• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:NL2011694A
    申请号:NL2011694
    申请日:2013-10-29
    公开日:2014-05-06
    发明作者:Luqiang Yu；Zhichao Yang；Jiangbo Chen；Yafeng Du；Qinyu Tong；Kang Sun；Yang Liu；Jie Zou；Lusheng Wang；Zengyue Dai；Zhong Tan；Jianxin Zhang
    申请人:China Petroleum & Chemical；Beijing Res Inst Chem Ind；
    IPC主号:
    专利说明:

    Method for preparation of propylene polymer Technical Field
    The present invention relates to a method for preparation of a propylene polymer, more particularly, relates to a method for preparation of a propylene homopolymer having high melt index and high rigidity as well as a propylene/a-olefine copolymer having both high melt index and a good rigidity-toughness balance.
    Background Art
    Most of propylene polymer products can be used for injection molding articles, and widely applied in many fields such as package, transportation, domestic appliances, automobiles, office supplies, daily necessities and medical articles. There are two trends for development of high performance propylene polymer products. The first trend is to increase melt flow rate (MFR, also referred as melt flow index (MFI)) of polymer, which may help to shorten molding period, reduce energy consumption, and make large thin-wall articles. At present, injection productions with MFR of 10-15g/10min are gradually replaced with products with MFR of 25-35 g/lOmin. The second trend is to seek the balance between rigidity and impact strength of propylene polymers, so as to meet the requirements on impact strength of propylene copolymers while improving rigidity, and thereby the thickness of product can be reduced and the production cost of articles can be also decreased. Since propylene polymers with high melt flow rate can shorten molding period, reduce energy consumption, meet the requirements on impact resistance and increase the rigidity of propylene polymers, such propylene polymers with high melt flow rate have predominant advantages in increase of product output, decrease of product cost and manufacture of large complicated thin-wall articles.
    The following methods are usually used to increase MFR of propylene polymers: (1) Using catalyst system sensitive to molecular weight regulation in polymerization process. By selectively combining different catalysts, cocatalysts and external electron donors, the polymerization catalyst system becomes more sensitive to the molecular weight regulator (e.g., hydrogen gas that is the commonest molecular weight regulator), so that polymer products with high MFR can be obtained in the presence of small amount of hydrogen gas .
    (2) Adding into the polymer a degradation agent after the polymerization. Usually are added one or more peroxides, so that polymer chains in the polymer are broken under certain conditions to increase MFR of the product. This technique is generally referred as controlled rheology technology.
    At present, many devices for production of polypropylene use the increased amount of hydrogen gas to produce propylene copolymer products with high MFR, but the amount of added hydrogen gas is limited due to the limitation of pressure design of devices, as is the case with the present liquid phase bulk polymerization process of propylene. The addition of a large amount of hydrogen gas may result in the following defects: a significant decrease of catalyst activity; a decrease of isotacticity of polymers, resulting in the decrease of rigidity of final polypropylene articles; and in addition, the existence of a large amount of hydrogen gas, which is a non-condensable gas, deteriorates heat transfer effect of heat exchange of the system, so that the production load of device is directly influenced and thus the production output decreases . There are also some methods, in which the amount of the hydrogen gas used is reduced by selecting a combination of different catalysts, cocatalyst and external electron donors, for example, the method as described in CN101270172A. The method disclosed by this invention can improve hydrogen-regulation sensitivity of propylene polymerization and render the isotacticity and MFR of the obtained polypropylene adjustable within a relatively broad range, but the use of hydrogen-regulation sensitive catalyst usually results in the decrease of isotacticity and the deterioration of rigidity-toughness balance of final product.
    The current polymerization processes can hardly give consideration to the requirements on polymerization activity, hydrogen-regulation sensitivity, and high isotacticity and high melt flow rate of propylene polymers. In order to meet the requirements on isotacticity and high melt flow rate of polypropylene products, propylene copolymers with high MFR are usually produced by controlled rheology technology, i.e., by using a method of adding a small amount of peroxide degradation agents to obtain propylene copolymers with high melt index. Due to the degradation of products caused by peroxide, polypropylene articles usually smell unpleasant and thus their applications are significantly limited.
    It is well known that in olefin polymerization process, Ziegler-Natta catalysts have many advantages with the elevation of olefin polymerization temperature. For example, as for the propylene polymerization, with the elevation of polymerization temperature, catalysts become more sensitive to molecular weight regulator (e.g., hydrogen gas), so that polymers with small molecular weight can be generated even in the presence of a very small amount of hydrogen gas, as is very favorable to the production of polypropylene products with high melt index. In addition, with the elevation of polymerization temperature, the isotacticity of the generated polypropylene is also improved, as is very favorable to the production of propylene homopolymer product with high rigidity and propylene copolymer with good balanced rigidity-toughness properties. At present, an amount of nucleating agent is usually required to improve the rigidity of polymer products, which results in the increase of production cost. Hence, it is an ideal option to improve the quality of polypropylene products by elevating polymerization temperature.
    For example, the Chinese Patent CN100457790C discloses a polymerization process, which comprises the following three-stage polymerization: (1) pre-polymerization of propylene, (2) low-temperature polymerization, (3) high-temperature polymerization. In this process, the polymerization temperature is gradually elevated and the proportion of polymers in each polymerization stage is controlled so as to obtain propylene polymers with high flexural modules and high bending strength. However, since the use of low-temperature polymerization in step (2) consumes most of polymerization activity of the catalyst, the improvement for the polymer properties that should be brought out by high-temperature polymerization is not fully achieved.
    In addition, the conventional Ziegler-Natta catalysts have limitation in adaption to polymerization temperature. Generally speaking, when the polymerization temperature exceeds 85°C, the catalyst activity usually declines quickly if no treatment is applied. In particular, when the polymerization temperature is higher than 100°C, the polymerization activity usually declines so low as to render the process worthless in the industrial application.
    In sum, there is still no propylene polymerization process and corresponding catalyst which can meet the requirements on polymerization activity, high isotacticity of polymers, and improved hydrogen-regulation property so that propylene polymers with high fluidity and high rigidity can be prepared while the catalyst still maintains high polymerization activity.
    Brief Description of the Invention
    The object of the present invention is to overcome the drawbacks in the prior art that the requirements on polymerization activity, hydrogen-regulation sensitivity and melt flow index, rigidity and impact resistance cannot be met simultaneously when producing propylene polymers having high melt flow rate, and to provide a method for preparing propylene polymers that can give consideration to all these requirements.
