CN116023545A - Catalyst for olefin polymerization, catalyst system, application and olefin polymerization method - Google Patents

Catalyst for olefin polymerization, catalyst system, application and olefin polymerization method Download PDF

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CN116023545A
CN116023545A CN202111256536.6A CN202111256536A CN116023545A CN 116023545 A CN116023545 A CN 116023545A CN 202111256536 A CN202111256536 A CN 202111256536A CN 116023545 A CN116023545 A CN 116023545A
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dimethoxypropane
catalyst
olefin polymerization
compound
methyl
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CN116023545B (en
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凌永泰
李威莅
周俊领
刘月祥
夏先知
冯再兴
陈龙
谢伦嘉
任春红
赵瑾
谭扬
高富堂
刘涛
谢吉嘉
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a catalyst for olefin polymerization, a catalyst system, application and an olefin polymerization method. The catalyst with novel composition can be obtained by taking the compound I as a carrier and the compound II and the compound III as internal electron donors, and has good particle morphology, particle size of less than 30 microns and narrow particle size distribution. The catalyst is used for realizing the function of self-regulating the molecular weight distribution of polypropylene by using a III compound when propylene is polymerized, and can reduce the falling time of polymers produced by the catalyst, particularly polypropylene particles. The catalyst for olefin polymerization has the advantages of small particle size, high activity, adjustable polymer molecular weight distribution width, good copolymerization performance and great industrial application prospect.

Description

Catalyst for olefin polymerization, catalyst system, application and olefin polymerization method
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for olefin polymerization, a catalyst system, application and an olefin polymerization method.
Background
In recent years, the polypropylene industry has been rapidly developed and competition has been increased, so that the need for polypropylene resins having special properties has been a goal of many manufacturers. The molecular weight distribution can influence the performance of the polypropylene resin, and the polypropylene resin with wide molecular weight distribution generally has better processability and mechanical property, and realizes better rigidity and toughness balance. Polypropylene for certain products, such as fibers, is required to have a relatively narrow molecular weight distribution width. Macroscopic parameters such as fall time of the polymer are an important aspect affecting the stability of the production, and if the values are large they tend to cause poor transport in the polymer reactor or in the pipes, affecting the balanced production of the polymer and even causing unplanned shut-down.
Meanwhile, polypropylene manufacturers are also striving to use catalysts with better process performance to achieve stable production over long periods. In general, small particle size supports not only reduce the fines of the prepared catalyst resulting in polymers but also are widely used in various gas phase polymerization processes.
Because of the poor impact resistance of homo-polypropylene, it is generally desirable to improve the properties of the product by copolymerizing ethylene and propylene. Different catalysts have different ethylene and propylene copolymerization capacities, and catalysts with better copolymerization capacities are often more popular in the market.
Therefore, it is important to find a new olefin polymerization catalyst which is suitable for process requirements and can realize the self-regulation of molecular weight distribution and has better copolymerization capability.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention proposes a catalyst component for olefin polymerization, and a catalyst and its use and a process for olefin polymerization.
In a first aspect, the present invention provides a catalyst component for the polymerization of olefins comprising component a, component B and component C;
the component A is a carrier, in particular to a sulfur-containing compound of magnesium, the structure of the component A is shown as a formula (I),
Figure BDA0003324268050000021
in the formula (I), R 1 Is C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl of (c);
R 2 and R is 3 Identical or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl of (a);
x is halogen;
m is 0.1-1.9, n is 0.1-1.9, m+n=2, 0< q is less than or equal to 0.5;
preferably, for R 1 、R 2 And R is 3 One or more hydrogens on the alkyl group may each independently be substituted with a halogen atom;
preferably, X is chloro or bromo;
preferably, m is 0.8-1.2, n is 0.8-1.2,0.005.ltoreq.q.ltoreq.0.2.
