CN104558273A - Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization and olefin polymerization method - Google Patents
Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization and olefin polymerization method Download PDFInfo
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- CN104558273A CN104558273A CN201310468309.9A CN201310468309A CN104558273A CN 104558273 A CN104558273 A CN 104558273A CN 201310468309 A CN201310468309 A CN 201310468309A CN 104558273 A CN104558273 A CN 104558273A
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Abstract
The invention provides a catalyst component for olefin polymerization and a preparation method thereof, a catalyst for olefin polymerization and an olefin polymerization method. The catalyst component for olefin polymerization contains a product obtained by carrying out a reaction of an olefin polymerization catalyst carrier, a titanium compound and an internal electron donor compound, wherein the olefin polymerization catalyst carrier contains a product obtained by carrying out a reaction of a carboxylic acid magnesium salt represented by the general formula of Mg(R4COO)2, a compound represented by the general formula of R1OH, an epoxy chloroethane compound having a structure represented by the formula (I) and an optional inert liquid medium. The olefin polymerization catalyst carrier has relatively good particle morphology, and when used in polymerization of olefin, the olefin polymerization catalyst prepared by the olefin polymerization catalyst carrier also has relatively high catalytic activity and basically has no special-shape material appearing.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polymerization, the preparation method of the catalyst component for olefinic polymerization, the catalyst component for olefinic polymerization prepared by aforesaid method, a kind of catalyzer for olefinic polymerization and olefine polymerizing process.
Background technology
As everyone knows, when the Ziegler-Natta catalyst of magnesium chloride alcohol adduct load is polymerized for alkene (particularly propylene), its performance is obviously better than the catalyzer of other carrier institute load.Therefore, mostly prepare by halogenated titanium being carried on magnesium chloride alcohol adduct for the catalyzer of olefinic polymerization at present.In order to obtain ball type carrier, extrude by spraying dry, spray cooling, high pressure, the method preparation such as high-speed stirring, mulser method and high-gravity rotating bed method, spherical alcohol adduct can be formed by quenching after high-speed stirring emulsified magnesium chloride alcohol adduct system under high temperature as WO99/44009 and US4399054 discloses.
But, when the catalyzer prepared by above-mentioned published magnesium chloride alcohol adduct is used for olefinic polymerization, is easy to the Fragmentation Phenomena that polymer particle occurs in the course of the polymerization process, thus causes fine polymer powder more.In order to overcome this defect, people attempt again electron donor compound to be incorporated in the preparation of magnesium chloride alcohol adduct carrier in advance, such as, known for industry internal electron donor phthalate compound is incorporated in the preparation of magnesium chloride alcohol adduct carrier by CN1397568A and CN1563112A, thus obtain " magnesium dichloride-alcohol-phthalic ester " complex spherical carrier, then by this carrier and titanium tetrachloride reaction to form catalyzer.But above-mentioned complex spherical carrier is easily clamminess in preparation process, be difficult to form the suitable spheroidal particle of size.
In addition, above-mentioned magnesium chloride alcohol adduct is all adopt the alcohol adduct melt of cryogenic quenching solidification high temperature to obtain, and not only, complicated process of preparation, palpus multiple reactor comparatively large to the consumption of the energy combine preparation, and the size distribution of obtained alcohol adduct is wider.In order to solve this problem, CN102040683A discloses a kind of method reacting to prepare carrier by magnesium halide alcohol adduct and epoxy monochloroethane compounds, and specifically disclose by magnesium halide alcohol adduct melting disperse after add epoxy monochloroethane compounds; Or in the reactor directly joining containing epoxy monochloroethane compounds after magnesium halide alcohol adduct melting is disperseed.But, adopt the method Kaolinite Preparation of Catalyst carrier to there is preparation process instability, easily carrier adhesion occurs, and the shortcoming that carrier molding effect is bad.
Summary of the invention
First object of the present invention is the above-mentioned defect overcoming the catalyzer for olefinic polymerization adopting existing carrier for olefin polymerization catalyst to prepare, and provides a kind of catalyst component for olefinic polymerization newly.
Second object of the present invention is to provide this preparation method for the catalyst component of olefinic polymerization.
3rd object of the present invention is to provide the catalyst component for olefinic polymerization prepared by above-mentioned preparation method.
4th object of the present invention is to provide a kind of catalyzer for olefinic polymerization.
5th object of the present invention is to provide a kind of olefine polymerizing process.
The invention provides a kind of catalyst component for olefinic polymerization, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, wherein, described carrier for olefin polymerization catalyst contains by general formula is Mg (R
4cOO)
2carboxylic acid magnesium salts, general formula be R
1the product that the compound of OH, the epoxy monochloroethane compounds with structure shown in formula I and optional inert liquid medium are obtained by reacting;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched.
