CN1043233C - Process for polymerizing olefins and polymerization catalyst thereof - Google Patents
Process for polymerizing olefins and polymerization catalyst thereof Download PDFInfo
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- CN1043233C CN1043233C CN 89107190 CN89107190A CN1043233C CN 1043233 C CN1043233 C CN 1043233C CN 89107190 CN89107190 CN 89107190 CN 89107190 A CN89107190 A CN 89107190A CN 1043233 C CN1043233 C CN 1043233C
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Abstract
An olefin polymerization catalyst formed from (A) a solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients, (B) an organoaluminum compound, and (C) an organosilicon compound containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative derived from any of these groups. A polymerization process which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst to form a homopolyolefin having high stereoregularity or a copolyolefin having a narrow composition distribution.
Description
The present invention relates to a kind of polymerization process of alkene and the catalyzer that polymerization is used thereof.More particularly, it relates to the olefin homo with high stereoregularity or has preparation method who forms the narrow olefin copolymer of distribution and the catalyzer that polymerization is used thereof.
People proposed many relevant be preparation method's the motion of the solid catalyst component of main component with magnesium, titanium, halogen and electron donor, and also known and used this class solid catalyst component in polymerization process, can make polymkeric substance with high yield with high stereoregularity with 3 alpha-olefins more than the carbon.
But many solid catalyst components of Ti Chuing can't be finished the determined performance of stereoregularity such as catalytic activity and polymkeric substance etc. of complete solution up to now, are still waiting room for improvement.
For example, the solid catalyst of stating in the use prepares the polyolefine of stereoregularity, in general, just no longer carries out the separating treatment operation of catalyzer after its polymerization.Its shortcoming is the amount height of the catalyzer that left behind in low, the prepared polyolefine of the polymerization yield of per unit solid catalyst, and polyolefinic quality is also low.
Have again,, caused the corrosion of molding device because the high polyolefine of solid catalyst containing ratio relatively just contains high halogen.In order to prevent of the corrosion of this residual halogen, so hope can make the high catalyzer of unit weight solid catalyst yield to molding device.
Based on above-mentioned requirement, it is the highly active titanium catalyst component, (B) organometallic compound of main component and (C) catalyzer formed of the catalyst component of some silicoorganic compound by (A) with magnesium, titanium, halogen and electron donor that the applicant has proposed a kind of; And (referring to Japanese publication: the spy opens clear 58-83006, spy and opens clear 58-138705, spy and open clear 58-138706, spy and open clear 58-138707, spy and open that clear 58-138708, spy open clear 58-138709, the spy opens clear 58-138710 and the clear 58-138715 of Te Kai to carry out the method for the polymerization or the copolymerization of alkene in the presence of this catalyzer.
Above-mentioned catalyzer has high catalytic activity, and uses these catalyzer can obtain the polymkeric substance of good stereoregularity.Yet people wish to develop and have the more catalyzer of high catalyst activity.
On the other hand, polypropylene for example, is widely used in the field of packaging film owing to its excellent physicals has been widely used.Yet, in this purposes, in order to improve the heat seal under the low temperature.Usually with the ethylene copolymer of it and 1～5 (weight) % so that propylene ethylene copolymers to be provided.This polypropylene film and the same low-density polyethylene film that is used as packaging film through modification are compared, and have advantages such as the good transparency and resistance to marring, but still have the shortcoming of heat seal difference under the low temperature.In order further to improve heat seal, known the method for the amount that can use further increase copolymerization of ethylene, yet in this case, the ratio that does not have a soluble copolymers of use value has increased and the yield of needed multipolymer has reduced, and this is the problem of its existence.And, in the slurry polymerization process, the slurry mis-behave during polymerization, make polymerization process be absorbed in the state of difficulty.
For fear of these problems, open clear 49-35487, spy the spy and open clear 51-79195 and specially open the catalyzer that has proposed to use traditional titanous chloride type among the clear 52-16588, in polypropylene, make ethene and contain the method for 4 alpha-olefin copolymers more than the carbon.According to aforesaid method, its ratio that dissolves in the polymkeric substance of solvent of comparing with the situation of the copolymerization of propylene and ethene has reduced, yet, its ratio that dissolves in the polymkeric substance of solvent of comparing with the independent polymeric situation of propylene has increased, and along with the increase of ethene or 4 alpha-olefin copolymer amounts more than the carbon, this tendency further increases.
The present inventor finds that the carried catalyst that titanium catalyst composition, Organometal compound catalyst composition and the electronation body catalyst composition of particular solid shape are formed is used for above-mentioned propylene, ethene and 4 alpha-olefin copolymer process and above-mentioned motions more than the carbon uses the situation of titanous chloride type catalyzer to compare, its soluble polymer can further reduce and yield, the catalyst efficiency of this required multipolymer can obtain extraordinary result, and these technology have been opened in the clear 54-26891 communique the spy and proposed.By this communique as can be seen owing to having used the catalyzer of specifically revealing that significant improvement has been arranged, yet under the situation of the quite high multipolymer of preparation ethylene content, because the multipolymer that has generated the congee shape worsens size performance, cause successive polymerization to become difficult, produced and to obtain enough difficult points of the solid polymer of high yield.If in order to prepare low-melting multipolymer and can not to improve the content of ethene, can only adopt the way that improves the above alpha-olefin content of 4 carbon so, yet, this alpha-olefin is very little to the effect that reduces fusing point, and the speed of copolymerization slows down, and therefore adopts the way that improves above this alpha-olefin content of 4 carbon a kind of good plan of can not saying so.
So the present inventor opens the spy and further proposed to obtain the multipolymer that a kind of heat seal is good, that be suitable for use as film, form distribute narrow propylene, ethene and 4 alpha-olefins more than the carbon in the clear 59-4721 communique, and its undesirable solubility copolymerization by product is low, its output and the high again method of yield.Yet, not having enough heat seals, heat seal bond, the transparency and block resistance with the resulting multipolymer of this method, the amount of its soluble hydrocarbons can't reduce to makes us pleasing oneself.
On the other hand, also know, be not by random copolymerization but can make polypropylene type multipolymer by block copolymerization.These segmented copolymers are used for container, trolley part, the easy heat seal film of low temperature and high impact-resistant film etc. more.
In general, in order to improve the shock strength of above-mentioned segmented copolymer layer, the method that adopt to increase rubbery copolymer content is effectively, but this often is attended by the polymer particle bonding that tendency increases, obtained polymer particle is attached to having brought problem such as trouble on the inwall of equipment and for operate continuously steadily in the long term.In gas-phase polymerization processes, the increase of being inclined to along with the polymer particle adhesion has brought mobile deterioration of polymer particle and operation to go up fatal defective especially.Have again, the amount of polymers that dissolves in solvent in the slurry polymerization process has increased, the inappropriate increase of tackiness of slurry has brought many troubles to converging operation, and the amount of the rubbery polymer that adds in solid polymer can not make it reach the desired degree that reaches.Therefore, by the polymer particle that makes under this dissatisfied state, there are many shortcomings in low, mobile difference of its loose density and the post-processing operation such as conveying and melt-processed.
Therefore, the purpose of this invention is to provide and a kind ofly have homopolymer high polymerization activity, that can obtain good stereoregularity or form to distribute the novel catalyzer of narrow multipolymer and the polymerization process that uses this catalyzer.
Another object of the present invention provide a kind of polymerization activity be not easy in time and reduce, can make catalyzer, and the olefine polymerizing process that uses this catalyzer at for olefines polymerization of the polyolefin polymer particle of excellent propertys such as size-grade distribution, particle diameter, particle shape and loose density.
A further object of the present invention provides a kind of catalyst for olefines polymerizing that use such as its polymerization activity under the situation of hydrogen equimolecular quantity conditioning agent also can not reduce in olefin polymerization process for the polymkeric substance that makes its melt flow rate of may command, and the olefine polymerizing process that uses this catalyzer.
A further object of the present invention provides a kind of and uses the prepared polymer phase of traditional catalyzer relatively, it is few and form the catalyst for olefines polymerizing of the narrow olefin polymer that distributes and the olefine polymerizing process that uses this catalyzer to obtain to dissolve in the component of hydrocarbon.
A further object of the present invention provide a kind of can obtain such as having heat seal, heat seal bond, the transparency and block resistance good, dissolve in the polymerizing catalyst of the few polypropylene type multipolymers such as random copolymer of propylene of the component of hydrocarbon, and the polymerization process that uses this catalyzer.
Of the present invention also have a purpose to provide a kind of can the acquisition such as the polymerizing catalyst with the good propylene type copolymer of the good processing property such as random copolymer of propylene of rigidity, shock-resistance, flowability, low temperature heat seal, and the polymerization process that uses this catalyzer.