The component B is an internal electron donor compound, in particular to alpha cyano succinate and substituted alpha cyano succinate, the structure of which is shown as a formula (II),
Figure BDA0003324268050000022
in the formula (II), R ', is' 1 ～R”' 2 Identical or different, each independently H, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl or C 7 -C 10 An aralkyl group;
R”' 3 ～R”' 4 identical or different, each independently C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl or C 7 -C 10 An aralkyl group;
preferably, R'. 1 And R'' 2 Can be bonded to each other to form one or more fused ring structures;
preferably, R'. 3 And R'. 4 Identical or different, each independently C 1 ～C 10 Straight-chain or branched alkyl, C 3 ～C 10 Cycloalkyl, C 6 ～C 20 Aryl, C 7 ～C 20 Alkylaryl or C 7 ～C 20 An aromatic hydrocarbon group;
preferably, the hydrogen on the benzene ring in the aryl or alkylaryl or aryl hydrocarbon group may be optionally substituted with other atoms.
The component C is an internal electron donor compound, and is specifically a 1, 3-diether compound; the structure is shown as a formula (III):
Figure BDA0003324268050000031
wherein R is 21 And R is 22 Each independently selected from hydrogen, C 1 -C 20 Straight-chain or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl group R of (2) 21 And R is 22 Optionally bonded to form a ring; r is R 23 And R is 24 Each independently selected from C 1 -C 10 Straight or branched alkyl groups of (a).
As a specific embodiment of the present invention, the 1, 3-diether compound is selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
Preferably, the diether compound is 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
As a specific embodiment of the invention, the catalyst further comprises titanium element and chlorine element; the titanium element and the chlorine element are from titanium tetrachloride.
As a specific embodiment of the invention, the synthetic raw materials of the component A comprise elemental sulfur and MgX in the general formula 1 Y is a magnesium halide of the formula R 1 OH compounds and oxirane compounds.
As a specific embodiment of the present invention, the general formula MgX 1 Y, X 1 Is halogen, Y is halogen, C 1 -C 5 Is an alkane of (2)Radical, C 1 -C 5 Alkoxy, C 6 -C 10 Aryl, C of (2) 6 -C 10 An aryloxy group of (a); and/or
The general formula R 1 In OH, R 1 Is C 1 -C 8 Alkyl, C of (2) 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl of (c); preferably, R 1 The hydrogen on the alkyl group may each independently be substituted with a halogen atom; and/or
The structure of the ethylene oxide compound is shown as a formula (IV):
Figure BDA0003324268050000041
in the formula (IV), R 2 And R is 3 Identical or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl of (a);
preferably, R 2 And R is 3 One or more hydrogens on the alkyl group may each independently be substituted with a halogen atom.
As a specific embodiment of the invention, the mass ratio of the active metallic titanium element to the magnesium element in the carrier to the internal electron donor (component B+component C) is 1 (5-15), 2-15, preferably 1 (6-13) and 3-12.
As a specific embodiment of the present invention, the preparation method of the sulfur-containing magnesium compound of the component a comprises the steps of:
s1: elemental sulfur with the general formula MgX 1 Y is a magnesium halide of the formula R 1 Mixing and heating OH compound, inert liquid medium and surfactant to obtain liquid mixture;
s2: and (3) carrying out contact reaction on the liquid mixture obtained in the step (S1) and an ethylene oxide compound.
In the step S1, the inert liquid medium is at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil; preferably, white oil;
the dosage of the inert liquid medium is 1mol of MgX 1 The magnesium halide of Y is 0.8-10L, preferably 2-8L;
the surfactant is at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, polymer of oxyalkylacrylate copolymer modified polyethyleneimine, 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyl trimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkylmethacrylate; preferably, at least one of polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer and polyethylene glycol;
the dosage of the surfactant is 1mol of MgX 1 1-20g of magnesium halide of Y as a reference;
the heating temperature is 80-120 ℃, and the reaction time is 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the reaction time is 0.5-3 hours;
in the step S2, the temperature of the contact reaction is 40-120 ℃ and the reaction time is 15-60 minutes; preferably, the contact reaction temperature is 60-100℃and the reaction time is 20-50 minutes.
