CN104558288A - Olefin polymer and preparation method thereof - Google Patents
Olefin polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an olefin polymer and a preparation method thereof. The preparation method comprises the following steps of (1) carrying out low-temperature reaction on an alpha-olefin monomer and an olefin polymerization catalyst at the temperature of higher than or equal to 0 DEG C and lower than 50 DEG C for 1-60 minutes, wherein the olefin polymerization catalyst contains a solid component A and a specific organic silicon compound C which are prepared through specific steps; and (2) carrying out high-temperature polymerization reaction on the low-temperature reaction product obtained in the step (1) at the temperature of 80-120 DEG C. By using the preparation method disclosed by the invention, the polymerization activity during high-temperature polymerization of alpha-olefin can be improved; and the obtained olefin polymer is high in melt index and can also be high in isotacticity and wide in molecular weight distribution.
Description
Technical field
The present invention relates to a kind of olefin polymer and preparation method thereof, particularly, relate to a kind of alpha-olefin and carry out the method that high temperature polymerization prepares olefin polymer, and olefin polymer obtained by this method.
Background technology
Alpha-olefinic polymer is important synthetic organic material.The use of this material, except requiring suitable mechanical property, also will have the performance that can adapt to processed and applied.Wherein, the degree of isotacticity of alpha-olefinic polymer, melting index and molecular weight distributing index (MWD) are the important factors affecting mechanical properties of polymer and processing characteristics.
The degree of isotacticity of alpha-olefinic polymer determines the rigidity of this polymkeric substance to a certain extent.Generally speaking, the rigidity of the higher alpha-olefinic polymer of degree of isotacticity also can be higher.Therefore, when requiring alpha-olefinic polymer to have higher rigidity, the degree of isotacticity improving alpha-olefinic polymer is favourable.Even some this polymkeric substance of application requiring degree of isotacticity (heptane extraction process measure, see the embodiment of the present invention, following term " polymer " degree of isotacticity " all measured by heptane extraction process) reach more than 99%.But the more difficult realization of prior art has the production of the alpha-olefinic polymer of so high degree of isotacticity.
Consider from processed and applied, the melting index of polymkeric substance is higher, and the mobility of polymkeric substance is better, is more conducive to the processing of polymkeric substance.Therefore, when comprehensive polymer performance and processed and applied, while mechanical property needed for guarantee material, wish that melt index is more high better.But in existing alpha-olefinic polymer technology of preparing, often while raising melting index, the degree of isotacticity of alpha-olefinic polymer can decline, and also namely the rigidity of polymkeric substance declines.Especially when the melting index of alpha-olefinic polymer also require higher than 3 even 5g/10min time, more difficult realization.Therefore, the production realizing taking into account the alpha-olefinic polymer of melting index and degree of isotacticity is that industrial production is pursued always.
The molecular weight distributing index of polymkeric substance is also affect the mechanical property of polymkeric substance and another important factor of processing characteristics.High molecular weight moieties determines the long term mechanical strength of polymkeric substance to a great extent, and low molecular weight fraction part determines its extrusion performance to a great extent.When production injection moulding homopolymer or anti-impact polymkeric substance, often wish not only polymkeric substance has high melting index but also have wide molecular weight distributing index simultaneously.This polymkeric substance is considered to intensity that existing good processing characteristics also had and rigidity.But, molecular weight distributing index and melt index closely related, generally, the polymkeric substance of high fusion index is difficult to obtain wider molecular weight distributing index.
As can be seen here, expect that alpha-olefinic polymer while acquisition high fusion index, can have high isotactic and wide molecular weight distribution index.
Obtain above-mentioned alpha-olefinic polymer, polymerization process is most important.In the research and development that alpha-olefinic polymer synthesis is produced, it has been recognized that, improve polymeric reaction temperature, Ziegler-Natta catalyst (alpha-olefinic polymer commonly uses polymerizing catalyst) can become more responsive to molecular weight regulator hydrogen, can have the trend producing the alpha-olefinic polymer with high fusion index and degree of isotacticity.But when using conventional Ziegler-Natta catalyst to carry out conventional olefine polymerizing process, improve polymerization temperature, polymerization activity meeting rapid decay, polymerisate yield declines, and is difficult to the production realizing polymkeric substance, can not get alpha-olefinic polymer product.