Other purpose of the present invention and advantage will become more obvious by the following description.
According to the present invention, above-mentioned purpose and advantage can and be carried out olefinic polymerization or copolymerization reaches as the olefine polymerizing process of its feature by the following catalyst for olefines polymerizing of forming in the presence of this catalyzer, and this catalyst component is:
(A) contain with magnesium, titanium and halogen be main component the solid titanium catalyst composition,
(B) organo-aluminium compound catalyzer composition and
(C) contain the organosilicon catalyst component of cyclopentyl, cyclopentenyl, cyclopentadienyl and derivative thereof.
The catalyzer of for olefines polymerization of the present invention is made up of solid titanium catalyst composition (A) and organo-aluminium compound catalyzer composition (B) and specific silicoorganic compound catalyzer composition (C).
Being used for solid titanium catalyst composition of the present invention (A) is the highly active catalyzer composition that contains magnesium, titanium and halogen at least.What especially preferentially select for use is the solid titanium catalyst composition that contains magnesium, titanium, halogen and electron donor, and it has high activity and makes polymkeric substance have high stereoregularity
This solid titanium catalyst composition (A) can be contacted with titanium compound and prepared by following magnesium compound.
The example of the titanium compound of solid titanium catalyst composition (A) preparation usefulness has the gX by structural formula Ti (OR) among the present invention
4-gShown tetravalent titanium compound (wherein R representation hydrocarbyl, the alkyl, the X that preferably contain 1-4 carbon represent halogen atom, 0≤g≤4).Concrete example has TiCl
4, TiBr
4, TiI
4Deng the quaternary halogenated titanium; Ti (OCH
3) Cl
3, Ti (OC
2H
5) Cl
3, TiO just-C
4H
9) Cl
3, Ti (OC
2H
5) Br
3, Ti (the different C of O
4H
9) Br
8Deng three halogenated alkoxy titaniums; Ti (OCH
3)
2Cl
2, Ti (OC
2H
5)
2Cl
2, Ti (O just-C
4H
9)
2Cl
2, Ti (OC
2H
5)
2Br
2Deng dihalo dialkoxy titanium; Ti (OCH
3)
3Cl, Ti (OC
2H
5)
3Cl, Ti (O just-C
4H
9)
3Cl, Ti (OC
2H
5)
3Halo tri-alkoxy titaniums such as Br; And Ti (OCH
3)
4, Ti (OC
2H
5)
4, Ti (O just-C
4H
9)
4Deng four titan-alkoxides or the like.
In these halogenous titanium compounds, what preferentially select for use is titanium tetrahalide, particularly titanium tetrachloride.These titanium compounds can use separately, also can be used in combination.These titanium compounds can use with hydrocarbon compound or halogenated hydrocarbon compound dilution back.
The example of the magnesium compound of solid titanium catalyst composition (A) preparation usefulness has the magnesium compound of reductibility and the magnesium compound of irreducibility among the present invention.
Here, the example of the magnesium compound of reductibility has magnesium compound magnesium and bond with carbon or the magnesium hydrogen bonding.The object lesson of these reductibility magnesium compounds has dialkyl magnesiums such as dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, ethyl-butyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium; Monoalkyl list halo magnesium such as ethyl-magnesium-chloride, chlorination propyl group magnesium, butyl magnesium chloride, chlorination hexyl magnesium, chlorination amyl group magnesium; The butyl magnesium ethylate; And butyl Grignard reagent or the like.These magnesium compounds can use separately, also can use and the following formed chromium complex of organo-aluminium compound.These magnesium compounds can be liquid also can be solid-state.
The object lesson of the magnesium compound of irreducibility has magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; Halogenated alkoxy magnesium such as chlorination magnesium methylate, chlorination magnesium ethylate, chlorination isopropoxy magnesium, chlorination butoxy magnesium, chlorination octyloxy magnesium; Halo aryloxy magnesium such as chlorination phenoxy group magnesium, methyl chloride phenoxy group magnesium; Magnesium ethylate, isopropoxy magnesium, butoxy magnesium, just-alkoxyl magnesium such as octyloxy magnesium, 2-ethyl hexyl oxy magnesium; Aryloxy magnesium such as phenoxy group magnesium, dimethyl phenoxy magnesium; And the carboxylate salt of magnesium such as Magnesium monolaurate, Magnesium Stearate or the like.
The magnesium compound of these irreducibility can be derived and obtained by above-mentioned reductibility magnesium compound, also can derive in the modulation catalyst composition and obtains.Derive by reductibility magnesium chemical combination and in the situation about making, for example the reductibility magnesium compound can contact with compounds such as polysiloxane compound, halogenous silane compound, halogenous aluminum compound, ester, alcohol and obtain at the magnesium compound of irreducibility.The compound of magnesium among the present invention except the magnesium chemical combination of above-mentioned reductibility magnesium compound and irreducibility, can also use the complex compound of above-mentioned magnesium compound and other metal, two compound or and the mixture of other metallic compound.These compounds also can two or more compositions mixture use.
In the present invention, in these compounds with the magnesium compound of irreducibility for well, particularly halogenous magnesium compound is better, that preferentially selects for use in them has magnesium chloride, chlorinated alkoxy magnesium and chloro aryloxy magnesium.
In the present invention, preferably use electron donor when (A) at preparation solid titanium catalyst composition, have alcohols, phenols, ketone, aldehydes, carboxylic-acid, organic or inorganic esters of gallic acid, ethers, amides, anhydrides etc. to contain nitrogenous electron donors such as positro donor and ammonia, amine, nitrile, isocyanide acids as the example of electron donor.Example has methyl alcohol, ethanol, propyl alcohol, amylalcohol, hexanol, octanol, 2-Ethylhexyl Alcohol, dodecanol, Stearyl alcohol, benzylalcohol, phenylethyl alcohol, cumic alcohol, Isobutyl Benzyl Carbinol etc. to have the alcohols of 1～18 carbon more specifically; Phenol, cresols, xylenol, ethylphenol, propylphenol, cumyl phenol, nonylphenol, naphthols etc. have the phenols that contains 6～25 carbon at last of alkyl; Acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl phenyl ketone, benzophenone etc. have the ketone of 3～15 carbon; Acetaldehyde, propionic aldehyde, octanal, benzaldehyde, tolyl aldehyde, naphthaldehyde etc. have the aldehydes of 2～15 carbon; Methyl-formiate, ethyl acetate, vinyl-acetic ester, propyl acetate, octyl acetate, hexalin acetate, ethyl propionate, methyl-butyrate, Valeric acid ethylester, Stearic ethyl stearate, the chloracetic acid methyl esters, the dichloro-ethyl acetate, methyl methacrylate, ethyl crotonate, dibutyl maleinate, the butyl malonic acid diethyl ester, dibutyltin diethyl malonate, the hexahydrobenzoic acid ethyl ester, 1,2-cyclohexane dicarboxylic acid diethyl ester, 1, the two 2-ethylhexyls of 2-cyclohexane dicarboxylic acid, the M-nitro benzoic acid methyl esters, ethyl benzoate, the M-nitro benzoic acid propyl ester, the M-nitro benzoic acid butyl ester, the M-nitro benzoic acid monooctyl ester, the M-nitro benzoic acid cyclohexyl, the M-nitro benzoic acid phenylester, the M-nitro benzoic acid benzyl ester, the toluic acid methyl esters, the toluic acid ethyl ester, the toluic acid pentyl ester, the ethyl ethyl benzoate, p-Methoxybenzoic acid methyl ester, ethyl anisate, the oxyethyl group ethyl benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), the r-butyrolactone, δ-Wu Neizhi, tonka bean camphor, the 2-benzofuranone, the desired organic acid ester described below that contains 2～30 carbon atoms in the titanium catalyst components such as NSC 11801; And organic acid ester such as tetraethyl silicate, butyl silicate, vinyltriethoxysilane, phenyl triethoxysilane, phenylbenzene diethoxy silane; The carboxylic acid halides class of 2～15 carbon such as Acetyl Chloride 98Min., benzoyl chloride, toluene acyl chlorides, anisyl chloride, phthalyl chlorine; The ethers of 2～20 carbon such as methyl ether, ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran (THF), phenylmethylether, phenyl ether; Amidess such as ethanamide, st-yrax acid amides, toluamide; St-yrax acid anhydrides, Tetra hydro Phthalic anhydride anhydrides; Amines such as methylamine, ethamine, diethylamine, Tributylamine, piperidines, tribenzylamine, aniline, pyridine, picoline, tetramethylethylened; Nitriles such as acetonitrile, benzene nitrile, toluic nitrile.