As a specific embodiment of the present invention, the above-mentioned production method may further comprise subjecting the product obtained by the contact reaction to solid-liquid separation, washing and drying the separated solid-phase product. The solid-liquid separation may be any of various existing methods capable of separating a solid phase from a liquid phase, such as suction filtration, pressure filtration or centrifugal separation, and preferably, the solid-liquid separation method is a pressure filtration method. The conditions for press filtration are not particularly limited in the present invention, so long as the separation of the solid phase and the liquid phase is achieved as sufficiently as possible. The washing may be performed by methods well known to those skilled in the art, and for example, the obtained solid phase product may be washed with an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline. The conditions for the drying are not particularly limited in the present invention, and examples thereof include: the drying temperature may be 20-70 ℃ and the drying time may be 0.5-10 hours. According to the present invention, the drying may be performed under normal pressure or reduced pressure.
As a specific embodiment of the present invention, the content of the above-mentioned components in the spherical support of the olefin polymerization catalyst may be selected and varied within a wide range, and preferably, the above-mentioned components are represented by the general formula MgX in an amount of 1mol 1 The usage amount of elemental sulfur is 0.0001-0.5mol based on the magnesium halide of Y, and the general formula is R 1 The dosage of the OH compound is 4-30mol, and the dosage of the ethylene oxide compound is 1-10mol; further preferably, the compound of formula (II) is MgX in an amount of 1mol 1 Y is based on magnesium halide and has a general formula of R 1 The amount of OH compound is 6-20mol, and the amount of oxirane compound is 2-6mol.
As a specific embodiment of the present invention, the elemental sulfur may be any subtype of elemental sulfur, including but not limited to: at least one of alpha-sulfur, beta-sulfur, gamma-sulfur, and polymeric sulfur. The elemental sulfur may be anhydrous elemental sulfur or elemental sulfur containing bound water. The elemental sulfur described above is commercially available.
As a specific embodiment of the present invention, a compound of the general formula MgX 1 Y, X 1 Preferably chlorine or bromine, Y preferably being chlorine, bromine, C 1 -C 5 Alkoxy or C of (2) 6 -C 10 An aryloxy group of (a). The C is 1 -C 5 The alkyl group of (C) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl, and the alkyl group of (C) 1 -C 5 The alkoxy group of (C) may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, the said C 6 -C 10 The aryl group of (C) may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl 6 -C 10 The aryloxy group of (a) may be, for example, phenoxy or naphthoxy. General formula (VI)Is MgX 1 The magnesium halide of Y may be one magnesium halide or a mixture of a plurality of magnesium halides. The general formula is MgX 1 Specific examples of the magnesium halide of Y may be, but are not limited to: at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxy magnesium chloride and n-butoxymagnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.
As a specific embodiment of the present invention, the general formula R 1 In OH, R 1 May be C 1 -C 8 Alkyl or C of (2) 3 -C 8 Cycloalkyl group of (C), wherein C 3 -C 8 The carbon atoms in the cycloalkyl radicals of (2) may be fully or partially involved in the ring formation, the said C 3 -C 8 The cycloalkyl group of (a) may be, for example, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl or cyclohexylmethyl. R is R 1 Preferably C 1 -C 8 Alkyl of (a); the C is 1 -C 8 The alkyl group of (a) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl. The general formula is R 1 Specific examples of the compound of OH may be, but are not limited to: at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexyl alcohol, and n-octanol.
As a specific embodiment of the present invention, R in the oxirane compound having the structure shown in the formula (II) 5 And R is 6 Preferably each independently is hydrogen, C 1 -C 3 Alkyl or C of (2) 1 -C 3 A haloalkyl group of (2); specific examples of the oxirane compound may be, but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, propylene oxide and butylene oxide.
The average particle size of the spherical support of the olefin polymerization catalyst of the present invention can be controlled within a wide range, for example, can be 10 to 100. Mu.m. According to a preferred embodiment of the present invention, the average particle diameter (D50) of the spherical support of the olefin polymerization catalyst can be controlled to 30 μm or less, preferably to 20 μm or less, and the particle size distribution ((D90-D10)/D50) is less than 1.2; the particle size distribution is preferably 0.8 or less. In the preferred embodiment, the catalyst prepared from the spherical support of the olefin polymerization catalyst is capable of obtaining an olefin polymer having a higher bulk density. In the present invention, the average particle diameter and particle size distribution of the spherical support of the olefin polymerization catalyst can be measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
As a specific embodiment of the present invention, the spherical support of the olefin polymerization catalyst may contain water derived from the synthesis feedstock and the trace amount of water carried by the reaction medium. According to the present invention, a trace amount of water in each of the above reactants may also participate in the reaction for forming the spherical support of the olefin polymerization catalyst.