Present invention also offers a kind of preparation method of the catalyst component for olefinic polymerization, the method comprises the following steps:
(1) be Mg (R by general formula
4cOO)
2carboxylic acid magnesium salts and general formula be R
1the compound of OH and the mixing of optional inert liquid medium, and the mixture heating that will obtain, make described carboxylic acid magnesium salts dissolve, obtain liquid form mixt;
(2) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and the epoxy monochloroethane compounds contact reacts with structure shown in formula I, carrier for olefin polymerization catalyst is obtained;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched;
(3) described carrier for olefin polymerization catalyst and titanium compound are reacted, and before and after, during the reaction of described carrier for olefin polymerization catalyst and titanium compound in one or more time periods in add internal electron donor compound.
The present invention also provides the catalyst component for olefinic polymerization prepared by aforesaid method.
Present invention also offers a kind of catalyzer for olefinic polymerization, this catalyzer contains:
(1) the above-mentioned catalyst component for olefinic polymerization;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
In addition, present invention also offers a kind of olefine polymerizing process, the method comprises: under olefin polymerization conditions, by one or more alkene and the above-mentioned catalyst exposure for olefinic polymerization.
The present inventor is surprised to find that in experimentation, the carrier for olefin polymerization catalyst prepared by method provided by the invention not only has good particle form, and when olefin polymerization catalysis prepared by described carrier for olefin polymerization catalyst being used for the polymerization of alkene (particularly propylene), also there is higher catalytic activity and substantially without the appearance of abnormity material, have prospects for commercial application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to a first aspect of the invention, catalyst component for olefinic polymerization provided by the invention contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, wherein, described carrier for olefin polymerization catalyst contains by general formula is Mg (R
4cOO)
2carboxylic acid magnesium salts, general formula be R
1the product that the compound of OH, the epoxy monochloroethane compounds with structure shown in formula I and optional inert liquid medium are obtained by reacting;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched.Preferably, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl.
Described C
1-C
5the example of alkyl of straight or branched include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl or neo-pentyl.Described C
1-C
5the chloro alkyl of straight or branched or the example of bromo alkyl include but not limited to: methyl chloride, methyl bromide, chloric ethane, bromic ether, chloro-propane, bromo propane, chloro-butane, butyl bromide, chloro-pentane or bromo pentane.
The consumption of the present invention to the above-mentioned each material in described carrier for olefin polymerization catalyst is not particularly limited, and such as, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH can be 4-30mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I can be 1-10mol; Preferably, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH is 6-20mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I is 1.5-6mol.
According to the present invention, the kind of described carboxylic acid magnesium salts can be that the routine of this area is selected, and such as, its specific examples includes but not limited to: one or more in magnesium formiate, magnesium acetate, propionic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium.From the angle that raw material is easy to get, described carboxylic acid magnesium salts is particularly preferably magnesium acetate.In addition, it should be noted that, described carboxylic acid magnesium salts is usually with crystal water, when preparing described carrier for olefin polymerization catalyst, can directly adopt carboxylic acid magnesium salts with crystal water as raw material, also first the crystal water in described carboxylic acid magnesium salts can be removed, then will the carboxylic acid magnesium salts after crystal water be removed as raw material.
According to the present invention, at general formula R
1in OH, R
1for C
1-C
8the alkyl of straight or branched, be preferably C
1-C
5the alkyl of straight or branched.Correspondingly, general formula is R
1the specific examples of the compound of OH can include but not limited to: one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol, is preferably one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol and primary isoamyl alcohol.
The concrete kind of the present invention to described epoxy chloroethane compound is not particularly limited, as long as have the structure shown in formula I, from the angle that raw material is ready availability, described epoxy chloroethane compound be particularly preferably in epoxy monochloroethane, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide one or more.
According to the present invention, the consumption of described inert liquid medium can be selected according to the consumption of carboxylic acid magnesium salts.Usually, with the described carboxylic acid magnesium salts of 1mol for benchmark, the consumption of described inert liquid medium can be 0.8-10L, is preferably 2-8L.Chemically interactive liquid medium can be there is not with reactant and reaction product in described inert liquid medium for conventional various in this area.Such as, described inert liquid medium can be silicone oil and/or inert liq varsol.Particularly, described inert liquid medium can be one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil, is particularly preferably white oil.
A preferred embodiment of the invention, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, is more preferably 35-60 micron; Size distribution is preferably less than 1.2, is more preferably 0.6-1.In this preferred implementation, the catalyzer prepared by this carrier for olefin polymerization catalyst has higher catalytic activity.In the present invention, the average particulate diameter of described carrier for olefin polymerization catalyst and size distribution can adopt Master Sizer2000 laser particle analyzer (being manufactured by Malvern InstrumentsLtd) to record.
The preparation method of the present invention to described carrier for olefin polymerization catalyst is not particularly limited, and under preferable case, described carrier for olefin polymerization catalyst prepares in accordance with the following methods:
(1) be Mg (R by general formula
4cOO)
2carboxylic acid magnesium salts and general formula be R
1the compound of OH and the mixing of optional inert liquid medium, and the mixture heating that will obtain, make described carboxylic acid magnesium salts dissolve, obtain liquid form mixt;
(2) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and the epoxy monochloroethane compounds contact reacts with structure shown in formula I;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched; Preferably, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl.
