene monomer used. The rubber used contains approximately 35% of the cis-1,4 structure; about 55% of trac-.4-structure; and about 10% vinyl-1,2-jet (with lypbf with Myrai viscosity rubber (ML 4, 100 C) with a value of 55. To 0.5% by weight of monomeric composition, add 0.5 parts by weight of white cineral oil, 0.1 parts by weight of octadecyl-3- (3, 5-di-tert-butyx-4-hydroxyphenyl) propionate and 40 parts by weight of recycled styrene monomer. This mogg composition is served in a non-continuous manner at a rate of 65 g / h. to a 380 l initial reactor stirred by a root mixer, which is filled to approximately 50% and which operates at 124 ° C under a nitrogen pressure of 1.4 kg / cm. The mixer is 79 cm wide and rotates at 65 rpm, the first piston of the mixture, containing about 28% polystyrene, is pumped out of this reactor at a constant speed so that the reactor is kept constant at 50%. Then the mixture is fed to the inlet to the second multistage reactor of the selected type, where it is also mixed. The capacity of the second reactor is 190 liters; it operates at a filling degree of about. The length of the reactor is 133 cm. The agitator consists of a horizontal rod, to which a row of blades or blades 5 cm wide, alternating from each other at right angles. Along the rod there are 4 rounds with it, with a gap of 1 cm in average, which climb at a speed of 15 rpm. These washers are designed to divide the reactor into 5 stages of approximately the same volume. The pressure in the reactor is maintained at 2.0 kg / cm. The second mixture on the last Stalin was kept close to it when it contains
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing impact-resistant polystyrene by radical polymerization in the mass of a mixture of styrene with 1-20 wt.% Polybutadiene rubber at 80-180 ° C, characterized in that, in order to increase the impact strength and elongation under tension of the polystyrene, the process is carried out in the presence of 0.045.0% by weight of the reaction mixture of an aliphatic monoolefin with a content of C 2 -C 6 in the chain or vinyl acetate.
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    同族专利:
    公开号 | 公开日
    AU2669477A|1979-01-04|
    SE7707580L|1978-01-02|
    BE856320A|1977-12-30|
    JPS535293A|1978-01-18|
    GB1558099A|1979-12-19|
    SE435189B|1984-09-10|
    US4185049A|1980-01-22|
    IL52428D0|1977-08-31|
    BR7704293A|1978-05-16|
    MX4581E|1982-06-23|
    ES460170A1|1978-05-16|
    FR2356681A1|1978-01-27|
    DE2729590A1|1978-01-12|
    AU513625B2|1980-12-11|
    IT1081126B|1985-05-16|
    IL52428A|1980-03-31|
    FR2356681B1|1981-05-08|
    AR221209A1|1981-01-15|
    CA1119337A|1982-03-02|
    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/701,844|US4185049A|1976-07-01|1976-07-01|Mass polymerization process for polyblends|
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