As a specific embodiment of the present invention, in the above-mentioned compound of the general formula (II), preferred groups are: r ', R'. 1 ～R”' 2 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, benzyl, p-toluylmethyl or phenethyl; r ', R'. 3 ～R”' 4 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, p-tolyl, o-tolyl, m-tolyl or benzyl.
In the compounds of the above general formula (II), particularly preferred groups are: r ', R'. 1 ～R”' 2 Is isopropyl; r ', R'. 3 ～R”' 4 Is ethyl;
the compound shown in the general formula (II) can be: diethyl 2, 3-diisopropyl-2-cyano succinate, diethyl 3-methyl-2-isopropyl-2-cyano succinate, diethyl 3-ethyl-2-isopropyl-2-cyano succinate, diethyl 3-propyl-2-isopropyl-2-cyano succinate, diethyl 3-butyl-2-isopropyl-2-cyano succinate, diethyl 3-phenyl-2-isopropyl-2-cyano succinate and the like.
Particular preference is given to compounds of the formula (IV).
Figure BDA0003324268050000071
It should be noted that the compound represented by the general formula (II) is preferably a cyano succinate compound because the cyano succinate compound has the ability to construct various active centers, and the wide molecular weight distribution is caused by a large difference in the molecular chain length of the polymer produced by catalysis as a catalyst component, whereas the molecular weight distribution is narrowed due to a relatively small number of active center species that can be constructed by the dimethoxypropane compound, and thus the cyano succinate compound is preferable to effectively control the width of the molecular weight distribution width of the final polymer.
The above-mentioned raw materials in the present invention are all self-made or commercially available, and the present invention is not particularly limited thereto.
In a second aspect, the present invention provides a catalyst system for the polymerization of olefins, the catalyst system comprising:
(1) The catalyst;
(2) An alkyl aluminum compound; and
(3) Optionally an external electron donor compound.
The alkyl aluminum compound may be various alkyl aluminum compounds commonly used in the olefin polymerization field which can be used as cocatalysts for Ziegler-Natta catalysts.
Preferably, the alkyl aluminum compound may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride, but is not limited thereto.
The external electron donor compound may be various external electron donor compounds commonly used in the field of olefin polymerization, which can be used as cocatalysts of Ziegler-Natta catalysts.
The external electron donor compound may be, but is not limited to, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl (sec-butyl) dimethoxysilane, tert-butylpentyldimethoxysilane tertiary butyl nonyl dimethoxy silane, tertiary butyl hexyl dimethoxy silane, tertiary butyl heptyl dimethoxy silane, tertiary butyl octyl dimethoxy silane, tertiary butyl decyl dimethoxy silane, methyl tertiary butyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl propyl dimethoxy silane, cyclohexyl isobutyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl tertiary butyl dimethoxy silane, cyclopentyl methyl dimethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclopentyl propyl dimethoxy silane, cyclopentyl tertiary butyl dimethoxy silane, dicyclopentyl dimethoxy silane, cyclopentyl cyclohexyl dimethoxy silane, bis (2-methylcyclopentyl) dimethoxy silane, diphenyl diethoxy silane, at least one of phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidyl-2-t-butyldimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidyl dimethoxysilane and (1, 1-trifluoro-2-propyl) -methyldimethoxysilane. More preferably, the external electron donor compound may be at least one of dicyclopentyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl tert-butyl dimethoxy silane, and tetramethoxy silane.
In a third aspect, the use of the catalyst system according to the invention in olefin polymerization reactions.
In a fourth aspect, the present invention provides a process for the polymerization of olefins, the process comprising: contacting one or more olefins with said catalyst system under olefin polymerization conditions.