    The present invention provides a method for preparing propylene polymers, comprising the following steps: (1) performing pre-polymerization of propylene or an olefin mixture containing propylene and other α-olefin comonomer (s) in a gas phase or a liquid phase in the presence of a Ziegler-Natta catalyst at -10°C to 50°C and 0.1-10.0 MPa to obtain a propylene prepolymer, wherein the pre-polymerization multiplication is controlled in the scope of 2-3000 g polymer/g catalyst, preferably 3-2000 g polymer/g catalyst; (2) performing a homopolymerization of propylene or copolymerization of propylene and other α-olefin comonomer (s) in a gas phase in the presence of the propylene prepolymer as obtained in step (1) under conditions of 91-150°C, preferably 91-130°C and more preferably 91-110°C and 1-6 MPa to obtain a propylene polymer, wherein the polymerization time is 0.5-4 h; (3) continuing the homopolymerization or copolymerization of propylene in a gas phase or a liquid phase in the presence of the product as obtained in step (2) under conditions of 50-150°C and 1-6 MPa.
    In addition, the present invention further provides a propylene homopolymer and a copolymer of propylene and other α-olefin comonomer(s) which are prepared by the method for polymerization of propylene according to the present invention.
    Detailed Description of the Invention
    The following terms and definitions thereof are applied to whole text of the description and claims of the present invention.
    In the present invention, the term "pre-polymerization multiplication" refers to a ratio of prepolymer weight to solid catalyst component weight as originally added. Generally, as for the intermittent pre-polymerization, the pre-polymerization multiplication can be calculated from dividing the weight of prepolymer as directly measured by the weight of catalyst as added; as for the continuous pre-polymerization, pre-polymerization multiplication can be indirectly controlled by regulating the residence time and polymerization temperature of the reaction. For different catalysts, different polymerization temperatures, different polymerization manners (gas phase, liquid phase bulk, etc.) and different polymerization pressures, pre-polymerization multiplications could be different even if the same residence time in pre-polymerization might be used, and could be obtained by integral computation according to reaction kinetic curve of catalyst.
    In the present invention, the phrase "weight ratio of the reacted polymers in steps (2) and (3)" refers to a ratio of the weight of polymers generated in propylene polymerization in step (2) to the weight of polymers generated in polymerization of propylene and other α-olefin comonomer (s) in step (3) . According to the present invention, although the weight ratio of the polymers in steps (2) and (3) is not specifically limited, the weight ratio of the polymers in steps (2) and (3) may be preferably 0.3-3, more preferably 0.5-2, further preferably 1.0-2.0 and 0.8-1.5, in view of isotacticity and melt flow rate of propylene copolymer.
    According to the present invention, the melt flow rate MFR of the polymer is measured according to ISO 1133 under conditions of 230°C and 2.16kg of load.
    In the method according to the present invention, the steps can be performed in one reactor for batch polymerization operation, or performed in different reactors for continuation polymerization operation.
    In one embodiment of the method of the present invention, in step (1), the pre-polymerization temperature is controlled in the scope of -10°C to 50°C, preferably 0-30°C, more preferably 10-25°C. The pre-polymerization pressure is 0.1-10.0 MPa, preferably 1.0-6.0 MPa, more preferably 1.5-5.5 MPa . The reaction time of this stage depends on the desired degree of pre-polymerization, which for example can be 8-16 min, preferably 10-14 min.
    According to the present invention, the phase state of propylene in the pre-polymerization of step (1) is not particularly limited, and the pre-polymerization can be performed in either gas phase or liquid phase. Preferably, the pre-polymerization in step (1) is carried out in liquid phase, especially in a liquid phase bulk pre-polymerization. During the liquid phase bulk pre-polymerization a full kettle operation can be employed and the pre-polymerization multiplication can be controlled with the residence time and reaction temperature, so that a continuous operation can be readily realized to reduce the operation cost. In this process, the pre-polymerization multiplication is 2-3000 g polymer/g catalyst, preferably 3-2000 g polymer/g catalyst, more preferably 3-1000 g polymer/g catalyst.
    In another embodiment of the method of the present invention, in step (2), the polymerization is carried out in the presence of the prepolymer as obtained in step (1), wherein the polymerization temperature is 91-150°C, preferably 91-130°C, more preferably 91-110°C and particularly 91-105°C, and the polymerization pressure is 1-6 MPa, preferably 2-4 MPa, more preferably 2-3 MPa. The reaction time can be controlled in the scope of, for example, 40-90min, preferably 50-70min. In this step, a gas phase homopolymerization of propylene is preferably carried out.
    The reaction can be carried by gas phase polymerization process, and can be carried in one reaction kettle or a plurality of reaction kettles in series. Although the type of reaction kettle is not specifically limited, the gas phase polymerization is preferably carried out in a gas phase horizontal reaction kettle. The horizontal reaction kettle has a horizontal agitating shaft and uses quench liquid to remove heat. According to the reaction mass and heat transfer property as well as the physiochemical parameters of propylene polymers, the gas phase horizontal reaction kettle is controlled with a stirring speed of 10-150 rpm, preferably 10-100 rpm, and more preferably 20-50 rpm. The shape of the agitating blade can be T-shape, rectangle shape, inclined paddle, door type, wedge-shape and a combination thereof. The polymerization reaction time or residence time is 0.5-4 h. The melt index of the polymer can be regulated with a molecular weight regulator. Under polymerization conditions of step (2), the obtained polymer has MFR of 10-2000 g/lOmin, preferably 15-1000 g/lOmin, more preferably 20-1000 g/lOmin, and most preferably 30-500 g/lOmin.
    In one embodiment of the present invention, as for the polymerization in step (3), in the presence of the product as obtained in step (2), the propylene homopolymerization or copolymerization proceeds in a gas phase at 55-110°C and under the reaction pressure of preferably 1.5-4 MPa, and more preferably 1.5-2.5 MPa, wherein the reaction time can be 30-90 min, more preferably 35-45 min. In the present invention, the polymerization temperature of step (3) is advantageously controlled substantively lower than the polymerization temperature of step (2) .
    According to the present invention, the copolymerization of propylene and other α-olefin comonomer(s) can be preferably carried out in step (3). Although the kind of α-olefin is not specifically limited in the present invention and various α-olefins capable of copolymerizing with propylene in the art can be used in the present invention, the α-olefin is preferably one or more selected from ethylene, butylenes and hexylene, more preferably ethylene. The amount of other α-olefin comonomer(s) is not specifically limited either, but the other a-olefin comonomer (s) , especially ethylene is used in an amount of 4-40wt%, preferably 6-30wt%, relative to the weight of the propylene homopolymer obtained in step (2).
    The weight ratio of the polymers of steps (2) and (3) is 0.3-3.0. In the polymerization method of the present invention, the weight ratio of the reacted polymers in step (2) and step (3) is preferably greater than 1, preferably 1.0-2.0. After the polymerization of step (3), the obtained polymer has a melt flow rate MFR of 1-500 g/lOmin, preferably 5-300 g/lOmin, more preferably 8-200 g/lOmin, and most preferably 10-150 g/lOmin.
    In the polymerization method of the present invention, the Ziegler-Natta catalyst can be any Ziegler-Natta catalyst as known in the art. Preferably, the catalyst comprises a reaction product of the following components: (1) a titanium-containing solid catalyst component; (2) an alkyl aluminum compound; and (3) optionally, an external electron donor component.