Wherein, described carboxylic acid magnesium salts, general formula are R
1the compound of OH, there is the epoxy monochloroethane compounds of structure shown in formula I, the kind of inert liquid medium and consumption describe hereinbefore, will repeat no more at this.
The condition of the present invention to heating described in step (1) is not particularly limited, as long as described carboxylic acid magnesium salts can be made to dissolve, such as, the condition of described heating comprises: the temperature of heating can be 60-120 DEG C, is preferably 80-100 DEG C; Heat-up time can be 0.5-5 hour, is preferably 0.5-2 hour.
According to the present invention, the liquid form mixt emulsification that well known to a person skilled in the art that step (1) obtains by various method can be adopted.Such as, described liquid form mixt can be carried out low velocity shear or high speed shear, thus by its emulsification.The stir speed (S.S.) of described low velocity shear is generally 400-800 rev/min.The method of described high speed shear is conventionally known to one of skill in the art, high-speed mixing method (that is, being stirred with the speed of 2000-5000 rev/min by the solution containing liquid halogenated magnesium adducts) disclosed in CN1151183C.In addition, by disclosed for described liquid form mixt emulsification: CN1267508C, the solution containing liquid halogenated magnesium adducts can also be carried out rotating dispersion (speed of rotation can be 100-3000 rev/min) in hypergravity bed with reference to method disclosed in following patent; CN1463990A is disclosed to be exported the solution containing liquid halogenated magnesium adducts with the speed of 1500-8000 rev/min in mulser; US6020279 disclosed by spray method by the emulsifying soln containing liquid halogenated magnesium adducts.
The present invention is not particularly limited the catalytic condition described in step (2), such as, generally includes: Contact Temperature can be 60-120 DEG C, is preferably 80-100 DEG C; Duration of contact can be 20-60 minute, is preferably 20-50 minute.
The preparation method of carrier for olefin polymerization catalyst provided by the invention can also comprise product contact reacts obtained and carry out solid-liquid separation, is washed by solid product and carries out drying.Described solid-liquid separation can be the existing various method that can realize solid phase and liquid phase separation, such as suction filtration, press filtration or centrifugation, and under preferable case, the method for described solid-liquid separation is filter press technique.The condition of the present invention to press filtration is not particularly limited, and is as the criterion with being separated of liquid phase to realize solid phase as far as possible fully.Described washing can adopt and well known to a person skilled in the art that various method is carried out, such as, inert hydrocarbon solvent (such as: pentane, hexane, heptane, sherwood oil and gasoline) can be adopted to wash the solid product obtained.The present invention is not particularly limited for the condition of described drying, and such as, the condition of described drying comprises: drying temperature can be 20-70 DEG C, and time of drying can be 0.5-10 hour.According to the present invention, described drying can be carried out under normal pressure or reduced pressure.
In the present invention, described in the catalyst component of olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound can be 1:5-15:2-15, is preferably 1:6-13:3-12.
In the present invention, there is no particular limitation for the condition of the reaction of described carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, under preferable case, the condition of this reaction can comprise: temperature of reaction is 80-130 DEG C, and the reaction times is 0.5-10 hour.
In the present invention, described titanium compound can be the conventional various titanium compounds used in process for the preparation of the catalyzer of olefinic polymerization.Usually, described titanium compound can be such as Ti (OR ') for general formula
3-az
aand/or Ti (OR ')
4-bz
bcompound, wherein, R ' is C
1-C
20alkyl, Z is F, Cl, Br or I, a is the integer of 1-3, and b is the integer of 1-4.Under preferable case, described titanium compound is one or more in titanium tetrachloride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride, oxyethyl group titanous chloride and titanous chloride.
In the present invention, described internal electron donor compound can be the conventional various internal electron donor compound used in the process for the preparation of the catalyzer of olefinic polymerization, can be such as one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane, be preferably one or more in unitary or polyhydric aliphatic race carboxylicesters, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.
Described unitary or polyhydric aliphatic carboxylicesters can be such as diethyl malonate, butyl ethyl malonate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-isopropyl dibutyl succinate, 2, 3-di-isopropyl succsinic acid dimethyl esters, 2, 2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl ethyl succinate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diethyl maleate, maleic acid n-butyl, one or more in naphthalene dicarboxylic acids diethyl ester and naphthalene dicarboxylic acids dibutylester.
Described unitary or polynary aromatic carboxylic acid esters can be such as one or more in ethyl benzoate, phthalic ester diethyl ester, phthalic ester diisobutyl ester, phthalic ester di-n-butyl, phthalic ester di-isooctyl, phthalic ester di-n-octyl, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester and pyromellitic acid four butyl ester.