The olefin is at least one of the formula CH 2 Olefins represented by =chr, wherein R is hydrogen or C 1 -C 6 Straight or branched alkyl of (a). The formula CH 2 Specific examples of the olefins expressed by=chr may include: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, 4-methyl-1-pentene. Preferably, the olefin represented by the formula ch2=chr is ethylene, propylene, 1-n-butene, 1-n-hexene, 4-methyl-1-pentene. More preferably, the formula CH 2 The alkene represented by =chr is propylene.
The olefin polymerization method of the present invention may be a homo-polymerization of a single olefin or a copolymerization of a plurality of olefins.
According to the olefin polymerization process of the present invention, the olefin polymerization conditions may be conventional conditions in the art. Generally, the olefin polymerization conditions include: the temperature is 0-150 ℃, the time is 0.1-8 hours, and the pressure is 0.01-10MPa. Preferably, the olefin polymerization conditions include: the temperature is 50-100deg.C, the time is 0.5-3 hours, and the pressure is 0.5-5MPa. The olefin polymerization catalyst may be used in various conventional amounts of prior art olefin catalysts.
It should be noted that, the internal electron donor compound (component B and component C) not only participates in the construction of the active center, but also affects the recrystallization process of magnesium chloride to further affect the structure and morphology of the carrier, and the structure and morphology of the catalyst also finally affect the structure and morphology of the polymer due to the effect of morphology replication. The morphology of the catalyst in which the two compounds (component B and component C) participate is more favourable for the flowability of the polymer and therefore the fall time of the resulting polymer is smaller.
The above-mentioned raw materials in the present invention are all self-made or commercially available, and the present invention is not particularly limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes the compound I (component A) as a carrier, and the compound II (component B) and the compound III (component C) as internal electron donors, thus obtaining the catalyst with novel composition, which has good particle morphology, particle size which can be realized to be less than 30 microns and narrower particle size distribution. When the catalyst is used for propylene polymerization, the function of self-regulating and controlling the molecular weight distribution of polypropylene is realized through the use of a II compound (component B), meanwhile, the falling time of a polymer produced by the catalyst, particularly polypropylene particles, can be reduced, the performance of propylene copolymer is good, and the propylene performance is improved.
2. The catalyst prepared by the sulfur-containing catalyst for olefin polymerization has the advantages of small particle size, high activity, adjustable polymer molecular weight distribution width, short falling time, good copolymerization performance and great industrial application prospect.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
In each of examples and comparative examples of the present invention, the average particle diameter and particle size distribution of the olefin polymerization catalyst carrier were measured using a Master Sizer 2000 particle Sizer (manufactured by Malvern Instruments Ltd).
In the examples and comparative examples of the present invention, the apparent morphology of the olefin polymerization catalyst support was observed by an optical microscope commercially available from Nikon corporation under the model Eclipse E200.
In each of the examples and comparative examples of the present invention, melt Flow Rate (MFR): measured according to ISO1133, 230℃under a load of 2.16 kg.
In the examples and comparative examples of the present invention, the bulk density of the polyolefin powder was measured by the method prescribed in GB/T1636-2008.
In each of the examples and comparative examples of the present invention, the time for passing the entire amount of the polymer powder from the hopper through which the powder passes the bulk density meter was recorded as the falling time.
Preparation example 1
This preparation example is for explaining the spherical support of the olefin polymerization catalyst used in the present invention and the preparation method thereof.
In a 0.6L reactor, 8.0g (0.08 mol) of magnesium chloride, 56mL (0.96 mol) of ethanol, 1g (0.03 mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant are added, the temperature is raised to 90 ℃ under stirring, 38mL (0.48 mol) of epichlorohydrin is added after the constant temperature reaction for 2 hours, the constant temperature reaction at 90 ℃ is continued for half an hour, the filter-pressed product is filter-pressed, the filter-pressed product is washed with hexane for 5 times, and finally the product is dried in vacuum, thus obtaining the spherical carrier Z1 of the catalyst for olefin polymerization.