    The component (1) is a reaction product of contacting an alkoxy magnesium compound, a titanium compound and an internal electron donor compound.
    The titanium compound is selected from at least one compound of Formula: Ti (OR) 4_nXn/ wherein R is selected from C1-C14 aliphatic hydrocarbonyl or aromatic hydrocarbonyl group (e.g., C7-C14 aromatic hydrocarbonyl group), X is halogen atom, n is an integer from 0 to 4; and in case of n being equal to or less than 2, the existing R groups can be identical or different. The said halogen atom can be chlorine, bromine or iodine.
    For example, the titanium compound is at least one selected from a group consisting of tetraalkoxy titanium, titanium tetrahalide, alkoxy titanium trihalide, dialkoxy titanium dihalide and trialkoxy titanium monohalide. More specifically, the said tetraalkoxy titanium is at least one selected from a group consisting of tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso-butoxy titanium, tetra-cyclohexyloxy titanium, tetraphenoxy titanium; the said titanium tetrahalide is at least one selected from a group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide; the said alkoxy titanium trihalide is at least one selected from a group consisting of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, ethoxy titanium tribromide; the said dialkoxy titanium dihalide is at least one selected from a group consisting of dimethoxy titanium dichloride, diethoxy titanium dichloride, di-n-propoxy titanium dichloride, di-iso-propxy titanium dichloride, diethoxy titanium dibromide; the said trialkoxy titanium monohalide is at least one selected from a group consisting of trimethoxy titanium monochloride, triethoxy titanium monochloride, tri-n-propoxy titanium monochloride, tri-iso-propoxy titanium monochloride. Herein the titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.
    The internal electron donor compound is one or more selected from alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones; preferably one or more selected from alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic ethers, C3-C4 cyclic ethers, C3-C6 saturated aliphatic ketones and 1,3-diether compounds.
    Preferably, the internal electron donor compounds can be phthalic acid ester compounds of Formula (III),
    In Formula (III), R4 and R5 are identical or different, independently from each other denote one selected from C1-C12 straight or branched alkyl, C3-C10 cyclic alkyl, C6-C20 alkylaryl and substituted or unsubstituted aryl; R6, R7, R8 and R9 are hydrogen, or three of them are hydrogen, and the other one is one selected from halogen, straight or branched alkyl with 1-4 carbon atoms and straight or branched alkoxy with 1-4 carbon atoms.
    The compound of Formula (III) is selected from diethyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-isooctyl phthalate. More preferably, it is diethyl phthalate.
    The internal electron donor compounds can be also selected from 1,3-diether compounds of Formula (IV),
    (IV)
    In Formula (IV), Rn and R12 are same or different, independently from each other selected from C1-C20 straight, branched or cyclic aliphatic groups; R13, Ri4r Ris, Ri6, Rn and Ris are same or different, independently from each other selected from hydrogen, halogen atoms and straight or branched Ci- C2o alkyl, C3-C20 cycloalkyl, Ce- C2o aryl, C7- C2o alkylaryl and C7-C20 arylalkyl, and optionally one or more of groups R13 to Ris can be bonded each other to form a ring.
    Preferably, Rn and R12 are same or different, independently selected from C1-C6 straight or branched alkyl; R15 and Ri6 are same or different, independently selected from straight or branched C1-C10 alkyl, or C3-C10 cycloalkyl.
    The diether compounds of Formula (VI) are but not limited to: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-di(methoxymethyl)fluorene, 2-isobutyl-2-isopropyl-l,3-dimethoxypropane, 2.2- dicyclopentyldimethoxypropane, 2.2- diphenyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-l,3-dimethoxypropane, 2.2- dicyclopentyl-l,3-dimethoxypropane, 2.2- diisobutyl-l,3-dimethoxypropane and the like.
    The alkoxy magnesium is at least one selected from the compounds of Formula (II) Mg (OR1) 2-m (OR2) m, wherein R1 and R2 are same or different, independently selected from Ci-Cs straight or branched alkyl, and 0<m<2.
    Preferably, R1 and R2 are independently from each other selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-hexyl, (2-ethyl)hexyl; more preferably, R1 is ethyl, R2 is (2-ethyl)hexyl, and 0.001<m<0.5. It should be pointed out that the alkoxy magnesium represented by this formula merely shows the composition of various alkoxy groups, i.e. their molar ratio, but does not illustrate the exact specific structure of alkoxy magnesium.
    The alkoxy magnesium compound has a sphere-like shape and an average particle size (D50) of 10-150μπι, preferably 15-100 pm, more preferably 18-80 pm. In addition, its particle size distribution index SPAN is < 1.1, preferably < 1.05, wherein SPAN is calculated by the following formula: SPAN = (D90-D10)/D50 (V)
    In Formula (V), D90 represents a particle diameter corresponding to a cumulative weight fraction of 90%, D10 represents a particle diameter corresponding to a cumulative weight fraction of 10%, and D50 represents a particle diameter corresponding to a cumulative weight fraction of 50%.
    The alkoxy magnesium compound according to the present invention is prepared by reaction of magnesium metal, alcohols corresponding to the alkoxy groups of Formula (II) and mixed halogenating agent in an inert atmosphere under refluxing, wherein the molar ratio of magnesium metal to halogen atoms in the mixed halogenating agent is 1:0.0002 to 1:0.2, preferably 1:0.001 to 1:0.08; the weight ratio of alcohol to magnesium is 4:1 to 50:1, preferably 6:1 to 25:1. The reaction temperature is from 0°C to the refluxing temperature of the reaction system. Preferably, the reaction temperature is the refluxing temperature of the reaction system. The reaction time is 2-30 h.
    The mixed halogenating agent is a combination of the halogen and halogen compound, which are selected from for example iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, ethoxy magnesium iodide, methoxy magnesium iodide, isopropoxy magnesium iodide, hydrogen chloride, chloroacetyl chloride, etc. The mixed halogenating agent is preferably a combination of iodine and magnesium chloride. The weight ratio of iodine to magnesium chloride is preferably 1:0.02 to 1:20, more preferably 1:0.02 to 1:10, more preferably 1: 0.05-1: 20, most preferably 1:0.1 to 1:10 .
    The inert atmosphere includes nitrogen gas atmosphere, argon gas atmosphere, preferably nitrogen gas atmosphere.
    The titanium-containing solid catalyst component according to the present invention can be prepared by a method comprising the following step: reacting the alkoxy magnesium with the internal electron donor compound and the titanium compound in the presence of inert diluent; washing the solid obtained in the reaction with inert diluent to yield the catalyst solid component. In this method, the amount of the used titanium compound, expressed in molar ratio to magnesium in the alkoxy magnesium compound, is (0.5-100):1, preferably (1-50):1, and the amount of the used electron donor compound, expressed in molar ratio to magnesium in the alkoxy magnesium compound, is (0.005-10) :1, preferably (0.01-1):1. The amount of the inert diluent, expressed in molar ratio to magnesium in the alkoxy magnesium compound, is (0.5-100):1, preferably (1-50):1. The reaction temperature is from -40° to 200°C, more preferably -20°C to 150°C, and the reaction time is from 1 min to 20 h, more preferably 5 min to 8 h. The inert diluent can be at least one selected from C6-C10 alkane or arene, preferably at least one of hexane, heptane, octane, decane, benzene, toluene, xylene or derivatives thereof, more preferably toluene.