In addition, can also use silicoorganic compound shown in following general formula (I) as electron donor:
R
nSi(OR
1)
4-n …(Ⅰ)
(R and R ' representation hydrocarbyl in the formula, 0≤n＜4)
The object lesson of the silicoorganic compound shown in the above-mentioned logical formula I has the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, the tert-butyl methyl dimethoxysilane, the tert-butyl methyldiethoxysilane, uncle-amyl group methyldiethoxysilane, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, the phenylbenzene diethoxy silane, two-neighbour-tolyl dimethoxy silane, two--tolyl dimethoxy silane, two-right-tolyl dimethoxy silane, two-right-the tolyl diethoxy silane, two ethylbenzene base dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, the cyclohexyl methyl diethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, vinyltrimethoxy silane, methyltrimethoxy silane, just-propyl-triethoxysilicane, the decyl Trimethoxy silane, the decyl triethoxyl silane, phenyltrimethoxysila,e, γ-Lv Daibingjisanjiayangjiguiwan, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, the tert-butyl triethoxyl silane, just-the butyl triethoxyl silane, different-the butyl triethoxyl silane, phenyl triethoxysilane, γ-An Jibingjisanyiyangjiguiwan, the chlorination triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, 2-norbornane Trimethoxy silane, 2-norbornane triethoxyl silane, 2-norbornane methyl dimethoxysilane, tetraethyl silicate, the silane butyl ester, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl three ('beta '-methoxy Ethoxysilane), vinyltriacetoxy silane and dimethyl tetraethoxy sily oxide or the like.
That preferentially selects for use in these organosilanes has an ethyl triethoxysilane, just-propyl-triethoxysilicane, the tert-butyl triethoxyl silane, vinyltriethoxysilane, phenyl triethoxysilane, vinyl three butoxy silanes, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, two-right-tolyl dimethoxy silane, right-the tolyl methyl dimethoxysilane, dicyclohexyl dimethoxy silane, cyclohexylmethyl dimethoxy silane, 2-norbornane triethoxyl silane, 2-norbornane methyl dimethoxysilane and phenylbenzene diethoxy silane.
Can also use the silicoorganic compound that contain ring the eleventh of the twelve Earthly Branches base, cyclopentenyl, cyclopentadienyl or their derivatives.Example as these silicoorganic compound has by the compound shown in the following logical formula II.
These electron donors can two or morely be used in combination.
The desired electron donor that contains is the ester class in the titanium catalyst composition.
The example of these ester classes has by the compound shown in the following general formula:
(R wherein
1Alkyl, the R of expression replacement or non-replacement
2, R
5And R
6Alkyl, the R of expression hydrogen atom or replacement or non-replacement
3And R
4Represent the alkyl of hydrogen atom or replacement or non-replacement, wherein have one at least for replacing or non-substituted hydrocarbon radical and R
3And R
4Bonding mutually.Above-mentioned R
1～R
6Substituted hydrocarbon radical is for containing heteroatomic alkyl such as N, O, S, for example C-O-C, COOR, COOH, OH, SO
3H ,-C-N-C-, NH
2Deng.
Wherein particularly preferred is R
1, R
2In have at least one to be the dicarboxylic diester of the above alkyl of 2 carbon.
Multi-carboxylate's object lesson has ethyl succinate, dibutyl succinate, the pyrovinic acid diethyl ester, Alpha-Methyl pentanedioic acid diisopropyl ester, butyl ethyl malonate, methyl-malonic ester, ethyl malonic acid diethylester, diethyl isopropyl, the butyl malonic acid diethyl ester, phenyl ethyl malonate, diethyl malonic ester, allyl diethyl malonate, diisobutyl propanedioic acid diisobutyl ester, two-just-butyl malonic acid diethyl ester, dimethyl maleate, single-ethylhexyl maleate, dioctyl maleate, dibutyl maleinate, the butyl dibutyl maleinate, the butyl ethyl maleate, Beta-methyl pentanedioic acid diisopropyl ester, the ethyl succinic acid diallyl, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, aliphatics multi-carboxylates such as citraconic acid dioctyl ester and citraconic acid dimethyl ester; 1,2-hexahydrobenzoic acid diethyl ester, 1, alicyclic multi-carboxylates such as 2-hexahydrobenzoic acid diisobutyl ester, tetrahydrophthalic acid diethyl ester, Nalidixic Acid diethyl ester; Phthalic acid mono ethyl ester, dimethyl phthalate.The phthalic acid methyl ethyl ester, phthalic acid list isobutyl ester, phthalic acid list-positive butyl ester, diethyl phthalate, phthalic acid ethyl isopropyl ester, the phthalic acid ethyl-just-butyl ester, phthalic acid is two-just-and propyl diester, diisopropyl phthalate, phthalic acid is two-just-and butyl ester, diisobutyl phthalate, phthalic acid is two-just-and the heptyl ester, phthalic acid is two-the 2-(ethyl hexyl) ester, phthalic acid is two-just-and the octyl group ester, phthalic acid two peopentyl esters, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, naphthyl dicarboxylic acid diethyl ester, naphthyl dicarboxylic acid dibutyl ester, triphen six triethylenetetraminehexaacetic acid base esters, aromatic series multi-carboxylates such as three mellic acid tributyl esters; 3, heterocycle multi-carboxylates such as 4-furans dicarboxylic acid etc.
The object lesson of polyol ester class has 1,2-diacetyl benzene, 1-methyl-2,3-diacetyl benzene, 2,3-diethyl naphthone, two PIVALIC ACID CRUDE (25) glycol esters and PIVALIC ACID CRUDE (25) butanediol ester etc.
The object lesson of the carboxylic acid esters that hydroxyl replaces has Whitfield's ointment benzoyl ethyl ester, Whitfield's ointment acetyl isobutyl ester and the acetyl of poplar acid forever methyl esters etc.
Multi-carboxylate's class in the available titanium catalyst component, except above-claimed cpd, also can use diethylene adipate, diisobutyl adipate, Wickenol 117, sebacic acid two-just-butyl ester, sebacic acid be two-just-octyl group ester, sebacic acid be two-the dicarboxylic ester class of long-chains such as 2-ethyl ester.
The compound that has above-mentioned general formula skeleton in these multifunctional ester classes is preferentially selected for use, especially the ester class that generates with the propanedioic acid of phthalic acid, toxilic acid or replacement etc. and two alcohol more than the carbon is for well, and especially the ester class with phthalic acid and 2 alcohol generations more than the carbon is best.
Other the example that can be used as electron donor in the titanium catalyst component has by RCOOR
1Shown monocarboxylate (wherein R and R ' are the fatty group that has (the including the fat cyclic) of side chain or contain ring for having substituent alkyl and having one at least).The object lesson that can be used as R and R ' base has (CH
3)
2CH-, C
2H
5CH (CH
3)-, (CH
3)
2CHCH
2-, (CH
3)
3C-, C
2H
5CH-, (CH
3) CH
2-,
Deng group.If have one among R and the R ' for above-mentioned group, another can be above-mentioned group and also can be other group so, for example straight chain shape or cyclic group.
Various monocarboxylates' object lesson has the various monoesters of dimethyl acetic acid, trimethylacetic acid, α-Jia Jidingsuan, Beta-methyl butyric acid, methacrylic acid and benzoyl acetate etc.; With by monocarboxylates that alcohols generated such as Virahol, isopropylcarbinol and uncle-butanols.
Can also use carbonic ether as electron donor.Its object lesson has diethyl carbonate, NSC 11801, carbonic acid diisopropyl ester, carbonic acid phenethyl ester and diphenyl carbonate.
But when these electron donors of precipitation, there is no need it is directly used as raw material, also can use those in the preparation process of titanium catalyst, can be transformed into the compound of these electron donors.
Other electron donor that in titanium catalyst component, can coexist, but since its a large amount of existence have bad influence thereby should limit it and exist slightly.
In the present invention, solid titanium catalyst composition (A) can preferably also have electron donor to contact and make by above-mentioned magnesium compound (or MAGNESIUM METAL) and titanium compound.In solid titanium catalyst composition (A) preparation process, can adopt known method, make highly active titanium catalyst composition by magnesium compound, titanium compound and electron donor.In addition, be preferably in and make the above-claimed cpd contact under the existence of other reaction reagents such as silicon, phosphorus, aluminium.
The preparation method of these solid titanium catalyst compositions (A) can lift numerical example and be summarized as follows.
(1) magnesium compound or the complex compound of forming by magnesium compound and electron donor and the titanium compound method of in liquid phase, reacting.This reaction can be carried out in the presence of disintegrator etc.Have, in above-mentioned reaction, the solid state compound is preferably pulverized earlier again.