The olefin polymerization catalyst spherical support Z1 had an average particle diameter (D50) of 15 μm and a particle size distribution ((D90-D10)/D50) of 0.6. The spherical carrier Z1 of the olefin polymerization catalyst has regular particle morphology, smooth surface, basically spherical shape, centralized particle size distribution and basically no abnormal particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z1 is:
Figure BDA0003324268050000111
example 1
This example is for illustrating the catalyst components and catalyst preparation and propylene polymerization process provided by the present invention, and the specific details are as follows:
(1) Preparation of olefin polymerization catalyst
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20 ℃, 40 g of the olefin polymerization catalyst carrier Z1 obtained in preparation example 1 was added thereto, and stirred at-20℃for 30 minutes. After that, the temperature was slowly raised to 110℃and 1.5mL of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (mass ratio of 8:2) were added during the temperature rise, and the liquid was filtered off after maintaining at 110℃for 30min. Then, titanium tetrachloride was added to wash for 2 times, and finally hexane was used to wash for 5 times, and then dried to obtain an olefin polymerization catalyst C1.
(3) Propylene polymerization
In a 5L stainless steel autoclave, purging was performed with a nitrogen gas stream, and then 1mmol of triethylaluminum in hexane (triethylaluminum concentration 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, and 10mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5L (standard volume) of hydrogen, and 2.5L of liquid propylene were introduced into the nitrogen gas stream. Heating to 70 ℃, reacting for 1 hour at the temperature, reducing the temperature, releasing the pressure, discharging and drying to obtain the polypropylene powder P1.
The olefin polymerization catalyst C1 had an average particle diameter (D50) of 14 μm, a particle size distribution of 0.6, a ratio of the amount of sulfur substance to the amount of magnesium substance in the catalyst of 0.0020, an activity of 35.3kg PP/g.cat, a melt flow rate index of 8.6g/10min of the polypropylene powder P1, a molecular weight distribution width of 9.2, and a falling time of 6.4s. In addition, the polypropylene powder has good particle morphology and basically no special-shaped material exists.
Example 2
This example is intended to illustrate the catalyst components and the preparation of the catalyst and the propylene polymerization process provided by the present invention.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out as in example 1, except that the mass ratio of diethyl 2, 3-diisopropyl-2-cyano succinate to 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was 5:5.
The olefin polymerization catalyst C1 had an average particle diameter (D50) of 14 μm, a particle size distribution of 0.6, a ratio of the amount of sulfur substance to the amount of magnesium substance in the catalyst of 0.0021, an activity of 38.5kg PP/g.cat, a melt flow rate index of 9.0g/10min for the polypropylene powder P1, a molecular weight distribution width of 8.1, and a falling time of 6.3s. In addition, the polypropylene powder has good particle morphology and basically no special-shaped material exists.
Example 3
This example is intended to illustrate the catalyst components and the preparation of the catalyst and the propylene polymerization process provided by the present invention.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out as in example 1, except that the mass ratio of diethyl 2, 3-diisopropyl-2-cyano succinate to 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was 2:5.
The olefin polymerization catalyst C1 had an average particle diameter (D50) of 14 μm, a particle size distribution of 0.6, a ratio of the amount of sulfur substance to the amount of magnesium substance in the catalyst of 0.0020, an activity of 42.5kg PP/g.cat, a melt flow rate index of 9.8g/10min of the polypropylene powder P1, a molecular weight distribution width of 6.0, and a falling time of 6.2s. In addition, the polypropylene powder has good particle morphology and basically no special-shaped material exists.
Example 4
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 1 except that at the end of polymerization, the remaining gas phase reaction mass in the system was vented, heated to 80℃and an ethylene/propylene mixture (mass ratio ethylene/(ethylene+propylene) was 0.45) was introduced and reacted for 20 minutes to discharge.
The ethylene content of the polymer was found to be 6.4% by analysis.
Example 5
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 2 except that at the end of polymerization, the remaining gas phase reaction mass in the system was vented, heated to 80℃and an ethylene/propylene mixture (mass ratio ethylene/(ethylene+propylene) was 0.45) was introduced and reacted for 20 minutes to discharge.
The ethylene content of the polymer was found to be 5.8% by analysis.
Example 5
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 2 except that at the end of polymerization, the remaining gas phase reaction mass in the system was vented, heated to 80℃and an ethylene/propylene mixture (mass ratio ethylene/(ethylene+propylene) was 0.45) was introduced and reacted for 20 minutes to discharge.