    In the preparation of the catalyst solid component according to the present invention, the order of adding the alkoxy magnesium support, the internal electron donor compound, the inert diluent and the titanium compound is not specifically limited. For example, these components can be mixed in the presence of the inert solvent, or they can be diluted with the inert diluent in advance and then mixed. It is not specifically limited either for how much times these components are mixed, and thus the mixing process can be performed for example once or several times.
    The component (2) of the catalyst of the present invention is alkyl aluminum compound of Formula (VI) , in which R10 is hydrogen or a hydrocarbonyl with 1-20 carbon atoms, X is halogen and n is a number of l^n^3. The compound of Formula (VI) can be selected from a group consisting of triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-octyl aluminum, diethyl aluminum monohydride, di-iso-butyl aluminum monohydride, diethyl aluminum monochloride, di-iso-butyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, preferably triethyl aluminum, tri-iso-butyl aluminum.
    AlR10nX3-n (VI)
    In the catalyst according to the present invention, the external electron donor component can be any of external electron donors known in the art, and thus is not specifically limited. It is preferably the organosilicon compound of Formula (VII), R1”m..R2'’n"Si(OR3”)4-m··- „· (VII) in which R1” and R2” are same or different, independently from each other denote one of halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl and C1-C20 halogenated alkyl; R3” is on each occurrence and independently from each other one of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl and C1-C20 halogenated alkyl; each of m” and n” is independengly an integer of 0-3, and m + n <4.
    The non-limiting examples of the organosilicon compound can be trimethylmethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, di(2-methylcyclopentyl)dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane etc. These organosilicon compounds can be used solely or in combination of two or more thereof. More preferably, the compounds as the external electron donor includes at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, methyltertbutyldimethoxysilane and tetraethoxysilane.
    In the catalyst of the present invention, the molar ratio of compound (2) to component (1), i.e., the molar ratio of the alkyl aluminum to the solid catalyst component, expressed in Al/Ti, is 20-500:1, preferably 25-100:1. The molar ratio of component (2) to component (3), expressed in Al/Si, is 1-200:1, preferably 3-100:1.
    In addition, the present invention further provides a propylene polymer as prepared by the method of the present invention. The elevation of the polymerization temperature in step (2) results in the propylene polymers with both high fluidity and high rigidity. Such propylene polymer articles with high fluidity and high rigidity have the following advantages: for example, as for the injection molding articles, the increase of fluidity can produce articles with more complicated structure; and due to the increased rigidity, the thickness of articles can be reduced so as to reduce the production cost. In the meantime, the polymerization method of the present invention uses a specific type of catalyst, which has a still relatively high polymerization activity when used at a higher polymerization temperature even after the pre-polymerization. Hence, the present invention is very promising in the industrial application.
    Examples
    The present invention is further illustrated in conjunction with the following examples, which are used for explanation rather than limiting the present invention.
    Measurement methods : 1. Titanium content in the catalyst was measured by using 721 spectrophotometer .
    2. Particle size and particle size distribution of the alkoxy magnesium and catalyst were measured by using Malvern Mastersizer TM 2000 laser diffraction method with n-hexane used as dispersing agent (in which, SPAN=(D90-D10)/D50).
    3. Measurement of 2-ethylhexyloxy magnesium in the support: IN hydrochloric acid solution was added to the obtained sample, stirred for 24 h for degradation, and the 2-ethylhexanol therein was quantified by gas chromatography and then calculation.
    4. Measurement of m value of the support: O.lg of support was taken up, added with 10ml of 1.2 mol/1 hydrochloric acid aqueous solution, then shaken for 24h for degradation. The ethanol and 2-ethylhexanol therein were quantified by gas chromatography and then m value was calculated by the following formula:
    wherein wl is the mass of 2-ethylhexanol, and w2 is the mass of ethanol.
    5. The content of internal electron donor in the olefin polymerization catalyst component was measured by using Waters 600E liquid chromatograph or gas chromatograph.
    6. Stereo regularity index (Isotacticity) was measured according to National Standard GB2412.
    7. Melt flow rate (MFR) was measured according to IS01133 under 230°C and 2.16kg of load.
    8. Tensile strength of resin was measured according to ASTM D638-00.
    9. Flexural Modulus of resin was measured according to ASTM D790-97.
    10. Izod impact strength was measured according to ASTM D256-00. Preparation Example 1
    In this preparation example, the catalyst solid component used in the method for preparing propylene copolymer of the present invention was prepared.
    In a 16L pressure-resistant reactor with a stirrer that was sufficiently purged with nitrogen gas, 10L of ethanol, 300 mL of 2-ethylhexanol, 11.2g of iodine, 8g of magnesium chloride and 640g of magnesium powder were added. Under stirring, the system was heated for refluxing until no more hydrogen gas was discharged. The reaction was terminated, and 3L of ethanol was used for washing. The dialkoxy magnesium support was obtained after filtration and drying. The dialkoxy magnesium support had D50=30.2 ym, Span value of 0.81, m value of 0.015.
    650 g of the dialkoxy magnesium support and 3250 mL of toluene were formulated to form a suspension. In a 16L pressure-resistant reactor that was repeatedly purged with high purity nitrogen gas, 2600 mL of toluene and 3900 mL of titanium tetrachloride were added and heated to 80°C. Then the formulated suspension was added to the reactor, kept at the temperature for 1 h. After adding 130 mL of diethyl phthalate, the temperature was slowly raised to 110°C and then kept for further 2 h. A solid was obtained by press-filtration. The obtained solid was added to a mixed liquid of 5070 mL of toluene and 3380 mL of titanium tetrachloride and then treated under stirring at 110°C for 1 h. Such a treatment was repeated for 3 times. After press-filtration, the obtained solid was washed with hexane for 4 times, 6000 mL per wash. The main catalyst solid component was finally obtained after press-filtration and drying. The obtained catalyst solid component had the content of the titanium atom of 2.4wt%, and had diethyl phthalate in an amount of 10.5%.
    Example 1
    This example is to illustrate the propylene copolymer and preparation method thereof as provided in the present invention.
    The experiment used the polymerization process comprising a continuous pre-polymerization kettle in gaseous connection in series with two horizontal kettles. The pre-polymerization kettle had a volume of 5L and was a vertical agitation kettle with jacket cooling device. The stirring paddle was turbine type inclined paddle, and the stirring speed was 500 rpm. The two horizontal gas phase reaction kettle that were of the same structure had a volume of 0.2 m3 and was a horizontal agitation kettle with the stirring paddle being T type inclined paddle and having an inclination angle of 10°. The stirring speed was 100 rpm. The gas phase homopolymerization of propylene in step (2) and the gas phase copolymerization of propylene and ethylene in step (3) were carried out respectively in two horizontal gas phase reaction kettle.