As can be seen here, prior art cannot realize at high temperature carrying out alpha-olefine polymerizing, can not get the alpha-olefinic polymer with high fusion index, high isotactic and wide molecular weight distribution index.Therefore a kind of polymerization process that can realize obtaining the alpha-olefinic polymer with high fusion index, high isotactic and wide molecular weight distribution index is needed.
Summary of the invention
The object of the invention is to overcome prior art cannot realize at high temperature carrying out alpha-olefine polymerizing, can not get the problem of the alpha-olefinic polymer with high fusion index, high isotactic and wide molecular weight distribution index, a kind of olefin polymer and preparation method thereof is provided.
To achieve these goals, the invention provides a kind of method preparing olefin polymer, the method comprises the following steps:
(1) 'alpha '-olefin monomers and olefin polymerization catalysis are carried out low-temp reaction, the temperature of described low-temp reaction is for being more than or equal to 0 DEG C and being less than 50 DEG C, and the time of described low-temp reaction is 1-60 minute;
(2) the low-temp reaction product that step (1) obtains is carried out high temperature polymerization reaction, the temperature of described high temperature polymerization reaction is 80-120 DEG C;
Described olefin polymerization catalysis contains solid ingredient A containing magnesium and titanium and silicoorganic compound C;
The described solid ingredient A containing magnesium and titanium is prepared by following steps:
A magnesium halide is dissolved in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent by (), form homogeneous solution, optionally add internal electron donor compound c;
B (), at-30 DEG C at 60 DEG C, the solution mixing first titanium compound and step (a) obtained, then adds precipitation additive solution, forms mixture; Or first precipitation additive solution is joined in the solution that step (a) obtains, then at-30 DEG C at 60 DEG C, mix with titanium compound, form mixture;
C the mixture obtained in step (b) is warming up to 60-110 DEG C by (), optionally internal electron donor compound d is added at temperature-rise period or after temperature, after temperature, stir 0.5-8 hour, elimination mother liquor, after inert diluent washing, obtain the solids containing magnesium and titanium;
The d mixture process of solids containing titanium compound, inert diluent and optional internal electron donor compound e 1 time containing magnesium and titanium that () will obtain in step (c), again by the mixture process containing titanium compound and inert diluent 1-2 time, use inert diluent washes clean subsequently, the obtained solid ingredient A containing magnesium and titanium;
Wherein precipitation additive solution is the mixing solutions containing precipitation additive a and precipitation additive b; In every mole of magnesium halide, organic epoxy compound thing is 0.2-10 mole, organo phosphorous compounds is 0.1-3 mole, titanium compound is 0.5-50 mole, precipitation additive A is 0.001-0.3 mole, and precipitation additive B is 0.001-0.5 mole, internal electron donor compound c is 0-3 mole, internal electron donor compound d and e is respectively 0-5 mole, and c+d+e is 0-5 mole;
Described silicoorganic compound C is at least one in dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane and tetraethoxysilane.
Present invention also offers the olefin polymer prepared by method provided by the invention.