The ethylene content of the polymer was found to be 4.8% by analysis.
Comparative example 1
This comparative example is used to illustrate the catalyst components and the reference preparation of the catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 1 except that diisobutyl phthalate was used in place of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to obtain olefin polymerization catalyst DC1 and polypropylene powder DP3.
The olefin polymerization catalyst DC1 had an average particle diameter (D50) of 14 μm, a particle size distribution of 0.6, a ratio of the amount of sulfur species to the amount of magnesium species in the catalyst of 0, an activity of 38.9kg PP/g.cat, a melt flow rate index of 12.0g/10min of the polypropylene powder DP3, a molecular weight distribution width of 4.8, and a falling time of 7.0s.
Comparative example 2
This comparative example is used to illustrate the catalyst components and the reference preparation of the catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the method of example 4 except that 2, 3-diisopropyl-2-cyano diethyl succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were replaced with 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
The ethylene content of the polymer was found to be 4.0% by analysis.
From the results, the catalyst prepared by the olefin polymerization sulfur-containing catalyst has small particle size, high activity, adjustable polymer molecular weight distribution width, short falling time, higher ethylene content in the process of post-copolymerization and great industrial application prospect.
Because of the ability of cyano succinates to build a wide variety of active sites, the molecular chain length of the polymers produced catalytically is greatly different, resulting in a wide molecular weight distribution, while the dimethoxypropane compounds can build relatively fewer active sites, resulting in a narrow molecular weight distribution, and thus the breadth of the molecular weight distribution of the final polymer can be effectively controlled by the former compounds.
Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (11)

1. A catalyst for olefin polymerization, characterized by comprising a component a, a component B and a component C;
the component A is a carrier, in particular to a sulfur-containing compound of magnesium, the structure of the component A is shown as a formula (I),
Figure FDA0003324268040000011
in the formula (I), R 1 Is C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl of (c);
R 2 and R is 3 Identical or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl of (a);
x is halogen;
m is 0.1-1.9, n is 0.1-1.9, m+n=2, 0< q is less than or equal to 0.5;
preferably, for R 1 、R 2 And R is 3 One or more hydrogens on the alkyl group may each independently be substituted with a halogen atom;
preferably, X is chloro or bromo;
preferably, m is 0.8-1.2, n is 0.8-1.2,0.005 and q is less than or equal to 0.2;
the component B is an internal electron donor compound, in particular to alpha cyano succinate and substituted alpha cyano succinate, the structure of which is shown as a formula (II),
Figure FDA0003324268040000012
in the formula (II), R ', is' 1 And R'. 2 Identical or different, each independently H, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl or C 7 -C 10 An aralkyl group;
R”' 3 and R'. 4 Identical or different, each independently C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl or C 7 -C 10 An aralkyl group;
preferably, R'. 1 With R ', R'. 2 Are mutually bonded to form one or more condensed ring structures;
preferably, R'. 3 And R'. 4 Identical or different, each independently C 1 ～C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl, C 3 ～C 10 Cycloalkyl, C 6 ～C 20 Aryl, C 7 ～C 20 Alkylaryl or C 7 ～C 20 An aromatic hydrocarbon group;
preferably, the aromatic ring such as hydrogen on the benzene ring in the aryl or alkylaryl or arylalkyl group may be optionally substituted with other atoms;
the component C is an internal electron donor compound, specifically a 1, 3-diether compound, and the structure of the component C is shown as a formula (III):
Figure FDA0003324268040000021
wherein R is 21 And R is 22 Each independently selected from hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl group R of (2) 21 And R is 22 Optionally bonded to form a ring; r is R 23 And R is 24 Each independently selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl groups of (a).
2. A catalyst component for the polymerization of olefins according to claim 1 in which the catalyst component is prepared by reacting, the 1, 3-diether compound is selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene;
preferably, the diether compound is 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
3. The catalyst for olefin polymerization according to claim 1, further comprising titanium element, chlorine element; the titanium element and the chlorine element are from titanium tetrachloride.
4. The catalyst for olefin polymerization according to claim 1, wherein the synthetic raw material of component a comprises elemental sulfur of the formula MgX 1 Y is a magnesium halide of the formula R 1 OH compounds and oxirane compounds.