    Pre-polymerization of step (1): react ion pressure was 2.5 MPa, reaction temperature was 10°C, reaction time was 12 minutes. The solid component as prepared in Preparation Example 1 was fed in a rate of 0.9g/h, triethyl aluminum was fed in a rate of 0.072 mol/h, a mixture of dicyclopentyldimethoxysilane and tetraethoxysilane (1:4 mol/mol) was fed in a rate of 0.012 mol/h. Al/Si (mol/mol) = 6.0; and the propylene was fed in a rate of 10 kg/h. The pre-polymerization multiplication is about 80.
    Gas phase homopolymerization of propylene in step (2): reaction temperature was 95°C, reaction pressure was 2.3 MPa and reaction time was 60 minutes. The propylene was fed in a rate of 30 kg/h, the hydrogen gas was fed in a rate of 1.1 g/h, and the molar ratio of hydrogen gas/propylene in the reaction gas phase was 0.02.
    Gas phase copolymerization of propylene and ethylene in step (3): reaction temperature was 66°C, reaction pressure was 2.3 MPa, and reaction time was 40min. The ethylene was fed in a rate of 7 kg/h, the propylene was fed in a rate of 30 kg/h and the hydrogen gas was fed in a rate of 0.5 g/h. The molar ratio of hydrogen gas/propylene in the reaction gas phase was 0.01 and the molar ratio of ethylene/propylene in the gas phase of the reaction system was 0.35.
    The experiment was continuously performed for 48 h under the conditions of Example 1, and the operation of device was stable. In the continuous experimental process, polymers in certain amounts were taken out from the reaction kettles of stages (2) and (3) and analyzed. The results were shown in Table 1.
    Example 2
    This example is to illustrate the propylene copolymer and preparation method thereof as provided in the present invention.
    The experiment used the polymerization process comprising a continuous pre-polymerization kettle in gaseous connection in series with two horizontal kettles. The pre-polymerization kettle had a volume of 5L and was a vertical agitation kettle with jacket cooling device. The stirring paddle was turbine type inclined paddle, and the stirring speed was 500 rpm. The horizontal gas phase reaction kettle had a volume of 0.2 m3 and was a horizontal agitation kettle with the stirring paddle being T type inclined paddle and having an inclination angle of 10°. The stirring speed was 100 rpm.
    Pre-polymerization of step (1) : reaction pressure was 2.5 MPa, reaction temperature was 10°C and reaction time was 12 minutes. The solid component as prepared in Preparation Example 1, triethyl aluminum, diisobutyldimethoxysilane (DIBDMS) were fed in a rate of l.lg/h, 0.088 mol/h and 0.015 mol/h, respectively; Al/Si (mol/mol) = 6.1. The propylene was fed in a rate of 10 kg/h.
    Gas phase homopolymerization of propylene in step (2): reaction temperature was 95°C, reaction pressure was 2.3 MPa and reaction time was 60 minutes. The propylene was fed in a rate of 30 kg/h, the hydrogen gas was fed in a rate of 1.7 g/h, and the molar ratio of hydrogen gas/propylene was 0.03.
    Gas phase copolymerization of propylene and ethylene in step (3): reaction temperature was 66 °C, reaction pressure was 2.3MPa, and reaction time was 40min. The ethylene was fed in a rate of 7 kg/h, the propylene was fed in a rate of 30 kg/h and the hydrogen gas was fed in a rate of 0.5 g/h. The molar ratio of hydrogen gas/propylene in the reaction gas phase was 0.01, and the molar ratio of ethylene/propylene in the gas phase of the reaction system was 0.35.
    The experiment was continuously performed for 48 h, and the operation of device was stable. In the continuous experimental process, polymers in certain amounts were taken out from reaction kettles of stages (2) and (3) and analyzed. The results were shown in Table 1.
    Comparison Example 1
    Example 2 was substantively repeated with the exception that the operation conditions for gas phase polymerization in step (2) were: reaction temperature was 66°C, reaction pressure was 2.3MPa and reaction time was 60min. The propylene was fed in a rate of 30kg/h, the hydrogen gas was fed in a rate of 1.7g/h and the molar ratio of hydrogen gas/propylene in the gas phase was 0.03.
    The experiment was continuously performed for 48 h, and the operation of device was stable. In the continuous experimental process, polymers in certain amounts were taken out from reaction kettles of stages (2) and (3) and analyzed. The results were shown in Table 1.
    Table 1: Properties of polymer samples
    K7726* was an impact resistant copolymer product K7726 that was commercially available product from Yanshan Petrochemical Company. This product was obtained by peroxide degradation to increase melt index of the product, and an amount of nucleating agent was added to improve the rigidity of product.
    By comparing Example 1 with K7726*, it can be seen that the present invention could lead to a high melt index product without using the peroxide and nucleating agent, and the obtained propylene copolymer has the rigidity and toughness comparable to the level of products containing the nucleating agent in the market. By comparing Example 2 with Comparison Example 1, it can be seen that the difference between them lies in the reaction temperature of stage (2), i.e. the temperature of Example 2 was 95°C, while the polymerization temperature of Comparison Example 1 was 66°C as conventionally used. Example 2 could lead to an impact resistant propylene copolymer with melt index of 50 g/min, while Comparison Example 1 could merely lead to an impact resistant propylene copolymer with melt index of 14 g/min.
    Therefore, the method of the present invention could yield a propylene copolymer product with high melt flow index, improved rigidity and impact resistance.
    Example 3: 1) Raw materials
    Diisobutyldimethoxysilane was used as external electron donor, and other conditions were the same as Example 1.
    2) Experimental equipment
    Identical to Example 1 3) Experimental conditions
    Pre-polymerization of step (1) : reaction pressure was 2.5 MPa, reaction temperature was 10°C and reaction time was 12 minutes. The catalyst, triethyl aluminum, diisobutyldimethoxysilane (DIBDMS) were fed in a rate of 0.6g/h, 0.048 mol/h (8ml/h) and 0.0078 mol/h (2.7ml/h), respectively; Al/Si (mol/mol) = 6.11. The propylene was fed in a rate of 10 kg/h.
    Gas phase homopolymerization of propylene in step (2): reaction temperature was 95°C, reaction pressure was 2.3 MPa and reaction time was 60 minutes. The propylene was fed in a rate of 30 kg/h, the hydrogen gas was fed in a rate of 1.6 g/h and the molar ratio of hydrogen gas/propylene in the reaction gas phase was 0.03.
    Gas phase copolymerization of propylene and ethylene in step (3): reaction temperature was 66°C, reaction pressure was 2.3 MPa and reaction time was 40 min. The ethylene was fed in a rate of 7 kg/h, the propylene was fed in a rate of 30 kg/h and the hydrogen gas was fed in a rate of 0.5 g/h. The molar ratio of hydrogen gas/propylene in the gas phase was 0.01 and the molar ratio of ethylene/propylene in the gas phase was 0.35.