Described binary alcohol esters can be the compound represented by following formula (1),
Wherein, R
14and R
15can be identical or different, and can be the C of halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or C
2-C
20alkylene; In formula (1), the contents table of bracket [] is shown with d carbon atom key company successively, and each carbon atom also replaces base key even with 2, i.e. total d carbon atom and R in bracket
1, R
2, R
3r
2ddeng 2d substituting group, R
10-R
13and R
1-R
2didentical or different, and be the C of hydrogen, halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
10-R
13and R
1-R
2din two or more bondings form saturated or undersaturated ring structure, described heteroatoms can be one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus, and d is the integer of 0-10, and as d=0, then in the binary alcohol esters shown in formula (1), substituting group is R
10, R
11carbon atom directly and substituting group be R
12, R
13carbon atom key connect.
Under preferable case, described binary alcohol esters is the compound represented by following formula (2):
Wherein, R
14and R
15identical with the definition in above-mentioned formula (1); R
10'-R
13', R
16and R
17can be identical or different, and can be the C of hydrogen, halogen, straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
10'-R
13', R
16and R
17in two or more bondings form saturated or undersaturated ring structure, described heteroatoms can be one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus.
In the present invention, described binary alcohol esters can be such as 1,3-PD dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, (R)-1-phenyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD two n Propanoic acid ester, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dibenzoate, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dipropionate, 1,3-di-t-butyl-2-ethyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD diacetate esters, 1,3-di-isopropyl-1,3-propyl alcohol two (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, 2,4-glycol dibenzoate, 3-butyl-2,4-glycol dibenzoate, 3,3-dimethyl-2,4-glycol dibenzoate, 2,4-pentanediol two (Chlorodracylic acid) ester, 2,4-pentanediol two (m-chlorobenzoic acid) ester, 2,4-pentanediol two (parabromobenzoic acid) ester, 2,4-pentanediol two (o-bromobenzoic acid) ester, 2,4-pentanediol two (p-methylbenzoic acid) ester, 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-pentanediol two (to butylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (Chlorodracylic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-butyl-1,3-pentanediol two (p-methylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol pivalate, 2-methyl isophthalic acid, 3-pentanediol phenylformic acid laurate, 2,2-dimethyl-1,3-glycol dibenzoate, 2,2-dimethyl-1,3-pentanediol phenylformic acid laurate, 2-ethyl-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2-allyl group-1,3-glycol dibenzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-propyl group-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 1,3-pentanediol two (Chlorodracylic acid) ester, 1,3-pentanediol two (m-chlorobenzoic acid) ester, 1,3-pentanediol two (parabromobenzoic acid) ester, 1,3-pentanediol two (o-bromobenzoic acid) ester, 1,3-pentanediol two (p-methylbenzoic acid) ester, 1,3-pentanediol two (p-tert-butyl benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 1,3-pentanediol phenylformic acid laurate, 1,3-pentanediol two laurate, 1,3-pentanediol dipropionate, 2,2,4-trimethylammonium-1,3-pentanediol di-isopropyl manthanoate, 1-trifluoromethyl-3-methyl-2,4-glycol dibenzoate, 2,4-pentanediol, two pairs of fluoromethyl benzoic ethers, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl group-6-heptene-2,4-heptanediol dibenzoate, 4-propyl group-6-heptene-2,4-heptanediol dibenzoate, 5-propyl group-6-heptene-2,4-heptanediol dibenzoate, 6-propyl group-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3-propyl group-3,5-heptanediol dibenzoate, 4-propyl group-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, two (benzoyloxy methyl) fluorenes of 9,9-, two ((meta-methoxy benzoyloxy) methyl) fluorenes of 9,9-, two ((m-chloro benzoyloxy) methyl) fluorenes of 9,9-, two ((to the chlorobenzene carboxyphenyl) methyl) fluorenes of 9,9-, two (Chinese cassia tree carboxymethyl group) fluorenes of 9,9-, 9-(benzoyloxy methyl)-9-(the third carboxymethyl group) fluorenes, two (the third carboxymethyl group) fluorenes of 9,9-, one or more in two (propylene carboxymethyl group) fluorenes of 9,9-and two (neo-pentyl carboxymethyl group) fluorenes of 9,9-, cited part binary alcohol esters can be commercially available, and other can with reference to the method synthesis described in CN1436796A.
Described binary ether can be the compound represented by following formula (3),
Wherein, R
18and R
19can be identical or different, and can be the C of straight chain or straight chain separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl or C
7-C
20aralkyl; R
20-R
25can be identical or different, and can be the C of hydrogen, halogen, straight chain or straight chain separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or R
20-R
25in the ring structure that formed of two or more bondings.In the preferred case, R
18and R
19identical or different, and be the C of straight chain or straight chain separately
1-C
10alkyl; R
20, R
21, R
24and R
25be hydrogen; R
22and R
23identical or different, and be the C of straight chain or straight chain separately
1-C
18alkyl, C
3-C
18cycloalkyl, C
6-C
18aryl, C
7-C
18aralkyl or R
22and R
23the ring structure that mutual bonding is formed.