(2) the liquid magnesium compound and the liquid titanium compound of irreducibility react in the presence of electron donor and separate out the method for solid titanium complex.
(3) reaction product that makes by (2) further with the method for titanium compound reaction.
(4) reaction product that makes by (1) or (2) method of further reacting with electron donor and titanium compound.
(5) magnesium compound or the complex compound be made up of magnesium compound and electron donor are pulverized the method that the solid product of back gained is handled with halogen, halogen compounds and aromatic hydrocarbons again in the presence of titanizing is closed.In the method, magnesium compound or the complex compound of forming by magnesium compound and electron donor, preferably existence such as disintegrator is pulverized down.Have again, magnesium compound or pulverize in the presence of titanium compound by the complex compound that magnesium compound and electron donor are formed after, give processing with reaction promoter again, subsequently, the most handy halogen etc. is handled.The example of these reaction promoters has organo-aluminium compound or halogenous silicon compound.
(6) method of handling with halogen or halogen compounds or aromatic hydrocarbons by compound that (1)～(4) make.
(7) method that the contact reacts product of metal oxide, dialkyl magnesium and halogen-containing alcohol is contacted with electron donor and titanium compound.
(8) method that magnesium compound and electron donor, titanium compound and/or the halogen-containing hydrocarbon of organic acid magnesium salts, aluminum alkoxide, aryloxy aluminium etc. reacted.
In above-mentioned (1)～(8) in the middle of the cited method for preparing solid titanium catalyst composition (A), in preparation, use the method for liquid halogenated titanium or after using titanium compound or to use the method for halon during using titanium compound be the method for preferentially selecting for use.
The consumption of solid titanium catalyst composition (A) used above-mentioned each component in preparation process, can not make unified regulation because of the method for preparation is different, for example, magnesium compound corresponding to 1 mole, about 0.01～5 mole of the consumption of electron donor, be preferably 0.05～2 mole, about 0.01～500 mole of the consumption of titanium compound, be preferably 0.05～300 mole.
The solid titanium catalyst composition (A) that makes like this contains major ingredient magnesium, titanium, halogen and electron donor.
In this solid titanium catalyst composition (A), halogen/titanium (atomic ratio) is about 4～200, preferably is about 5～100, above-mentioned electron donor/titanium (mol ratio) is about 0.1～10, preferably is about 0.2～6, and magnesium/titanium (atomic ratio) is about 1～100, preferably is about 2～50.
This solid catalyst composition (A) is compared with commercially available magnesium halide, contains less crystal grain magnesium halide, and its specific surface area is approximately greater than 50 meters usually
2/ restrain, preferably be about 60～1000 meters
2/ gram better is about 100～800 meters
2/ gram.Because above-mentioned composition is to make the as a whole catalyzer composition that constituted, therefore use hexane wash, can not change the composition of this solid titanium catalyst composition (A) in essence.
This solid titanium catalyst composition (A) can use separately, also can be with such as re-using after mineral compound such as silicon compound, aluminum compound, polyolefine or the organic compound dilution.In the occasion of thinner use, though littler than above-mentioned specific surface area, but show high catalytic activity.
The method for preparing the high activated catalyst component that can adopt among the present invention is described in following Japanese patent gazette.They are that the spy opens clear 50-108385, same 50-126590, same 51-20297, same 51-28189, same 51-64586, same 51-92885, same 51-136625, same 52-87489, same 52-100596, with the same 52-104593 of 52-147688, same 53-2580, same 53-40093, same 53-40094, same 53-43094, same 55-135102, same 55-135103, same 55-152710, same 56-811, same 56-11908, same 56-18606, same 58-83006, same 58-138705, same 58-138706, same 58-138707, same 58-138708, same 58-138709, with the same 58-13815 of 58-138710, same 60-23404, same 61-21109, same 61-37802, with 61-37803 or the like.
As organic compound catalyzer composition (B), can use the compound that in molecule, has an aluminium-bond with carbon at least.The example of this compounds is as follows:
(I) general formula R
11 mAl (OR
12) nHPX
1 qThe organo-aluminium compound of expression
(R in the formula
11And R
12Be generally and contain 1～15 carbon, preferably contain the alkyl of 1～4 carbon, they can be the same or different.X
1The expression halogen atom, 0＜m≤3,0≤n＜3,0≤P＜3,0≤q＜0 and m+n+P+q=3),
(II) formula M
1AlR
11 4The first family metal of expression and the complexing alkylide (M in the formula of aluminium
1Be Li, Na, K, R
11As previously mentioned) organo-aluminium compound that belongs to above-mentioned (I) is listed below: general formula R
11 mAl (OR
12)
3-mShown compound (R in the formula
11And R
12As previously mentioned, m is preferably 1.5≤m≤3), general formula R
11 mAlX
1 3-mShown compound (R in the formula
11X as previously mentioned,
1Represent halogen, m to be preferably 0＜m＜3), general formula R
11 mAlH
3-mShown compound
(R in the formula
11As previously mentioned, m is preferably 2≤m＜3),
General formula R
11 mAl (OR
12)
nX
1 qShown compound
(R in the formula
11And R
12X as previously mentioned,
1Represent halogen, 0＜m≤3,0≤n＜3,0≤q＜3, m+n+q=3)
The object lesson that belongs to the organo-aluminium compound of (I) has trialkylaluminiums such as triethyl aluminum and tri-butyl aluminum; Three alkenyl aluminium such as three pseudoallyl aluminium;
Aluminum dialkyl alkoxide such as diethyl aluminum ethylate, dibutyl aluminium butanolate;
Aluminum alkyls sesquialter alkoxide such as aluminium triethyl sesquialter ethylate and butyl aluminium sesquialter butanolate;
Use R
2.5Al (OR
12)
0.5In its average form part alkoxylated alkyl group aluminium of expression;
Dialkylaluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide;
Aluminum alkyls sesquihalide such as ethyl aluminium sesqui chloride, butyl aluminium sesquichloride and aluminium triethyl sesquialter bromide;
Partially halogenated aluminum alkylss such as alkyllithium dihalide such as ethyl aluminum dichloride, propyl group aluminium dichloride, butyl aluminium dibromide; Dialkyl aluminum hydrides such as diethyl aluminum hydride, dibutyl alanate; The hydrogenant aluminum alkyls of other parts such as aluminum alkyls dihydride such as aluminium triethyl dihydride, propyl group aluminium dihydride;
Part alkoxylate and halogenated aluminum alkylss such as aluminium triethyl oxyethyl group muriate, butyl aluminium butoxy muriate, aluminium triethyl oxyethyl group bromide.
Can use in addition oxygen or nitrogen-atoms and two or above aluminium atom mutually bonding with (ⅰ) similar organo-aluminium compound, its example has: (C
2H
5)
2AlOAl (C
2H
5)
2, (C
4H
9)
2AlOAl (C
4H
5)
2,
And methyl Lv oxane.
The example that belongs to the compound of above-mentioned (ⅱ) has LiAl (C
2H
5)
4, LiAl (C
7H
15)
4Deng.
Wherein preferentially select for use trialkylaluminium or above-mentioned more than two kinds the aluminum compound bonding and the aluminum alkyls that generates.
As catalyst component (C), operable the silicoorganic compound that contain cyclopentyl, cyclopentenyl, cyclopentadienyl or their deriveding group in its structure are arranged.