    4) Experimental results
    The experiment was continuously performed for 48 h according to the above conditions, and the operation of equipment was stable. The polymer obtained by reactions was analyzed and the results were shown in Table 2.
    Comparison Example 2: 1) Raw materials
    Except that tetraethoxysilane was used as an external electron donor, other conditions were the same as Example 1.
    It should be pointed out that the obtained polymer should have comparable melt flow rate so as to compare with the polymer of Example 3 in mechanical properties. If Comparison Example 2 used the same external electron donor (diisobutyldimethoxysilane) as Example 3, it could be impossible to obtain a polymer with a melt flow rate comparable to that of Example 3, that is to say that a melt flow rate could not reach 55 (merely about 7 as can be seen in Comparison Example 3), in case that the reaction temperature in step (2) is 66°C. Under such circumstances, tetraethoxysilane, an external electron donor more sensitive to hydrogen regulation, was used.
    2) Experimental equipment
    Identical to Example 3 3) Experimental conditions
    Pre-polymerization of step {1) : reaction pressure was 2.5 MPa, reaction temperature was 10°C and reaction time was 12 minutes. The catalyst, triethyl aluminum, tetraethoxysilane were fed in a rate of 0.5g/h, 0.048 mo1/h (8ml/h) and 0.0078 mo1/h (2.7ml/h), respectively; Al/Si (mol/mol) = 6.11. The propylene was fed in a rate of 10 kg/h.
    Gas phase homopolymerization of propylene in step (2) : except that the reaction temperature was 66°C, hydrogen gas was fed in a rate of 0.8 g/h and the molar ratio of hydrogen gas/propylene in the reaction gas phase was 0.015, other conditions were the same as that in Example 3.
    Gas phase copolymerization of propylene and ethylene in step (3) : the reaction conditions and operation were the same as that in Example 3.
    4) Experimental results
    The experiment was continuously performed for 48 h according to the above conditions, and the operation of equipment was stable. The polymer obtained by reactions was analyzed and the results were shown in Table 2.
    Comparison Example 3:
    Except that the polymerization temperature of the gas phase propylene homopolymerization in step (2) was 66°C, other conditions were the same as that in Example 3 . The polymer obtained by reactions was analyzed and the results were shown in Table 2.
    Comparison Example 4: 1) Raw materials
    The used main catalyst was prepared according to Example 1 of Chinese Patent CN85100997, while other conditions were the same as that in Example 3.
    2) Experimental equipment
    Identical to Example 3 3) Experimental conditions
    Identical to Example 3 4) Experimental results
    The experiment was continuously performed for 48 h according to the above conditions, and the operation of equipment was stable. The polymer obtained by reactions was analyzed and the results were shown in Table 2.
    Table 2: Analysis results of polymers obtained in Example 2 and Comparison Example 2
    The data of Table 2 show that: (1) Comparison of Example 3 and Comparison Example 3: with the same solid catalyst, the propylene polymer with high melt flow rate of the present invention could not be obtained if the temperature of step (2) is relatively low. Under the same conditions, the polymer obtained in Example 3 had a melt flow rate of 55, while that of Comparison Example 3 merely had a melt flow rate of 7.6.
    (2) Comparison of Example 3 and Comparison Example 2: when the temperature of step (2) was relatively low, although a specific external electron donor in catalyst was used in Comparison Example 2 so as to obtain a propylene polymer with the melt flow rate comparable to that of Example 3, the polymer of Example 3 had the mechanical properties such as rigidity and toughness that were far superior to Comparison Example 2, and the polymerization activity was also much higher than Comparison Example 2.
    (3) Comparison of Example 3 and Comparison Example 4: with a conventional catalyst in the art, the activity usually decreased to a very low level of only 5000 multiplication if the polymerization temperature of step (2) was relatively high. However, in the present invention, after the high-temperature polymerization in step (2), the copolymerization in step (3) was still of a relatively high polymerization activity.
    The above data comparison shows that the elevation of polymerization temperature in step (2) can lead to a propylene polymer with both high fluidity and high rigidity. In particular, the catalyst composition of the present invention had a relatively high activity and thus is promising for the industrial applications.
    CLAUSES
    1. A method for polymerization of propylene, comprising the following steps: (1) performing pre-polymerization of propylene or an olefin mixture containing propylene and other a-olefin comonomer(s) in a gas phase or a liquid phase in the presence of a Ziegler-Natta catalyst at -10°C to 50°C and 0.1-10.0 MPa to obtain a propylene prepolymer, wherein the pre-polymerization multiplication is controlled in the scope of 2-3000 g polymer/g catalyst, preferably 3-2000 g polymer/g catalyst; (2) performing a homopolymerization of propylene or copolymerization of propylene and other a-olefin comonomer(s) in a gas phase in the presence of the propylene prepolymer as obtained in step (1) under conditions of 91-150°C, preferably 91-130°C and more preferably 91-110°C and 1-6 MPa to obtain a propylene polymer, wherein the polymerization time is 0.5-4 h; (3) continuing the homopolymerization or copolymerization of propylene in a gas phase or a liquid phase in the presence of the product as obtained in step (2) under conditions of 50-150°C and 1-6 MPa.
    2. The method for polymerization of propylene according to claim 1, characterized in that the individual steps can be performed in one reactor for the batch polymerization operation, or performed in different reactors for continuation polymerization operation.
    3. The method for polymerization of propylene according to any of the previous claims, characterized in that in step (1), the pre-polymerization temperature is 0-30°C, preferably 10-25°C, and the pre-polymerization pressure is 1.0-6.0 MPa, preferably 1.5-5.5 MPa.
    4. The method for polymerization of propylene according to any of the previous claims, characterized in that the said other α-olefin comonomer(s) is/are at least one α-olefin having the carbon atoms number of 2 to 6 but not 3.
    5. The method for polymerization of propylene according to any of the previous claims, characterized in that the gas phase polymerization of propylene in step (2) is performed in a horizontal reaction kettle having a horizontal agitating shaft and a stirring speed of 10-150 rpm, in which the agitating blade is selected from T-shape, rectangle shape, inclined paddle, door shape, wedge-shape and any combination thereof, and the reaction kettle uses a quench liquid to remove heat.
    6. The method for polymerization of propylene according to any of the previous claims, characterized in that the polymer obtained in step (2) has a melt flow rate MFR of 20-1000 g/lOmin, as measured according to IS01133 under 230°C and 2.16kg load.
    7. The method for polymerization of propylene according to any of the previous claims, characterized in that the gas phase homopolymerization or copolymerization of propylene in step (3) is performed at the polymerization temperature of 55-110°C, and the polymer obtained in step (3) has a melt flow rate MFR of l-500g/10min, as measured according to IS01133 under 230°C and 2.16kg load.