In the present invention, described binary ether can be such as 2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-butyl-1,3-Propanal dimethyl acetal, 2-sec-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-1,3-Propanal dimethyl acetal, 2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1,3-Propanal dimethyl acetal, 2-(2-cyclohexyl-ethyl)-1,3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1,3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1,3-Propanal dimethyl acetal, two (2-cyclohexyl-ethyl)-1, the 3-Propanal dimethyl acetal of 2,2-, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two (cyclohexyl methyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, one or more in 2-cyclohexyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal and 9,9-dimethoxy-methyl fluorenes.
According to a third aspect of the present invention, present invention also offers a kind of preparation method of the catalyst component for olefinic polymerization, the method comprises the following steps:
(1) be Mg (R by general formula
4cOO)
2carboxylic acid magnesium salts and general formula be R
1the compound of OH and the mixing of optional inert liquid medium, and the mixture heating that will obtain, make described carboxylic acid magnesium salts dissolve, obtain liquid form mixt;
(2) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and the epoxy monochloroethane compounds contact reacts with structure shown in formula I, carrier for olefin polymerization catalyst is obtained;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched; Preferably, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl;
(3) described carrier for olefin polymerization catalyst and titanium compound are reacted, and before and after, during the reaction of described carrier for olefin polymerization catalyst and titanium compound in one or more time periods in add internal electron donor compound.
In the preparation method of the above-mentioned catalyst component for olefinic polymerization, step (1) is identical with (2) with the step (1) in the preparation method of the carrier for olefin polymerization catalyst described above with (2), and therefore not to repeat here.
In the preparation method of the described catalyst component for olefinic polymerization, step (3) described carrier for olefin polymerization catalyst and titanium compound react and mode same as the prior art can be adopted to carry out, concrete, such as, in step (3), the concrete operation method that described carrier for olefin polymerization catalyst and titanium compound react is preferably included: titanium compound is cooled to less than 0 DEG C (being preferably-5 to-25 DEG C), then the carrier for olefin polymerization catalyst obtained in step (2) is added, and be uniformly mixed 10-60 minute at such a temperature, be warming up to temperature of reaction (i.e. about 80-130 DEG C) afterwards, and 0.5-10 hour is maintained under this temperature of reaction.In the preparation method of the described catalyst component for olefinic polymerization, described internal electron donor compound before and after, during the reaction of described carrier for olefin polymerization catalyst and titanium compound in one or more time periods in add, preferably added before the reaction of described carrier for olefin polymerization catalyst and titanium compound.Time period before the reaction of described carrier for olefin polymerization catalyst and titanium compound refers to the time period after described carrier for olefin polymerization catalyst adds in reactor and before being warming up to temperature of reaction.
In the preparation method of the described catalyst component for olefinic polymerization, in step (3), in the carrier for olefin polymerization catalyst of magnesium elements, for 1:20-150:0.005-1,1:30-120:0.01-0.6 can be preferably in the mol ratio of the add-on of the titanium compound of titanium elements and internal electron donor.
In the preparation method of the described catalyst component for olefinic polymerization, the middle titanium compound described is identical with internal electron donor respectively with above for described titanium compound and internal electron donor, and therefore not to repeat here.
According to a third aspect of the present invention, present invention also offers the catalyst component for olefinic polymerization prepared by aforesaid method.
According to a fourth aspect of the present invention, present invention also offers a kind of catalyzer for olefinic polymerization, this catalyzer contains:
(1) the described catalyst component for olefinic polymerization;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
Composition of the described catalyst component for olefinic polymerization and preparation method thereof is described in detail in the preceding article, does not repeat them here.
Improvements of the present invention are mainly the described catalyst component for olefinic polymerization, and the kind of described alkylaluminium cpd and external donor compound and consumption all can be same as the prior art.In addition, when the described catalyzer being used for olefinic polymerization is used as the catalyzer of olefinic polyreaction, higher polymerization activity can not only be demonstrated, and the good polymkeric substance of particle shape can be prepared, substantially occur without abnormity material.
Usually, described in the catalyzer of olefinic polymerization, for 1-2000:1,20-500:1 can be preferably in the alkylaluminium cpd of aluminium with in the mol ratio of the catalyst component for olefinic polymerization of titanium; The mol ratio of described external donor compound and alkylaluminium cpd can be 0.005-0.5:1, is preferably 0.01-0.4:1.
The various alkylaluminium cpds that described alkylaluminium cpd can be commonly used for this area.Such as, described alkylaluminium cpd can be one or more in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro one aluminium triethyl, dichloro one aluminium isobutyl, dichloro one n-butylaluminum and dichloro one n-hexyl aluminium.
Described external donor compound can be the conventional various external donor compounds in this area, and such as, described external electron donor can be one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicoorganic compound; Preferably, described external electron donor is silicoorganic compound.The example of described silicoorganic compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane and (1,1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane and (1, the fluoro-2-propyl group of 1,1-tri-)-methyl dimethoxysilane.