As this silicoorganic compound, preferably use the compound shown in following general formula (II):
SiR
21R
22 m(OR
23)
3-m …(Ⅱ)
In formula II, 0≤m＜3, best 0≤m≤2, m=2 better; R
21Represent cyclopentyl, cyclopentenyl, cyclopentadienyl or their deriveding group.The preferred example of these deriveding groups has by 1～4 cyclopentyl that alkyl replaced that contains 1～4 carbon atom, by the alkyl that contains 2～4 carbon atoms (this cyclopentyl can be replaced by 1～4 alkyl that contains 1～4 carbon atom) of 1 cyclopentyl replacement, by 1～4 cyclopentenyl that contains the alkyl replacement of 1～4 carbon atom, by 1～4 cyclopentadienyl that contains the alkyl replacement of 1～4 carbon atom, and can be by 1～4 indenyl, indanyl, tetrahydroindenyl or fluorenyl that contains the alkyl replacement of 1～4 carbon atom.As R
21Object lesson cyclopentyl arranged, the 2-methylcyclopentyl, the 3-methylcyclopentyl, 2-ethyl cyclopentyl, 3-propyl group cyclopentyl, 3-sec.-propyl cyclopentyl, 3-butyl cyclopentyl, 3-tertiary butyl cyclopentyl, 2, the 2-dimethylcyclopentyl, 2, the 3-dimethylcyclopentyl, 2, the 5-dimethylcyclopentyl, 2,2,5-trimethylammonium cyclopentyl, 2,3,4,5-tetramethyl-ring amyl group, 2,2,5,5-tetramethyl-ring amyl group, 1-cyclopentyl propyl group, 1-methyl isophthalic acid-cyclopentyl ethyl, cyclopentenyl, the 2-cyclopentenyl, the 3-cyclopentenyl, 2-methyl isophthalic acid-cyclopentenyl, 2-methyl-3-cyclopentenyl, 3-methyl-3-cyclopentenyl, 2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl, 2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl--3-cyclopentenyl, 2,2,5,5-tetramethyl--3-cyclopentenyl, 1, the 3-cyclopentadienyl, 2, the 4-cyclopentadienyl, 1, the 4-cyclopentadienyl, the 2-methyl isophthalic acid, the 3-cyclopentadienyl, 2-methyl-2, the 4-cyclopentadienyl, 3-methyl-2, the 4-cyclopentadienyl, 2-ethyl-2, the 4-cyclopentadienyl, 2,2-dimethyl-2, the 4-cyclopentadienyl, 2,3-dimethyl-2, the 4-cyclopentadienyl, 2,5-dimethyl-2, the 4-cyclopentadienyl, 2,3,4,5-tetramethyl--2, the 4-cyclopentadienyl, indenyl, 2-methyl indenyl, the 2-ethyl-indenyl, the 2-indenyl, 1-methyl-2-indenyl, 1,3-dimethyl-2-indenyl, indanyl, 2-methyl indan base, the 2-indanyl, 1,3-dimethyl-2-indanyl, 4,5,6, the 7-tetrahydroindenyl, 4,5,6,7-tetrahydrochysene-2-indenyl, 4,5,6,7-tetrahydrochysene-1-methyl-2-indenyl, 4,5,6,7-tetrahydrochysene-1,3-dimethyl-2-indenyl, fluorenyl or the like.
In formula II, R
22And R
23It can be identical or different alkyl.R
22And R
23Example alkyl such as alkyl, cycloalkyl, aryl, aralkyl are arranged.
Have again, in formula II, R
21And R
22Can get up for good with the alkyl bridge joint.
In the middle of this, R
21Be cyclopentyl, R
22Be alkyl or cyclopentyl, R
23For the silicoorganic compound of alkyl (particularly methyl or ethyl) are particularly preferred.
Silicoorganic compound as above-mentioned formula II, concrete example has cyclopentyl Trimethoxy silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, 2,5-dimethylcyclopentyl Trimethoxy silane, cyclopentyl triethoxyl silane, cyclopentenyl Trimethoxy silane, 3-cyclopentenyl Trimethoxy silane, 2, trialkoxysilanes such as 4-cyclopentadienyl Trimethoxy silane, indenyl Trimethoxy silane, fluorenyl Trimethoxy silane;
Dicyclopentyl dimethoxyl silane, two (2-methylcyclopentyl) dimethoxy silane, two (3-tertiary butyl cyclopentyl) dimethoxy silane, two (2,3-dimethylcyclopentyl dimethoxy silane, two (2, the 5-dimethylcyclopentyl) dimethoxy silane, two cyclopentyl diethoxy silanes, dicyclopentenyl dimethoxy silane, two (3-cyclopentenyl) dimethoxy silane, two (2,5-dimethyl-3-cyclopentenyl) dimethoxy silane, two-2,4-cyclopentadienyl dimethoxy silane, two (2,5-dimethyl-2, the 4-cyclopentadienyl) dimethoxy silane, two (1-methyl isophthalic acid-cyclopentyl ethyl) dimethoxy silane, cyclopentyl cyclopentenyl dimethoxy silane, cyclopentenyl cyclopentadienyl dimethoxy silane, two indenyl dimethoxy silane, two (1,3-dimethyl-2-indenyl) dimethoxy silane, cyclopentadienyl indenyl dimethoxy silane, two fluorenyl dimethoxy silane, cyclopentyl fluorenyl dimethoxy silane, dialkoxy silicane classes such as indenyl fluorenyl dimethoxy silane;
Three cyclopentyl methoxy silane, three cyclopentenyl methoxy silane, three cyclopentadiene methoxylsilanes, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane, two cyclopentyl ethyl methoxy silane, two cyclopentyl-methyl Ethoxysilanes, cyclopentyl dimethyl methyl TMOS, cyclopentyl diethyl methoxy silane, the cyclopentyl dimethylethoxysilane, two (2, the 5-dimethylcyclopentyl) cyclopentyl methoxy silane, two cyclopentyl, two cyclopentyl cyclopentenyl methoxy silane, monoalkoxy silane such as two cyclopentyl cyclopentadiene methoxy silane and two indenyl rings amyl group methoxy silane; And
Ethylenebis cyclopentyl methoxy silane or the like.
In polymerization process of the present invention, in the presence of above-mentioned catalyzer, carry out the polymerization of alkene, but preferably carry out following prepolymerization before earlier carrying out this polymerization (main polymerization).
In prepolymerization, the organo-aluminium compound (B) with above-mentioned solid titanium catalyst composition (A) and above-mentioned at least a portion is used in combination together usually.At this moment can partly or entirely carry out polymerization in the presence of the silicoorganic compound (C).
In prepolymerization, can use than catalyst concn higher in the main polymerization system.
The concentration of solid titanium catalyst composition (A) in prepolymerization with respect to 1 liter of following unreactive hydrocarbons medium and be converted into titanium atom and calculate and to be about 0.01～200 mmole usually, preferably is about 0.05～100 mmole.
The consumption of organo aluminum catalyst composition (B), preferably be preferably 0.3～300 gram for well can generate 0.1～500 gram polymkeric substance with respect to 1 gram solid titanium catalyst composition, promptly with respect to 1 mole of titanium atom in the solid titanium catalyst composition (A), be about 0.1～100 mole usually for well.
Pre-polymerization process is preferably in the unreactive hydrocarbons medium and adds alkene and above-mentioned catalyzer composition and carry out under mild conditions.
Object lesson of used unreactive hydrocarbons medium has aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene in the middle of this; Alicyclic hydro carbons such as ring the eleventh of the twelve Earthly Branches alkane, hexanaphthene and methylcyclopentane; Benzene, toluene and dimethylbenzene etc. are aromatic hydrocarbon based; Halogenated hydrocarbon such as ethylene chloride and chlorinated benzene; And their mixture.In these unreactive hydrocarbons media especially to use aliphatic hydrocarbon for well.
In addition, in the present invention, can use liquefied olefines to come partly or wholly to substitute above-mentioned unreactive hydrocarbons medium.
The alkene that uses in prepolymerization can be identical or different with employed alkene in the main polymerization described later.
The temperature of prepolymerization reaction, the temperature that best prepolymer with generation is insoluble to the unreactive hydrocarbons medium basically is advisable, and is about-20～+ 100 ℃ usually, preferably is about-20～+ 80 ℃, is about in 0～+ 40 ℃ of scope better.
In prepolymerization, can use the molecular weight regulator such as hydrogen.The consumption of this molecular weight regulator can use in this wise and make the polymkeric substance that obtains is measured in 135 ℃ naphthalane in the prepolymerization limiting viscosity (η) more than 0.2 deciliter/gram, preferably be about 0.5～10 deciliter/gram.
As mentioned above, pre-polymerization process preferably makes titanium catalyst composition with respect to 1 gram can generate in this wise to be about 0.1～1000 and restrains, preferably is about 0.3～500 polymkeric substance that restrains.Excessive as the amount of polymers that generates in the polymerization process, the productive rate that generates olefin polymer so in main polymerization will reduce, and when simultaneously the olefin polymer that is obtained being processed into finished product such as film, will generate " flake " easily.
Pre-polymerization process can adopt intermittent type also can adopt the continous way process.
After having carried out above-mentioned pre-polymerization process, perhaps do not carry out pre-polymerization process, can in the presence of the catalyzer of for olefines polymerization of forming by above-mentioned solid titanium catalyst composition (A), organo aluminum catalyst composition (B) and organosilicon catalyzer composition (C), carry out the main polymerization of alkene.
The example of used alkene has ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-octene, 1-hexene, 3-Methyl-1-pentene, 3-methyl-1-butene, 1-decene, tetradecene and 1-eicosylene etc. to have the alpha-olefin of 2～20 carbon atoms in main polymerization.
In polymerization process of the present invention, these alkene can use separately also can mix use.
In a specific embodiments of the present invention, can use propylene or 1-butylene to carry out equal polymerization, perhaps using with propylene or 1-butylene is that the mixed olefins of main composition carries out copolymerization.Under the situation of using mixed olefins, more than the %, be preferably in 70 (moles) more than the % at 50 (moles) usually as the propylene of major ingredient or the content of butylene.