    8. The method for polymerization of propylene according to any of the previous claims, characterized in that a liquid phase bulk pre-polymerization of propylene is performed at 0-30°C in step (1) ; a gas phase homopolymerization of propylene is performed at 91-110°C in step (2); and the gas phase homopolymerization or copolymerization of propylene is continued in the presence of the product as obtained in step (2) at 55-110°C in step (3), wherein the weight ratio of the reacted polymers in steps (2) and (3) is 0.3-3, preferably 1.0-2.0.
    9. The method for polymerization of propylene according to any of the previous claims, characterized in that a homopolymerization of propylene is performed in steps (1) and (2), while a copolymerization of propylene and other a-olefin comonomer(s) is performed in step (3).
    10. The method for polymerization of propylene according to any of the previous claims, characterized in that the said other α-olefin comonomer (s) is/are one or more selected from ethylene, butylene and hexylene, preferably ethylene.
    11. The method for polymerization of propylene according to any of the previous claims, characterized in that in step (3) the copolymerization is performed using ethylene in an amount of 4-40 wt%, preferably 6-30 wt% relative to the weight of propylene homopolymer as obtained in step (2).
    12. The method for polymerization of propylene according to any of the previous claims, characterized in that the Ziegler-Natta catalyst comprises a reaction product of the following components: (1) a titanium-containing solid catalyst component; (2) an alkyl aluminum compound; and (3) optionally, an external electron donor component.
    13. The method for polymerization of propylene according to any of the previous claims, characterized in that the titanium-containing solid catalyst component of the component (1) is a reaction product of contacting an alkoxy magnesium compound, a titanium compound and an internal electron donor compound, wherein the titanium compound is at least one compound of Formula: Ti (OR) 4-nXn, in which R is selected from C1-C14 aliphatic or aromatic hydrocarbonyl group, X is a halogen atom, n is an integer from 0 to 4 and in case of n being equal to or less than 2, the existing R groups can be same or different; the internal electron donor compound is one or more selected from alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones, preferably selected from alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-Cs aromatic carboxylic acids, C2-C6 aliphatic esters, C3-C4 cyclic ethers, C3-C6 saturated aliphatic ketones and 1,3-diether compounds.
    14. The method for polymerization of propylene according to any of the previous claims, characterized in that the alkoxy magnesium compound is at least one selected from the compounds of Formula Mg (OR1) 2-m (OR2) m, wherein R1 and R2 are same or different and independently selected from straight or branched alkyl having 1-8, preferably 3-8 carbon atoms, and 0^m^2.
    15. The method for polymerization of propylene according to any of the previous claims, characterized in that R1 is ethyl, R2 is (2-ethyl)hexyl, and 0.001^m^0.5, preferably 0.OOl^m^O.25, more preferably O.OOl^m^O.l.
    16. The propylene polymers obtained by the method for polymerization of propylene according to any of the previous claims .
    权利要求:
    Claims (16)
    [1]
    A method for the polymerization of propylene comprising the following steps: 1. performing a prepolymerization of propylene or an olefin mixture comprising propylene and other alpha-olefin comonomers in a gas phase, or a liquid phase, in the presence of a Ziegler -Natta catalyst at -10 ° C to 50 ° C and 0.1-10.0 MPa to obtain a propylene prepolymer, the prepolymerization multiplication being controlled in the range of 2-3000 g of polymer / g of catalyst , preferably 3-2000 g of polymer / g of catalyst; 2. carrying out a homopolymerization of propylene or a copolymerization of propylene and other α-olefin comonomers in a gas phase in the presence of the prepolymer obtained in step (1) under the conditions of 91-150 ° C, preferably 91- 130 ° C and more preferably 91-110 ° C and 1-6 MPa for obtaining a propylene polymer, the polymerization time being 0.5-4 hours; 3. continuing the homopolymerization or the copolymerization of propylene in a gas phase or a liquid phase in the presence of a product as obtained in step (2) under the conditions of 50-150 ° C and 1-6 MPa.
    [2]
    Process for the polymerization of propylene according to claim 1, characterized in that the individual steps can be carried out in one reactor for a batch polymerization operation or they can be carried out in different reactors for a continuous polymerization operation.
    [3]
    Method for the polymerization of propylene according to one of the preceding claims, characterized in that in step (1) the prepolymerization temperature is 0-30 ° C, preferably 10-25 ° C, and the prepolymerization pressure 1.0-6, Is 0 MPa, preferably 1.5-5.5 MPa.
    [4]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that said other α-olefin is comonomer / comonomers or is at least one α-olefin with 2 to 6 carbon atoms but not 3 carbon atoms.
    [5]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the gas-phase polymerization of propylene in step (2) is carried out in a horizontal reaction vessel with a horizontal stirring shaft and a stirring speed of 10-150 rpm with the stirring blade is selected from a T-shape, a rectangular shape, an angled blade, a door shape, a triangle shape and any combination thereof, and the reaction boiler uses a quench liquid to remove the heat.
    [6]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the polymer obtained in step (2) has a melt flow rate MFR of 20-1000g / 10 minutes as measured according to IS01133 at 230 ° C and 2 , 16 kilograms load.
    [7]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the gas phase homopolymerization or copolymerization of propylene in step (3) is carried out at a polymerization temperature of 55-110 ° C, and the polymer obtained in step (3) has a melt flow rate MFR of 1 - 500 g / 10 minutes as measured according to IS01133 at 230 ° C and 2.16 kilograms of loading.
    [8]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that a liquid phase bulk prepolymerization of propylene is carried out at 0-30 ° C in step (1); a gas phase homopolymerization of propylene is carried out at 91-110 ° C in step (2); and a gas phase homopolymerization or copolymerization of propylene is continued in the present of the product as obtained in step (2) at 55-110 ° C in step (3), the weight ratio of the reacted polymers in steps (2) and (3) is 0.3-3, preferably 1.0-2.0.
    [9]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that a homopolymerization or copolymerization in steps (1) and (2) is carried out and a copolymerization of propylene and other α-olefin comonomer / monomers is carried out in step (3).
    [10]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that said other α-olefin comonomer / comonomers are one or are selected from ethylene, butylene and hexylene, preferably ethylene.
    [11]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that in step (3) the copolymerization is carried out by using ethylene in an amount of 4-40% by weight, preferably 6-30% by weight relative to the weight of the propylene homopolymer obtained in step (2).
    [12]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the Ziegler-Natta catalyst comprises a reaction product of the following components: (1) a titanium-containing solid catalyst component; (2) an alkyl aluminum compound; and (3) optionally an external electron donor component.