Method provided by the invention can at high temperature be carried out alpha-olefin polymerization and have polymerization activity, and polymeric articles while having higher melting index, can also have high isotactic and wide molecular weight distribution index.In method provided by the invention, use the solid ingredient A and the specific olefin polymerization catalysis being used as the silicoorganic compound C of external electron donor that prepare containing ad hoc approach, first 'alpha '-olefin monomers being carried out low-temp reaction when carrying out polyreaction carries out high temperature polymerization reaction more simultaneously.Such as embodiment 1, containing solid ingredient A1 and specific DCPMS in olefin polymerization catalysis, first rare earth polymerizing catalyst carried out complex reaction during polymerization and carry out low-temp reaction, and then at 95 DEG C, carry out the high temperature polymerization reaction of propylene monomer, can obtain polymerization activity is 39.5Kg/gcat, the melting index (MI) of the polypropylene product obtained is 5.4g/10min, degree of isotacticity (II) be 99.5% and molecular weight distributing index (MWD) be 5.7.In embodiment 2 at 110 DEG C be polymerized, still can obtain the polymerization activity of 34.6Kg/gcat, the polypropylene product melting index (MI) obtained is 8.1g/10min, degree of isotacticity (II) be 99.0% and molecular weight distributing index (MWD) be 6.0.Although and in comparative example 2 use A1, DCPMS, but there is no low-temp reaction, therefore the polymerization activity of pyroreaction only has 26.1Kg/gcat, the melting index (MI) of the polypropylene product obtained is 5.2g/10min, degree of isotacticity (II) be 99.0% and molecular weight distributing index (MWD) be 5.7.
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.
The invention provides a kind of method preparing olefin polymer, the method comprises the following steps:
(1) 'alpha '-olefin monomers and olefin polymerization catalysis are carried out low-temp reaction, the temperature of described low-temp reaction is for being more than or equal to 0 DEG C and being less than 50 DEG C, and the time of described low-temp reaction is 1-60 minute;
(2) the low-temp reaction product that step (1) obtains is carried out high temperature polymerization reaction, the temperature of described high temperature polymerization reaction is 80-120 DEG C;
Described olefin polymerization catalysis contains solid ingredient A containing magnesium and titanium and silicoorganic compound C;
The described solid ingredient A containing magnesium and titanium is prepared by following steps:
A magnesium halide is dissolved in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent by (), form homogeneous solution, optionally add internal electron donor compound c;
B (), at-30 DEG C at 60 DEG C, the solution mixing first titanium compound and step (a) obtained, then adds precipitation additive solution, forms mixture; Or first precipitation additive solution is joined in the solution that step (a) obtains, then at-30 DEG C at 60 DEG C, mix with titanium compound, form mixture;
C the mixture obtained in step (b) is warming up to 60-110 DEG C by (), optionally internal electron donor compound d is added at temperature-rise period or after temperature, after temperature, stir 0.5-8 hour, elimination mother liquor, after inert diluent washing, obtain the solids containing magnesium and titanium;
The d mixture process of solids containing titanium compound, inert diluent and optional internal electron donor compound e 1 time containing magnesium and titanium that () will obtain in step (c), again by the mixture process containing titanium compound and inert diluent 1-2 time, use inert diluent washes clean subsequently, the obtained solid ingredient A containing magnesium and titanium;
Wherein precipitation additive solution is the mixing solutions containing precipitation additive a and precipitation additive b; In every mole of magnesium halide, organic epoxy compound thing is 0.2-10 mole, organo phosphorous compounds is 0.1-3 mole, titanium compound is 0.5-50 mole, precipitation additive A is 0.001-0.3 mole, and precipitation additive B is 0.001-0.5 mole, internal electron donor compound c is 0-3 mole, internal electron donor compound d and e is respectively 0-5 mole, and c+d+e is 0-5 mole;
Described silicoorganic compound C is at least one in dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane and tetraethoxysilane.
In method provided by the invention, before carrying out 'alpha '-olefin monomers high temperature polymerization reaction, first olefin polymerization catalysis and 'alpha '-olefin monomers are carried out low-temp reaction, then 'alpha '-olefin monomers is carried out high temperature polymerization reaction further; The solid ingredient A that wherein olefin polymerization catalysis contains is prepared through specific step, selects specific silicoorganic compound C as external electron donor.Therefore, in the present invention, 'alpha '-olefin monomers can carry out high temperature polymerization and have high polymerization activity, and can obtain the olefin polymer product with high fusion index, high isotactic and wide molecular weight distribution index.