5. The catalyst for the polymerization of olefins according to claim 4, characterized in that the general formula MgX 1 Y, X 1 Is halogen, Y is halogen, C 1 -C 5 Alkyl, C of (2) 1 -C 5 Alkoxy, C 6 -C 10 Aryl, C of (2) 6 -C 10 An aryloxy group of (a); and/or
The general formula R 1 In OH, R 1 Is C 1 -C 8 Alkyl, C of (2) 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl of (c); preferably, R 1 The hydrogen on the alkyl group may each independently be substituted with a halogen atom; and/or
The structure of the ethylene oxide compound is shown as a formula (IV):
Figure FDA0003324268040000031
in the formula (IV), R 2 And R is 3 Identical or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl of (a);
preferably, R 2 And R is 3 One or more hydrogens on the alkyl group may each independently be substituted with a halogen atom.
6. The catalyst for olefin polymerization according to claim 1, wherein the preparation method of the sulfur-containing magnesium compound of the component a comprises the steps of:
s1: elemental sulfur with the general formula MgX 1 Y is a magnesium halide of the formula R 1 OH compounds, inert liquid medium, surfactant blendsCombining and heating to obtain a liquid mixture;
s2: and (3) carrying out contact reaction on the liquid mixture obtained in the step (S1) and an ethylene oxide compound.
7. The catalyst for olefin polymerization according to claim 6, wherein in S1, the inert liquid medium is at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil; preferably, white oil; and/or
The dosage of the inert liquid medium is 1mol of MgX 1 The magnesium halide of Y is 0.8-10L, preferably 2-8L; and/or
The surfactant is at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, polymer of oxyalkylacrylate copolymer modified polyethyleneimine, 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyl trimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkylmethacrylate; preferably, at least one of polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer and polyethylene glycol; and/or
The dosage of the surfactant is 1mol of MgX 1 1-20g of magnesium halide of Y as a reference;
the heating temperature is 80-120 ℃, and the reaction time is 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the reaction time is 0.5-3 hours; and/or
In the step S2, the temperature of the contact reaction is 40-120 ℃ and the reaction time is 15-60 minutes; preferably, the contact reaction temperature is 60-100℃and the reaction time is 20-50 minutes.
8. The catalyst for olefin polymerization according to any one of claims 1 to 7, wherein the mass ratio of the active metallic titanium element, the magnesium element in the carrier and the internal electron donor compound is 1 (5-15): 2-15, preferably 1 (6-13): 3-12.
9. A catalyst system for the polymerization of olefins, characterized in that it comprises:
(1) The catalyst of any one of claims 1-8;
(2) An alkyl aluminum compound; and
(3) Optionally an external electron donor compound.
10. Use of the catalyst system of claim 9 in olefin polymerization reactions.
11. A process for the polymerization of olefins, the process comprising: contacting one or more olefins under olefin polymerization conditions with the catalyst system of claim 9.
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Publication number Priority date Publication date Assignee Title
JPH09169808A (en) * 1995-09-01 1997-06-30 Toho Titanium Co Ltd Solid catalyst component for olefin polymerization and catalyst therefor
CN102603932A (en) * 2011-01-19 2012-07-25 中国石油化工股份有限公司 Solid catalyst component and catalyst for olefinic polymerization
CN111072808A (en) * 2018-10-19 2020-04-28 中国石油化工股份有限公司 Catalyst component, catalyst, application thereof and olefin polymerization method
CN111072797A (en) * 2018-10-19 2020-04-28 中国石油化工股份有限公司 Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09169808A (en) * 1995-09-01 1997-06-30 Toho Titanium Co Ltd Solid catalyst component for olefin polymerization and catalyst therefor
CN102603932A (en) * 2011-01-19 2012-07-25 中国石油化工股份有限公司 Solid catalyst component and catalyst for olefinic polymerization
CN111072808A (en) * 2018-10-19 2020-04-28 中国石油化工股份有限公司 Catalyst component, catalyst, application thereof and olefin polymerization method
CN111072797A (en) * 2018-10-19 2020-04-28 中国石油化工股份有限公司 Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application

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