According to a fifth aspect of the present invention, present invention also offers a kind of olefine polymerizing process, the method comprises: under olefin polymerization conditions, and by one or more alkene and catalyst exposure, wherein, described catalyzer is the above-mentioned catalyzer for olefinic polymerization.
Described alkene can be such as one or more in ethene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-amylene, 2-amylene, 1-hexene and vinylbenzene, is preferably one or more in ethene, propylene, 1-butylene, 2-butylene and vinylbenzene.
According to olefine polymerizing process of the present invention, described olefinic polymerization can be carried out according to the ordinary method of this area.Such as, described olefinic polymerization can be mass polymerization, vapour phase polymerization or slurry polymerization.According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area, and such as, polymerization temperature can be 0-150 DEG C, is preferably 60-90 DEG C; Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples.But should be understood that, these embodiments, only for instruction and explanation of the present invention, are not limited to the present invention.
In preparation example and contrast preparation example:
1, the average particulate diameter of carrier for olefin polymerization catalyst and size distribution adopt Masters S I zer2000 particle size analyzer (being manufactured by Malvern Instruments Ltd) to measure;
2, the apparent form of carrier for olefin polymerization catalyst is observed by the opticmicroscope that to be purchased from the model of Nikon company be Eclipse E200.
Preparation example 1
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 20g(0.09mol) magnesium acetate (containing four crystal water), 95mL(1.6mol) ethanol, under agitation be warming up to 90 DEG C and isothermal reaction after 1 hour, by the mixture high-speed stirring obtained, (stir speed (S.S.) is 1600rpm, lower same) disperse 30 minutes, to carry out emulsification, obtain emulsification product.And 35mL(0.45mol is added in above-mentioned emulsification product) epoxy chloropropane, temperature is controlled press filtration after 90 DEG C of reaction half hours.Solid product hexane press filtration obtained washs 5 times, finally that product vacuum is dry, obtains carrier for olefin polymerization catalyst Z1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z1 is 40 microns, and size distribution ((D90-D10)/D50) is 1.0.Arrived by observation by light microscope, the particle form of carrier for olefin polymerization catalyst Z1 is more regular, smooth surface, is substantially all spherical, and there is no that irregular particle exists.
Preparation example 2
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 300mL white oil, 12.8g(0.09mol) anhydrous acetic acid magnesium (by what obtain containing the magnesium acetate Dehydration of four crystal water), 99mL(1.7mol) ethanol, under agitation be warming up to 100 DEG C and isothermal reaction after 0.5 hour, by the mixture stirring at low speed obtained, (stir speed (S.S.) is 800 revs/min, lower same) disperse 30 minutes, to carry out emulsification, obtain emulsification product.And 12.5mL(0.16mol is added in above-mentioned emulsification product) epoxy chloropropane, temperature is controlled 100 DEG C of reaction press filtrations after 20 minutes.Solid product hexane press filtration obtained washs 5 times, has washed rear press filtration at every turn, finally that product vacuum is dry, obtains carrier for olefin polymerization catalyst Z2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z2 is 35 microns, and size distribution ((D90-D10)/D50) is 0.9.Arrived by observation by light microscope, the particle form of carrier for olefin polymerization catalyst Z2 is more regular, smooth surface, is substantially all spherical, and there is no that irregular particle exists.
Preparation example 3
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 15.3g(0.09mol) propionic acid magnesium, 68mL(0.54mol) ethanol, be under agitation warming up to 80 DEG C and isothermal reaction after 2 hours, the mixture high-speed stirring obtained disperseed 30 minutes, to carry out emulsification, obtain emulsification product.And 23mL(0.27mol is added in above-mentioned emulsification product) epoxy bromopropane, temperature is controlled 80 DEG C of reaction press filtrations after 50 minutes.Solid product hexane press filtration obtained washs 5 times, finally that product vacuum is dry, obtains carrier for olefin polymerization catalyst Z3.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z3 is 40 microns, and size distribution ((D90-D10)/D50) is 0.8.Arrived by observation by light microscope, the particle form of carrier for olefin polymerization catalyst Z3 is more regular, smooth surface, is substantially all spherical, and there is no that irregular particle exists.
Embodiment 1
This embodiment is preparing the application in alkene for illustration of carrier for olefin polymerization catalyst provided by the invention.
(1) for the preparation of olefin polymerization catalyst components:
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100mL and be cooled to-20 DEG C, the described carrier for olefin polymerization catalyst Z1 obtained of 40 grams being added wherein, and stir 30min by preparation example 1 at-20 DEG C.Afterwards, be slowly warming up to 110 DEG C, in temperature-rise period, add the diisobutyl phthalate of 1.5mL, elimination liquid maintain 30min at 110 DEG C after.Then, add titanium tetrachloride and wash 2 times, finally wash 3 times with hexane, after drying, obtain olefin polymerization catalyst components C1.Adopt grating spectrophotometer, according to the content of the titanium elements in this olefin polymerization catalyst components of spectrophotometry; The content of the magnesium elements in this olefin polymerization catalyst components is detected according to complexometry; Detect the content of the diisobutyl phthalate in this catalyst component according to liquid phase chromatographic analysis method, the weight ratio that result records titanium elements, magnesium elements and diisobutyl phthalate in this olefin polymerization catalyst components is 3:16:8.