According to the present invention, low-temp reaction can carry out under above-mentioned preferable case, and the prepolymerized polymerisate of acquisition can have high polymerization activity in high temperature polymerization reaction.Preferably, the temperature of described low-temp reaction is 10 DEG C to 30 DEG C, and the time of described low-temp reaction is 1-20 minute, and the pressure of described low-temp reaction is 0.1-3MPa; More preferably, the time of described low-temp reaction is 5-15 minute, and the pressure of described low-temp reaction is 0.2-2.5MPa.In the present invention, control described low-temp reaction under these conditions, the prepolymerization polymkeric substance being suitable for reacting with the high temperature polymerization that high polymerization activity carries out can be obtained.
According to the present invention, described olefin polymerization catalysis can comprise the solid ingredient A containing magnesium and titanium prepared by specific step.When the solid ingredient A containing magnesium and titanium prepared by above-mentioned steps is in for method of the present invention, be conducive to can obtaining higher polymerization activity carrying out high temperature polymerization reaction.The described solid ingredient A containing magnesium and titanium can be Primary Catalysts.
In the present invention, containing in the middle of the process of the solid ingredient A of magnesium and titanium described in above-mentioned preparation, described precipitation additive solution in step (b) can for containing the mixing solutions of precipitation additive a and precipitation additive b, and described precipitation additive a can for being selected from the one in the diol-lipid compound shown in following general formula (I):
R in formula (I)
1-R
6, R
1-R
2ngroup can be identical or different, and is the C of hydrogen, halogen or substituted or unsubstituted straight or branched independently of one another
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene or C
10-C
20fused ring aryl; But R
1and R
2can not be hydrogen, optional R
3-R
6and R
1-R
2nat least two in group are linked up into ring; N can be the integer of 0-10; Described precipitation additive b can for being selected from general formula (II) R
i ar
iI bsi (OR
iII)
cthe one of shown organosilane compounds, R in formula (II)
i, R
iIand R
iIIcan be identical or different, and can be C independently of one another
l-C
10alkyl, C
3-C
10cycloalkyl or C
6-C
10aromatic yl group, wherein a and b can be the integer of 0-2, and c can be the integer of 1-4, and (a+b+c)=4; Preferred R
i, R
iIcan be C independently of one another
l-C
8alkyl, C
3-C
6cycloalkyl or C
6-C
10aromatic yl group, R
iIIcan be C
l-C
10alkyl, organosilane compounds can as tetraethoxysilane (TEOS), Cyclohexylmethyldimethoxysilane (CHMMS), dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane (DCPMS), diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane particularly.
In the present invention, described precipitation additive a is disclosed in Chinese patent CN1436766A and CN1436796A, and disclosed in this patent, associated viscera introduces the present invention as a reference.
In the present invention, described precipitation additive a in the binary alcohol esters compounds shown in above-mentioned general formula (I), the compound shown in preferred formula (IV):
R in formula (IV)
1-R
6, R
1-R
2group is as the definition in general formula (I), particularly can be as: 2-ethyl-1, ammediol dibenzoate, 2-propyl group-1, ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1, 3 propylene glycol dibenzoates, 1, 3-butyleneglycol mesitylenic acid ester, 2-methyl isophthalic acid, 3-butyleneglycol two m-chlorobenzoic acid ester, 2, 3-dimethyl-1, 3-butyleneglycol dibenzoate, 1, 3-pentanediol pivalate, 2, 4-glycol dibenzoate, 2, 2-dimethyl-1, 3-glycol dibenzoate, 2, 4-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 2, 3-di-isopropyl-1, 4-butyleneglycol dibenzoate, 3, 5 heptanediol dibenzoates or 4-ethyl-3, 5 heptanediol dibenzoates.Preferably, can as 2,4-glycol dibenzoate, 3,5 heptanediol dibenzoates or 4-ethyl-3,5 heptanediol dibenzoate.
In the present invention, general formula (II) R
i ar
iI bsi (OR
iII)
cshown precipitation additive b, particularly can be as: tetraethoxysilane (TEOS), Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane (DDS), methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-methyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane or vinyltrimethoxy silane.Preferably, can as tetraethoxysilane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane or second, isobutyl dimethoxy silane.