In this embodiment, when using in the above-mentioned pre-polymerization process used catalyzer, can be 2～10 by carbon number, be preferably 3～10 alpha-olefin and make polymkeric substance with high crystalline.
According to the situation of carrying out of pre-polymerization process, can adjust the activity of such catalysts degree that uses in the main polymerization, through such adjustment, can tend to obtain the big powder polymer of loose density.Have, when carrying out prepolymerization, the powder shape of the polymkeric substance of Sheng Chenging is a spheric especially again, and under the situation of slurry polymerization, makes the slurry performance become excellent.
Also have, in this embodiment, especially with carbon number when the alpha-olefin more than 3 carries out polymerization, can high catalytic efficiency ground prepare and have high stereoregularity exponential polymkeric substance.
In the equal polymerization process or copolymerization process of these alkene, can use compound such as conjugated diolefine or non-conjugated diene as comonomer with a plurality of unsaturated link(age)s.
In polymerization process of the present invention, the main polymerization of alkene is carried out in gas phase or liquid phase usually.
When the situation of slurry polymerization form was adopted in main polymerization, above-mentioned inertia hydro carbons was made reaction medium, also can use the alkene that is in a liquid state under temperature of reaction as reaction medium.
In polymerization process of the present invention, the consumption of above-mentioned titanium catalyst component (A), the polymerization volume with respect to every liter also are converted into Ti atom meter, are about 0.001～0.5 mmole usually, preferably are about 0.005～0.5 mmole.Also have, the consumption of the catalyst component of organo-aluminium compound (B), with respect to every mole of titanium atom in the titanium catalyst component in the polymerization system (A), the consumption in the organo-aluminium compound catalyst component (B) in the atoms metal, be about 1～2000 mole usually, preferably be about 5～500 moles.Have again, the consumption of silicoorganic compound catalyzer composition (C), with respect to the every mole metal atom in the organo-aluminium compound catalyzer composition (B) and be converted into Siliciumatom meter in the silicoorganic compound catalyzer composition (C), usually be about 0.001～10 mole, preferably be about 0.02～2 mole, be about 0.05～1 mole particularly well.
In polymerization process of the present invention, titanium catalyst composition (A), organo-aluminium compound catalyzer composition (B) and silicoorganic compound catalyzer composition (C) can contact when main polymerization, also can for example contact when prepolymerization before main polymerization.When before main polymerization, contacting, can at random select any two kinds of compositions to contact, also can select the part of each composition to carry out contact between both or the three.
In polymerization process of the present invention, before polymerization, can under inert atmosphere, also can under alkene atmosphere, make each catalyzer composition contact.
Partly use in prepolymerization under the situation of organo-aluminium compound catalyzer composition (B) and organosilicon catalyzer composition (C), the catalyzer that uses in the prepolymerization can use together with residual catalyzer.In this case, the catalyzer that uses in the prepolymerization can contain and gives polymerized product.
In main polymerization process, use hydrogen can regulate the molecular weight of prepared polymkeric substance, still, the melt flow rate of resulting polymers is big.In this case, in polymerization process of the present invention, the stereoregularity index of the polymkeric substance of generation can not reduce, and catalyst activity can not reduce yet.
In the present invention, the temperature of olefinic polymerization is about 20～200 ℃ usually, preferably is about 50～180 ℃, and its pressure is generally normal pressure～100 kg/cm, is preferably about 2～50 kg/cm.In the method for the invention, can adopt intermittent type, semi continuous or continous way to carry out polymerization.Polymerization process can be carried out respectively in two different above stages at reaction conditions.
The olefin polymer that makes like this can be homopolymer, random copolymers or segmented copolymer.
In the present invention, because the yield of the stereoregularity polymkeric substance that is obtained with respect to the solid catalyst composition of unit vol is very high, the catalyst residue in the polymkeric substance, particularly content of halogen can relatively reduce.Therefore, remove the operating process of catalyzer in the polymkeric substance and can save, can effectively prevent the corrosion of metal die when the olefin polymer that generates is processed into goods.
Owing to use in the obtained polymkeric substance of catalyzer of the present invention atypic polymkeric substance composition considerably less, the composition that therefore dissolves in hydrocarbon seldom, the surface viscosity that makes film with these polymer processing is very low.
The polyolefine that polymerization process according to the present invention makes, good and its prepared multipolymer of its size-grade distribution, particle diameter and loose density have very narrow composition and distribute.
In another preferential embodiment of the present invention, in the presence of above-mentioned catalyzer, alpha-olefin propylene and 2 carbon or that have 2～20 carbon is carried out copolymerization.At this moment can use the above-mentioned catalyzer used in the polymerization that gives.
According to the situation that prepolymerization is carried out, can adjust activity of such catalysts degree in the main polymerization, this adjustment is tended to generate has the high powder polymer of loose density.In addition, when carrying out pre-polymerization process, the polymer powder of generation be shaped as spheric, and under the situation of slurry polymerization, it is excellent that the performance of its slurry becomes.Therefore, the manufacture method of propylene list multipolymer according to the present invention, prepared copolymer powder or multipolymer slurry become and handle easily.
The alpha-olefin of 2 carbon is an ethene, and used carbon number is that 4～20 alpha-olefin has 1-butylene, 1-heptene, 4-methyl isophthalic acid-heptene, 1-octene, 1-hexene, 3-methyl isophthalic acid-heptene, 3-methyl-1-butene, 1-decene and tetradecene etc.
In main polymerization, propylene can carry out copolymerization with alpha-olefin above-mentioned more than two kinds, and for example, propylene and ethene and 1-butylene carry out copolymerization.
In the present invention, propylene and ethylene copolymerization or propylene and 1-butylene copolymerization or propylene and ethene and 1-butylene copolymerization are particularly preferred.
The segmented copolymer process of propylene and other alpha-olefin can be divided into last stage polymerization and latter stage polymerization process.
The polymerization of last stage can be that the equal polymerization of propylene also can be the copolymerization of propylene and other alpha-olefin.The preferably copolymerization of propylene and ethene, the perhaps copolymerization of propylene and ethene and butylene.
In the last stage polymeric amount preferably account for about 50 (weight) %～about 95 (weight) % of final product, better for about 60 (weight) %～about 90 (weight) %.In the present invention, the polymerization process of this last stage also can be further be aggregated in this case more than in two steps, and each step can also can carried out under different conditions under the identical condition.
In the latter stage polymerization, the mol ratio of propylene and other alpha-olefin is preferably in 10/90～90/10, better 20/80～80/20, good especially be to carry out polymerization 30/70～70/30 time.
In the polymerization engineering in above-mentioned stage, be designed to also be suitable for other alpha-olefin crystallinity homopolymer or multipolymer.
The propylene series copolymer that makes like this can be random copolymers or above-mentioned segmented copolymer.It is 2 or 4～20 alpha-olefin that this propylene series copolymer preferably contains carbon number, its amount is 7～50 moles of %, be that preferably to contain carbon number in the random copolymers be that the consumption of the alpha-olefin of 2 or 4～20 carbon is 7～20 moles of %, is 7～18 moles of % better especially at propylene, be 8～15 moles of % particularly well, and in the propylene based block copolymer, the amount that preferably contains carbon number and be the alpha-olefin of 2 or 4～20 carbon is 10～50 moles of %, is 20～50 moles of % better, is 25～45 moles of % particularly well.
The tensile strength of the propylene series copolymer that is generated (FM) below 8,000 kg/cm, is preferably in below 6,000 kg/cm usually.
Aforesaid propylene be the fusing point (being designated hereinafter simply as the DSC fusing point) measured of the differential scanning calorimetry of random copolymers, preferably 90～130 ℃, better 95～175 ℃, be in 100～120 ℃ scope particularly well.In the fusing point measuring process, used the DSC-7 type survey meter of パ-キ Application ェ Le マ-corporate system, the thickness that left standstill after the moulding 20 hours is 0.1 millimeter the compressing tablet that adds, be heated to 200 ℃, and be cooled to after 25 ℃ again with 10 ℃/minute speed and rise to 200 ℃ with 10 ℃/minute heat-up rate by 25 ℃ to measure the temperature T m shown in its maximum endothermic peak be the DSC fusing point.