    [13]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the titanium-containing solid catalyst component of the component (1) is a reaction product of an alkoxy magnesium compound, a titanium compound and an internal electron donor compound, wherein the titanium compound is at least one compound of the formula: Ti (OR) 4-n X n where R is selected from a C 1 -C 14 aliphatic or aromatic hydrocarbonyl group, X is a halogen atom, n is an integer from 0 to 4 and in the case that n is equal to or less than 2, the existing R groups may be the same or different; the internal electron donor compound there is one or more selected from the group of alkyl esters or aliphatic and aromatic monocarboxylic acids, alkyl esters or aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones, preferably selected from alkyl esters of C1- C 4 saturated aliphatic carboxylic acids, alkyl esters of C 7 -C 8 aromatic carboxylic acids, C 2 -C 6 aliphatic esters, C 3 -C 4 cyclic ethers, C 3 -C 6 saturated aliphatic ketones and 1,3-diether compounds.
    [14]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that the alkoxy magnesium compound is at least one selected from the compounds of the formula Mg (OR1) 2-m (OR2) m where R1 and R2 be the same or different and independently selected from a straight or branched chain alkyl of 1-8, preferably 3-8 carbon atoms and 0 ^ m <2.
    [15]
    Process for the polymerization of propylene according to one of the preceding claims, characterized in that R 1 is ethyl, R 2 is (2-ethyl) hexyl, and 0.001 <m <0.5, preferably 0.001 ^ m ^ 0, 25 and more preferably, 0.001 .mu.m. 0.1.
    [16]
    Propylene polymers obtainable by a propylene polymerization process according to any of the preceding claims.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR102263502B1|2021-06-11|Catalyst system for polymerization of an olefin
    EP3083718B1|2019-05-01|Procatalyst for polymerization of olefins
    KR102329438B1|2021-11-23|Procatalyst for polymerization of olefins comprising a monoester and an amidobenzoate internal donor
    US10640586B2|2020-05-05|Catalyst system for polymerization of an olefin
    KR101653422B1|2016-09-01|Internal donor for olefin polymerization catalysts
    EP3083717B1|2019-08-28|Catalyst system for polymerization of an olefin
    JP2016510835A|2016-04-11|1-mixed internal donor structure for olefin polymerization catalyst
    NL2011694C2|2015-04-01|Method for preparation of propylene polymer.
    US8889898B2|2014-11-18|Process for preparing di-substituted succinates
    CN107810206B|2021-01-19|Procatalyst for olefin polymerization comprising aminobenzoate internal donor and 1, 3-diether internal donor in specific ratios
    BE1021588B1|2015-12-16|PROCESS FOR THE PREPARATION OF PROPYLENE POLYMER
    CN108148153B|2021-08-10|Solid catalyst and method for preparing propylene polymer or copolymer using the same
    EP3083724B1|2018-07-25|Catalyst system for polymerization of an olefin
    CN110234663B|2022-03-08|Process for producing polyolefin
    KR101624036B1|2016-05-25|A solid catalyst for propylene polymerization and a method for preparation of polypropylene using the catalyst
    同族专利:
    公开号 | 公开日
    TW201428007A|2014-07-16|
    JP2014114435A|2014-06-26|
    DE102013221849B4|2021-07-29|
    ZA201308121B|2015-03-25|
    NL2011694C2|2015-04-01|
    US9751965B2|2017-09-05|
    TWI529178B|2016-04-11|
    ITMI20131798A1|2014-05-01|
    KR20140056093A|2014-05-09|
    KR101742714B1|2017-06-01|
    BR102013027915A2|2014-10-21|
    DE102013221849A1|2014-04-30|
    BR102013027915B1|2020-04-14|
    US20140121337A1|2014-05-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA1053846A|1974-12-16|1979-05-01|The Standard Oil Company|Horizontal reactor for the vapor phase polymerization of monomers|
    US4308357A|1980-10-20|1981-12-29|El Paso Polyolefins Company|Block copolymerization process and product|
    CN1006071B|1985-04-01|1989-12-13|中国石油化工总公司|Catalyst system used for alkene poly-and copolymerization|
    IT1246614B|1991-06-03|1994-11-24|Himont Inc|PROCEDURE FOR THE GAS PHASE POLYMERIZATION OF OLEFINS|
    TW303368B|1992-08-08|1997-04-21|Hoechst Ag|
    JPH07247311A|1994-03-09|1995-09-26|Asahi Chem Ind Co Ltd|Production of propylene block copolymer|
    US6303709B1|1997-06-05|2001-10-16|Solvay Polyolefins Europe-Belgium |Continuous process for obtaining propylene polymers|
    US6350054B1|1997-12-08|2002-02-26|Bp Corporation North America Inc.|Agitator for a horizontal polymerization reactor having contiguous paddle stations with paddles and sub-stations with sub-station paddles|
    JP2001114848A|1999-10-19|2001-04-24|Idemitsu Petrochem Co Ltd|Method of producing propylene-based block copolymer and propylene-based block copolymer|
    JP5058400B2|1999-10-19|2012-10-24|出光興産株式会社|Propylene-based block copolymer production method and propylene-based block copolymer|
    CN1171916C|2001-11-28|2004-10-20|中国石油化工股份有限公司|Propylene polymerizing or copolymerizing process|
    JP2003268060A|2002-03-19|2003-09-25|Idemitsu Petrochem Co Ltd|Propylene block copolymer, method for producing the same and molded product thereof|
    ES2399823T3|2004-09-02|2013-04-03|Borealis Technology Oy|A polymer pipe without pressure, a composition for it, and a process for its preparation|
    CN100457790C|2005-09-29|2009-02-04|中国石油化工股份有限公司|Propylene polymerization or copolymerization and its multipolymer|
    JP2009545659A|2006-08-04|2009-12-24|バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ|Gas phase process for producing heterophasic propylene copolymers|
    JP5028081B2|2006-12-15|2012-09-19|日本ポリプロ株式会社|Method for continuous gas phase production of propylene-based block copolymer|
    CN101270172B|2007-03-20|2012-12-12|中国石化扬子石油化工有限公司|High flow polypropylene polyalcohol catalyst system and application|
    RU2487897C2|2008-08-21|2013-07-20|ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи|High melt flow rate, impact-resistant propylene copolymer and method for production thereof|
    ES2363653T3|2008-07-16|2011-08-11|Borealis Ag|HIGH-RIGID HETEROPHASE POLYMERIC COMPOSITION.|
    ES2804259T3|2010-09-16|2021-02-05|China Petroleum & Chem Corp|Catalyst support for olefin polymerization, solid catalyst component and catalyst|KR101836008B1|2016-12-05|2018-03-07|한화토탈 주식회사|Process of manufacture of catalyst and propylene polymer that use this or copolymer for propylene polymerization|
    WO2021058607A1|2019-09-24|2021-04-01|Sabic Global Technologies B.V.|Polymerization process for olefins|
    CN112745442A|2019-10-30|2021-05-04|中国石油化工股份有限公司|Polypropylene copolymer powder and preparation method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CN201210425478.XA|CN103788274B|2012-10-30|2012-10-30|Propylene copolymer and preparation method thereof|
    CN201210425055|2012-10-30|
    CN201210425055.8A|CN103788258B|2012-10-30|2012-10-30|A kind of polymerization of propylene|
    CN201210425478|2012-10-30|
    [返回顶部]