(2) propylene polymerization:
In the stainless steel autoclave of a 5L, adopt stream of nitrogen gas to purge, in stream of nitrogen gas, then introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of 1mmol, olefin polymerization catalyst components C1,1.5L(standard volume obtained by step (1) of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg) hydrogen and the liquid propene of 2.5L.Be warming up to 70 DEG C, and react 1 hour at such a temperature, lower the temperature afterwards and bleed off pressure, discharging drying obtains polypropylene powder particle J1.As calculated, the polymerization activity of this olefin polymerization catalysis is 3.0kgPP/gCat.In addition, described polypropylene powder particle J1 form is good, substantially there is not abnormity material.
Embodiment 2
This embodiment is preparing the application in alkene for illustration of carrier for olefin polymerization catalyst provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z2 that described carrier for olefin polymerization catalyst Z1 preparation example 2 obtains substitutes, and obtains olefin polymerization catalysis and polypropylene powder particle J2.As calculated, the polymerization activity of described olefin polymerization catalysis is 3.6kgPP/gCat.In addition, described polypropylene powder particle J2 form is good, substantially there is not abnormity material.
Embodiment 3
This embodiment is preparing the application in alkene for illustration of carrier for olefin polymerization catalyst provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z3 that described carrier for olefin polymerization catalyst Z1 preparation example 3 obtains substitutes, and obtains olefin polymerization catalysis and polypropylene powder particle J3.As calculated, the polymerization activity of described olefin polymerization catalysis is 3.0kgPP/gCat.In addition, described polypropylene powder particle J3 form is good, substantially there is not abnormity material.
As can be seen from the above results, the size distribution of the carrier for olefin polymerization catalyst adopting method of the present invention to prepare is better, and the catalyzer that the carrier for olefin polymerization catalyst of gained prepares is used for alkene (particularly propylene) when being polymerized, also there is higher activity and substantially without the appearance of abnormity material, have prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. the catalyst component for olefinic polymerization, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, it is characterized in that, it is Mg (R that described carrier for olefin polymerization catalyst contains by general formula
4cOO)
2carboxylic acid magnesium salts, general formula be R
1the product that the compound of OH, the epoxy monochloroethane compounds with structure shown in formula I and optional inert liquid medium are obtained by reacting;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched.
2. catalyst component according to claim 1, wherein, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl.
3. catalyst component according to claim 1 and 2, wherein, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH is 4-30mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I is 1-10mol; Preferably, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH is 6-20mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I is 1.5-6mol.
4. catalyst component according to claim 1 and 2, wherein, described carboxylic acid magnesium salts is one or more in magnesium formiate, magnesium acetate, propionic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium; Preferably, general formula is R
1the compound of OH is one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol and primary isoamyl alcohol; Preferably, the epoxy monochloroethane compounds with structure shown in formula I is one or more in epoxy monochloroethane, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
5. catalyst component according to claim 1 and 2, wherein, with the described carboxylic acid magnesium salts of 1mol for benchmark, the consumption of described inert liquid medium is 0.8-10L, and described inert liquid medium is silicone oil and/or inert liq varsol; Preferably, described inert liquid medium is one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
6. catalyst component according to claim 1 and 2, wherein, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, and size distribution is less than 1.2; Preferably, the average particulate diameter of described carrier for olefin polymerization catalyst is 35-60 micron, and size distribution is 0.6-1.
7. catalyst component according to claim 1 and 2, wherein, described carrier for olefin polymerization catalyst prepares in accordance with the following methods:
(1) be Mg (R by general formula
4cOO)
2carboxylic acid magnesium salts and general formula be R
1the compound of OH and the mixing of optional inert liquid medium, and the mixture heating that will obtain, make described carboxylic acid magnesium salts dissolve, obtain liquid form mixt;
(2) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and the epoxy monochloroethane compounds contact reacts with structure shown in formula I;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched;
Preferably, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl.
8. catalyst component according to claim 7, wherein, in step (1), the condition of described heating comprises: Heating temperature is 60-120 DEG C, and heat-up time is 0.5-5 hour; Preferably, in step (2), described catalytic condition comprises: Contact Temperature is 60-120 DEG C, and duration of contact is 20-60 minute.