The aforesaid propylene based block copolymer is dissolved under 23 ℃ in the positive decane, and its solvable composition is preferably in 20～70 weight %, better at 30～60 weight %, particularly well in the scope of 40～60 weight %.This multipolymer just is being dissolved under 23 ℃-the Ding decane in, solvable one-tenth component is pressed the row method and is measured.In 1 liter of flask of agitating vane is housed, the multipolymer test portions of 3 grams of packing into, add 20 milligrams 2, the decane of 6-two-tertiary butyl-4-cresylol and 500 milliliters places it in 145 ℃ the oil bath and makes molten Jie of multipolymer.Treat after molten Jie of multipolymer, at room temperature naturally cooling is 8 hours, be placed on subsequently in 23 ℃ the oil bath 20 hours, and with the glass filter of G-4 with the multipolymer of separating out and contain soluble polymer just-decane separates, the solution of gained descends with 10 milliliters of Hg dryings till constant at 150 ℃, measure its weight,, and represent with percentage ratio with the solubility component of dissolved multipolymer in the above-mentioned mixing solutions weight divided by the test portion multipolymer.
Being construed as the same that compound, polymerization process, catalyst consumption and catalytic condition etc. that do not mention spendable have many unsaturated link(age)s and above-mentioned embodiment put down in writing here all will be suitable for.
According to the present invention, polypropylene-based multipolymer such as low-melting polypropylene-based random copolymers can high yield, make with high yield, and in addition, the amount of by product that dissolves in the multipolymer of hydrocarbon can reduce.Can be in the suspension polymerization process without any carrying out polyreaction troublesomely.Because the output of the multipolymer that per unit titanium obtained is very big, removes the operating process of catalyzer after the polymerization and can omit.
The polypropylene-based segmented copolymer that makes according to the present invention has good heat seal, heat seal tackiness, the transparency, block resistance.Because the composition that dissolves in hydrocarbon seldom, its is suitable for film field, particularly packaging film field, for example food packing film such as shrinkable film.
In addition, can high catalytic efficiency according to the present invention and good processing property make polypropylene-based segmented copolymer with good melt fluidity, formability, rigidity, shock-resistance and powder flowbility.
To explain the present invention by the following examples, be not restriction the present invention but exemplify these embodiment.Embodiment 1
The preparation of solid titanium catalyst composition (A)
Magnesium Chloride Anhydrous 7.14 gram (75 mmole), 37.5 milliliters of decane and 2-Ethylhexyl Alcohol 35.1 milliliters (225 mmole) 130 ℃ of following reacting by heating 2 hours, are made it to become uniform solution.Interpolation Tetra hydro Phthalic anhydride 1.67 restrains (11.3 mmole) in this solution subsequently, further mixes Tetra hydro Phthalic anhydride is dissolved in the above-mentioned uniform solution under 130 ℃.
Institute is obtained homogeneous solution be cooled to after the room temperature, within one hour it is all being splashed among the titanium tetrachloride of 200 milliliters (1.8 moles) remaining under-20 ℃.After having added, in 4 hours, gained solution is warming up to 110 ℃, when reaching 110 ℃, adds the o-benzene butyl phthalate ester of 5.03 milliliters (18.8 mmoles).
Under said temperature, further stirred 2 hours.After reaction in 2 hours, collect the TiCl that obtains solid part, this solid part is suspended in 275 milliliters through heat filtering
4Among, again 110 ℃ of following reacting by heating 2 hours.
After reaction ends, collect through heat filtering again and obtain solid part, wash with 110 ℃ decane and hexane again, till in washings, not detecting titanium compound.
Above-mentioned synthetic solid titanium catalyst composition (A) is that the form with the hexane slurry makes.Get its a part of catalyzer and carry out drying.The exsiccant product is analyzed, and what its result showed the above-mentioned solid titanium catalyst composition (A) that makes consists of titanium 2.5 (weight) %, chlorine 58 (weight) %, magnesium 18 (weight) % and diisobutyl phthalate 13.8 (weight) %.
Prepolymerization
In 400 milliliters that cross with purging with nitrogen gas glass reactor, add 200 milliliters of purified hexanes, and afterwards at the above-mentioned titanium catalyst composition (A) that adds 20 mmole triethyl aluminums, 4 mmole dicyclopentyl dimethoxyl silanes and 2 mmoles (calculating) with titanium atom, with 5.9 standard liters/hour speed fed propylene totally 1 hour, can make the propylene polymerizations of 2.8 grams with respect to the Ti catalyzer composition (A) of 1 gram.
After prepolymerization ends, remove liquid portion after filtration, with isolated solid part redispersion in decane.
Main polymerization
At internal volume is the propylene that add 500 grams in 2 liters the autoclave, under 60 ℃, add the above-mentioned solid titanium catalyst composition (A) that polymerization uses (calculating) that gives of 0.6 mmole triethyl aluminum, 0.06 mmole dicyclopentyl dimethoxyl silane and 0.006 mmole with titanium atom, add again after 1 liter of hydrogen, be warming up to 70 ℃, made propylene polymerization 40 minutes.
With the polymkeric substance drying of above-mentioned generation, its weight of weighing, the full production capacity of this polymkeric substance are 279 grams.
This polymkeric substance through ebullient just-residual rate after the heptane extraction is 99.2%, its MFR is 6.3 Grams Per Minutes.Therefore, Ci Shi polymerization activity is 46,500 gram-propylene/mmole titanium.
Used polymerization catalyst activity, institute obtain polyacrylic through boiling just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 1.
Embodiment 2
Repeat the test of embodiment 1, just the amount of triethyl aluminum is changed into 6 mmoles and is not added dicyclopentyl dimethoxyl silane by 20 mmoles in giving polymerization.
Used polymerization catalyst activity, the polyacrylic boiling that is obtained just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 1.
Embodiment 3
The preparation of solid titanium catalyst composition (A)
's 2 liters high-speed stirring apparatus (special machine chemical industry (strain) system) with nitrogen with internal volume
Carry out sufficient purge, add 700 milliliters of purified kerosene, the commercially available MgCl of 10 grams
2, 24.2 gram ethanol and 3 gram dehydrated sorbitol distearates (trade(brand)name ェ マ ゾ-Le 320, flower king ア ト ラ ス (strain) system), system stir is heated up, under 120 ℃, stirred 30 minutes with 800 rev/mins.
In another Jie's capacity is 2 liters the glass flask that agitator is housed, add 1 liter of purified kerosene, be cooled to-10 ℃.
With 5 millimeters teflon pipe, with the above-mentioned MgCl that contains
2Kerosene raffinate be moved in the kerosene raffinate of above-mentioned being cooled to-10 ℃.
The solid part that generates is collected after filtration, and fully wash obtained carrier with hexane.
After at room temperature being suspended in the 7.5 gram carriers that make in 150 milliliters the titanium tetrachloride, adding 1.3 milliliters of o-benzene butyl phthalate esters, be warming up to 120 ℃.Under 120 ℃, after mixing 2 hours, solid part filtered collect, again it is suspended in 150 milliliters the titanium tetrachloride, under 130 ℃, mixed again 2 hours.
Then, collect the reaction solid product after filtration, and wash, made solid titanium catalyst composition (A) with the refined hexane of q.s.
This solid catalyst composition (A) through atom conversion titaniferous 2.2 (weight) %, chloride 63 (weight) %, contain magnesium 20 (weight) %, contain o-benzene butyl phthalate ester 5.0 (weight) %.
Prepolymerization
The above-mentioned solid titanium catalyst composition (A) (calculating with titanium atom) that add 200 milliliters of purified hexanes in 400 milliliters of glass reactors of crossing with purging with nitrogen gas, adds the dicyclopentyl dimethoxyl silane of triethyl aluminum, 4 mmoles of 20 mmoles and 2 mmoles more afterwards, with 5.9 standard liters/hour speed supplied with propylene 1 hour, can make 2.8 gram propylene polymerizations with respect to the solid titanium catalyst composition (A) of 1 gram.
Carry out after the prepolymerization, remove after filtration liquid portion, more isolated solid part redispersion in decane.
Main polymerization
In the main polymerization of embodiment 1, except using above-mentioned catalyzer as the solid titanium catalyst composition (A), all the other carry out the polymerization of propylene by embodiment 1 identical method.
Used polymerization catalyst activity, the polyacrylic boiling that obtains just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 1.Embodiment 4
Repeat the method for embodiment 3 and carry out the polymerization of propylene, only be to use two (2-methylcyclopentyl) dimethoxy silane to substitute dicyclopentyl dimethoxyl silane.
Used polymerization catalyst activity, the polyacrylic boiling that obtains just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 1.Embodiment 5
Repeat the method for embodiment 1 and carry out the polymerization of propylene, only be to use twoly-2,4-cyclopentadienyl dimethoxy silane substitutes dicyclopentyl dimethoxyl silane.
Used polymerization catalyst activity, the polyacrylic boiling that obtains just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 1.