Step (b) can be identical with titanium compound described in step (d), can be general formula (III) TiX
n(OR)
4-nshown compound, in formula (III), R can be C1-C20 alkyl, and X can be halogen, n=1-4; Particularly, described titanium compound can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or their mixture, preferred titanium tetrachloride.
In the present invention, described internal electron donor compound c, d, e can select at least one in the alkyl ester of the binary alcohol esters compounds shown in general formula (I), the alkyl ester of aliphatics or aromatic monocarboxylate, aliphatics or aromatic polycarboxylic acid, fatty ether, cycloaliphatic ether and aliphatic ketone; Preferred aliphat or aromatic binary carboxylic acid ester and/or diether compound; More preferably phthalate, malonic ester class, succinate compound, glutarate class, pivalate or carbonates.Specifically can be as: diethyl phthalate (DEP), diisobutyl phthalate, n-butyl phthalate (DNBP), dimixo-octyl phthalate, dinoctyl phthalate, 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, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids dibutylester, 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 or pyromellitic acid four butyl ester.Select different internal electron donors, catalyzer will show different directional properties and hydrogen regulation performance.Described internal electron donor compound c, d, e can identical also can be different, preferably identical.
In the present invention, preferably, in every mole of magnesium halide, organic epoxy compound thing can be 0.5-4 mole, and organo phosphorous compounds can be 0.3-1.5 mole, and titanium compound can be 5-15 mole, precipitation additive a can be 0.01-0.1 mole, precipitation additive b can be 0.01-0.3 mole, and electron donor compound c can be 0-0.3 mole, and electron donor compound d and e can be respectively 0-1 mole; C+d+e can be 0.02-1 mole.
In the present invention, a kind of in the derivative that described magnesium halide can be replaced for one of them halogen atom alkoxy or halogenated alkoxy in the complex compound of the water of magnesium dihalide, magnesium dihalide and alcohol, magnesium dihalide molecular formula or their mixture; The alcohol adduct of preferred magnesium dihalide or magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, diiodinating magnesium and their alcohol adduct.
In the present invention, described organic epoxy compound thing can comprise at least one in C2-C8 aliphatics alkene, the oxide compound of diolefine or halogenated aliphatic alkene or diolefine, glycidyl ether and inner ether.Particular compound can be as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether or diglycidylether, preferred epoxy chloropropane.
In the present invention, described organo phosphorous compounds can comprise hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or halo hydrocarbyl carbonate or phosphorous acid, specifically can be as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or tricresyl phosphite benzene methyl, preferred ortho-phosphoric acid tri-n-butyl.
In the present invention, described inert diluent can adopt a kind of in hexane, heptane, octane, decane, benzene,toluene,xylene or their mixture.
In the present invention, in the method for solid ingredient A containing magnesium and titanium described in preparation, step (a) preferably can for being dissolved in the solvent system that is made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent by magnesium halide, after forming homogeneous solution, continue to add internal electron donor compound c, form homogeneous solution; Step (b) can be preferably: at-30 DEG C at 60 DEG C, is added by precipitation additive a and precipitation additive b in the solution that step (a) obtains, then adds in titanium compound, forms mixture.
According to the present invention, described silicoorganic compound C can as external electron donor component.Under preferable case, described silicoorganic compound C can be formula (VI) R
1' '
m''r
2' '
n''si (OR
3' ')
4-m''-n''shown compound, in formula (VI), R
1' ' and R
2' ' can be identical or different, and can be the one in halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl and C1-C20 haloalkyl independently of one another; R
3' ' can be one in C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl and C1-C20 haloalkyl; M'' and n'' can be the integer of 0-3 respectively, and m''+n''<4.Object lesson as described silicoorganic compound C can enumerate trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane (DCPMS), cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl Trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes.These silicoorganic compound can individually use, and also two or more can be combinationally used.More preferably described silicoorganic compound C can be at least one in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane (CHMMS), dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane and tetraethoxysilane (TEOS).