9., for a preparation method for the catalyst component of olefinic polymerization, the method comprises the following steps:
(1) be Mg (R by general formula
4cOO)
2carboxylic acid magnesium salts and general formula be R
1the compound of OH and the mixing of optional inert liquid medium, and the mixture heating that will obtain, make described carboxylic acid magnesium salts dissolve, obtain liquid form mixt;
(2) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and the epoxy monochloroethane compounds contact reacts with structure shown in formula I, carrier for olefin polymerization catalyst is obtained;
Wherein, R
1for C
1-C
8the alkyl of straight or branched, R
4not exist or for C
1-C
6the alkyl of straight or branched, R
5for hydrogen, C
1-C
5the alkyl of straight or branched or haloalkyl, R
6for halogen or C
1-C
5the haloalkyl of straight or branched; Preferably, R
1for C
1-C
5the alkyl of straight or branched, R
4not exist or for C
1-C
5the alkyl of straight or branched, R
5for hydrogen, R
6for bromine, chlorine, C
1-C
5the chloro alkyl of straight or branched or bromo alkyl;
(3) described carrier for olefin polymerization catalyst and titanium compound are reacted, and before and after, during the reaction of described carrier for olefin polymerization catalyst and titanium compound in one or more time periods in add internal electron donor compound.
10. preparation method according to claim 9, wherein, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH is 4-30mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I is 1-10mol; Preferably, with the described carboxylic acid magnesium salts of 1mol for benchmark, general formula is R
1the consumption of the compound of OH is 6-20mol, and the consumption with the epoxy monochloroethane compounds of structure shown in formula I is 1.5-6mol.
11. preparation methods according to claim 9 or 10, wherein, described carboxylic acid magnesium salts is one or more in magnesium formiate, magnesium acetate, propionic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium; Preferably, general formula R
1the compound of OH is one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol and primary isoamyl alcohol; Preferably, the epoxy monochloroethane compounds with structure shown in formula I is one or more in epoxy monochloroethane, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
12. preparation methods according to claim 9 or 10, wherein, in step (1), the condition of described heating comprises: Heating temperature is 60-120 DEG C, and heat-up time is 0.5-5 hour; Preferably, in step (2), described catalytic condition comprises: Contact Temperature is 60-120 DEG C, and duration of contact is 20-60 minute.
13. preparation methods according to claim 9 or 10, wherein, with the described carboxylic acid magnesium salts of 1mol for benchmark, the consumption of described inert liquid medium is 0.8-10L, and described inert liquid medium is silicone oil and/or inert liq varsol; Preferably, described inert liquid medium is one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
14. catalyst components for olefinic polymerization prepared by the method in claim 9-13 described in any one.
15. 1 kinds of catalyzer for olefinic polymerization, this catalyzer contains:
(1) catalyst component for olefinic polymerization in claim 1-8 and 14 described in any one;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
16. 1 kinds of olefine polymerizing process, the method comprises: under olefin polymerization conditions, by one or more alkene and catalyst exposure, it is characterized in that, described catalyzer is the catalyzer for olefinic polymerization described in claim 15.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543307A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
| CN106543299A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application and the method for olefinic polymerization |
| CN106543300A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN111072803A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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| US4170568A (en) * | 1976-03-01 | 1979-10-09 | Bp Chemicals Limited | Polymerization catalyst |
| US4361685A (en) * | 1981-06-01 | 1982-11-30 | The Dow Chemical Company | Polymerization of olefins in the presence of catalyst prepared from organo zirconium-chromium mixtures |
| FI75845C (en) * | 1986-04-01 | 1988-08-08 | Neste Oy | CATALYTIC COMPONENT FOR POLYMERING CATALYST AV ALFAOLEFINER OCH FOERFARANDE FOER DERAS FRAMSTAELLNING. |
| CA1293242C (en) * | 1986-06-17 | 1991-12-17 | Gregory Gerasimos Arzoumanidis | Olefin polymerization catalyst |
| JP2922923B2 (en) * | 1989-07-13 | 1999-07-26 | 昭和電工株式会社 | Method for producing olefin polymerization catalyst and method for polymerizing olefin |
| IT1251462B (en) * | 1991-07-12 | 1995-05-15 | Enichem Polimeri | SOLID COMPONENT OF CATALYST FOR THE (CO) POLYMERIZATION OF ETHYLENE AND ALPHA OLEFINS. |
| DK1114070T3 (en) * | 1999-06-04 | 2004-03-01 | Lg Chemical Ltd | Process for Preparation of Polyolefin Polymerization Catalysts |
| AU2001219847A1 (en) * | 2000-12-15 | 2002-06-24 | Beijing Research Institute Of Chemical Industry, Sinopec | Spherical catalyst for (co)polymerization of ethylene, preparation and use of the same |
| CN100513438C (en) * | 2005-10-31 | 2009-07-15 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
| CN101544710B (en) * | 2008-03-28 | 2012-04-18 | 中国石油化工股份有限公司 | Magnesium halide alcohol adduct and preparation method and application thereof |
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| CN106543307A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
| CN106543299A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application and the method for olefinic polymerization |
| CN106543300A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN106543299B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application and the method for olefinic polymerization |
| CN106543300B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN111072803A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
| CN111072803B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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