Table 1 embodiment polymerization activity II MFR AD
(%) 1 46,500 99.2 6.3 0.46 2 45,100 98.9 6.0 0.46 3 45,800 98.9 6.0 0.46 4 33,300 94.3 5.7 0.45 5 42,600 95.2 6.2 0.43 embodiment 6
Main polymerization
In inner capacities is the propylene that add 500 grams in 2 liters the autoclave, under 60 ℃, add the catalyzer composition (A) (calculating) that uses in the prepolymerization of embodiment 3 of two ring the eleventh of the twelve Earthly Branches base Trimethoxy silanes of triethyl aluminum, 0.06 mmole of 0.6 mmole and 0.006 mmole with titanium atom, add again after 1 liter of hydrogen, be warming up to 70 ℃, made propylene polymerization 40 minutes.Dried full polymeric output be 345 grams, ebullient just-heptane extraction residual rate is 98.7%, MFR is that 1.0 grams/10 minutes, apparent specific gravity are 0.47 grams per milliliter.
Therefore, Ci Shi polymerization activity is 57,500 gram-propylene/mmole titanium.Embodiment 7
Repeat the method for embodiment 6 and carry out the polymerization of propylene, only be to use two-2,4-cyclopentadienyl dimethoxy silane substitutes dicyclopentyl dimethoxyl silane.
Used polymerization catalyst activity, the polyacrylic ebullient that is obtained just-heptane extraction residual rate, MFR and apparent specific gravity are as shown in table 2.
Table 2 embodiment polymerization activity II MFR AD
(％)
6 57,500 98.7 1.0 0.47
7 53,700 98.9 1.2 0.46 embodiment 8
Main polymerization
In the internal volume with the abundant purge of nitrogen is 2 liters stainless steel autoclave, add 150 gram sodium-chlor (with the pure medicine superfine of light), 90 ℃ of following drying under reduced pressure 1 hour.Then, temperature in the reaction system is cooled to after 65 ℃, adds the mixture of the solid titanium catalyst composition (A) (calculating) that prepolymerization is used among the embodiment 3 of 1 mmole triethyl aluminum, 0.1 mmole dicyclopentyl dimethoxyl and 0.01 mmole with titanium atom.And then the hydrogen of the 150 standard milliliters (Nml) of packing into and begin to supply with propylene/ethylene mixed gas (93.1/6.9 moles/mole).Keep total pressure under 5 kg/cm gauge pressures and 70 ℃, carry out polymerization 1 hour.Polymerization washes with water and removes sodium-chlor after ending.The polymkeric substance that stays with methanol wash descends dry 1 evening at 80 ℃ at last again.
The MFR of used polymerization catalyst activity, the polymkeric substance that is obtained, ethylene content, the fusing point of measuring with DSC and just-decane solubility component is as shown in table 3.Embodiment 9
Repeat the method for embodiment 8 and carry out polymerization, just replace dicyclopentyl dimethoxyl silane with two (2-methylcyclopentyl) dimethoxy silane.
Used polymerization catalyst activity, the MFR of the polymkeric substance that is obtained, ethylene content, the fusing point of measuring with DSC and just-decane solubility component is as shown in table 3.
Table 3 embodiment polymerization activity MFR C
11 2Tm decane solubility component 88,500 1.3 6.1 133.0 4.9 97,200 1.4 6.2 133.2 6.2 embodiment 10
Repeat the method for embodiment 8 and carry out copolymerization, just replace used gaseous mixture among the embodiment 8 with propylene, ethene and butylene gaseous mixture (74.8/8.8/7.8 (mol ratio)).
The polymerization activity of used catalyzer is 7, the MFR of 400 gram propylene/mmole titaniums, prepared polymkeric substance is 3.3 grams/10 minutes, apparent bulk density is that 0.34 grams per milliliter, ethylene content are that 5.3 moles of %, butene content are that 6.2 moles of %, tensile strength are 2,300 kg/cm, the fusing point of measuring with DSC be 103 ℃, just-decane solubility component is 42 (weight) %.Embodiment 11
Repeating the method for embodiment 10 and carry out copolymerization, is that the mixed gas of being supplied with consists of propylene/ethylene/butene (88.5/5.3/6.2 moles/mole/mole).
Used polymerization catalyst activity is 6,400 gram-propylene/mmole titanium, the MFR of obtained polymkeric substance is 2.5 grams/10 minutes, apparent bulk density is that 0.38 grams per milliliter, 2.8 moles of % of ethylene content, 6.4 moles of % of butene content, tensile strength are 4,600 kg/cm, the fusing point measured with DSC be 121.1 ℃, just-the solubility component of decane is 8.2 (weight) %.Embodiment 12
At room temperature, in 17 liters polymerization reactor, add 2.5 kilograms of propylene and 9 standards and rise hydrogen, heat up then, the catalyzer composition (A) that uses in two pentamethylene dimethoxy silane of the triethyl aluminum of adding 15 mmoles, 1.5 mmoles and 0.05 mmole embodiment, 3 prepolymerizations under 50 ℃ (calculating with titanium atom), reactor temperature remains on 70 ℃.Reaching 70 ℃ after 10 minutes, opening purging valve discharging propylene and in reactor, reach till the normal pressure.Proceed polymerization after the venting, just ethene with 480 standard liters/hour, propylene with 720 standard liters/hour, hydrogen with 12 standard liters/hour speed feed in reactor.The aperture of conditioned reaction device blow-off valve, making reactor internal pressure is 10 kg/cm gauge pressures.Temperature remains on 70 ℃ during the copolymerization.After the copolymerization effluxion 85 minutes, shed pressure, make 2.8 kilograms polymkeric substance.MFR under 230 ℃, 2 kilograms loadings is that 1.8 kilograms/10 minutes, the content of ethene are that 29 moles of %, apparent bulk density are that 0.43 kilogram/cubic centimetre, tensile strength are 3600 kilograms/cubic centimetre.In addition, 23 ℃ just-the solubility component of decane is that ethylene content in 41 (weight) %, this solubility composition is 43 (mole) %.
Claims (3)
1. the catalyzer of a for olefines polymerization is characterized in that it is made up of following component
(A) contain the solid titanium catalyst composition that magnesium, titanium and halogen are major ingredient.
(B) organo-aluminium compound catalyzer composition and
(C) by the silicoorganic compound catalyzer composition shown in the following general formula.
SiR
21R
22 m(OR
23)
3-m
R in the formula
21Represent cyclopentyl, cyclopentenyl, cyclopentadienyl and by they deutero-groups, R
22And R
23Can be the same or different, and representation hydrocarbyl separately, 0≤m＜3.
2. the catalyzer of for olefines polymerization according to claim 1, R therein
21Definition in, this deriveding group is to be selected from by 1-4 to contain the cyclopentyl that the alkyl of 1-4 carbon atom replaces, the alkyl that is replaced by cyclopentyl that contains 2-4 carbon atom, wherein the cyclopentyl cyclopentenyl that may be replaced by 1-4 alkyl that contains 1-4 carbon atom, be replaced by 1-4 alkyl that contains 1-4 carbon atom, by the cyclopentadienyl of the individual alkyl replacement that contains 1-4 carbon atom of 1-4 and may be by individual indenyl, indanyl, tetrahydroindenyl or the fluorenyl that contains the alkyl replacement of 1-4 carbon atom of 1-4.
3. the purposes of the described catalyzer of claim 1 is used for the polymerization or the copolymerization of alkene.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP149503/88 | 1988-06-17 | ||
| JP14950388 | 1988-06-17 | ||
| JP14595/89 | 1989-01-24 | ||
| JP1459589A JP2723137B2 (en) | 1988-06-17 | 1989-01-24 | Olefin polymerization method and olefin polymerization catalyst |
| JP50871/89 | 1989-03-02 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98116349A Division CN1113904C (en) | 1988-06-17 | 1998-07-18 | Olefin polymerization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040379A CN1040379A (en) | 1990-03-14 |
| CN1043233C true CN1043233C (en) | 1999-05-05 |
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ID=26350562
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89107190 Expired - Lifetime CN1043233C (en) | 1988-06-17 | 1989-06-16 | Process for polymerizing olefins and polymerization catalyst thereof |
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| CN (1) | CN1043233C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100334163B1 (en) | 1998-12-04 | 2002-10-25 | 삼성종합화학주식회사 | Olefin Polymerization or Copolymerization Method |
| CN102791762B (en) * | 2010-01-14 | 2015-07-15 | 日本瑞翁株式会社 | Cyclopentene-ring-opened polymer and production process thereof |
| US9815918B2 (en) | 2012-03-19 | 2017-11-14 | Formosa Plastics Corporation, U.S.A. | Catalyst component for high activity and high stereoselectivity in olefin polymerization |
| CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof |
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1989
- 1989-06-16 CN CN 89107190 patent/CN1043233C/en not_active Expired - Lifetime
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