According to the present invention, described high temperature polymerization reaction can be carried out under above-mentioned preferable case, can also the further preferred described high temperature polymerization temperature of reacting be 85-110 DEG C.High temperature polymerization is conducive to obtaining the olefin polymer with high fusion index, high isotactic and wide molecular weight distribution index, but too high temperature can affect the output of the polymkeric substance of acquisition, therefore can control high temperature polymerization of the present invention in above-mentioned scope.
According to the present invention, other conditions of described high temperature polymerization reaction can be the normal conditions of this area.Under preferable case, the pressure of described high temperature polymerization reaction is 0.1-6MPa, and the time of described high temperature polymerization reaction is 0.1-5 hour; The pressure of preferred described high temperature polymerization reaction is 0.5-5MPa, and the time of described high temperature polymerization reaction is 0.5-4 hour.
According to the present invention, polyreaction can be all polymerizations of alpha-olefin, also can be the copolymerization of multiple alpha-olefin.As long as the consumption of the monomer of described alpha-olefin can meet the requirement of polyreaction, obtain the olefin polymer expected; The consumption of described olefin polymerization catalysis can for realizing the consumption of katalysis.Under preferable case, the weight ratio of described monomer and described olefin polymerization catalysis is 50000-200000.In the present invention, olefinic polyreaction carries out according to the weight ratio of above-mentioned monomer and olefin polymerization catalysis, to adapt with the low-temp reaction of olefin polymerization catalysis that first carries out in method of the present invention, thus realizes object of the present invention.
According to the present invention, can be by general formula CH for 'alpha '-olefin monomers of the present invention
2the alkene that=CHR represents, R can be hydrogen or C1-C6 alkyl.Under preferable case, described monomer is at least one in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; Preferred described monomer is at least one in ethene, propylene and 1-butylene; Further preferred described monomer is propylene.
According to the present invention, although goal of the invention of the present invention can be realized containing the described solid ingredient A containing magnesium and titanium in described olefin polymerization catalysis, but do not get rid of in described olefin polymerization catalysis and can also comprise other materials, such as, can improve the material of described olefin polymerization catalysis performance further.Under preferable case, described olefin polymerization catalysis also includes machine aluminium compound B.
According to the present invention, described olefin polymerization catalysis can containing solid ingredient A, organo-aluminium compound B and the silicoorganic compound C containing magnesium and titanium.Under preferable case, aluminium element in described organo-aluminium compound B and the described mol ratio containing the titanium elements in the solid ingredient A of magnesium and titanium are 5-5000:1, and the aluminium element in preferred described organo-aluminium compound B is 20-1000:1 with the mol ratio of the titanium elements in the described solid ingredient A containing magnesium and titanium; More preferably, the aluminium element in described organo-aluminium compound B and the described mol ratio containing the titanium elements in the solid ingredient A of magnesium and titanium are 50-500:1; The mol ratio of the aluminium element in described organo-aluminium compound B and described silicoorganic compound C is 0.1-500:1, aluminium element in preferred described organo-aluminium compound B and the mol ratio 1-300:1 of described silicoorganic compound C, the aluminium element more preferably in described organo-aluminium compound B and the mol ratio 3-100:1 of described silicoorganic compound C.
In the present invention, described organo-aluminium compound B can as promotor, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst can commonly used for field of olefin polymerisation.In the preferred case, described organo-aluminium compound B can be formula V AlR'
n'x'
3-n'shown compound, in formula V, R' can be hydrogen, C1-C20 alkyl or C6-C20 aryl, and X' can be halogen, and n' can be the integer of 1-3.The object lesson of preferred described organo-aluminium compound B can be at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferably, described organo-aluminium compound B can be triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, when using described olefin polymerization catalysis to carry out olefin high-temperature polymerization of the present invention reaction, solid ingredient A, the organo-aluminium compound B and silicoorganic compound C that contain magnesium and titanium can be added in system monomer respectively and carry out polyreaction, but above-mentioned A, B can also be carried out complex reaction with component C first contact before contacting with olefinic monomer by the method for olefinic polymerization of the present invention.Under preferable case, described method is also included in before described olefin polymerization catalysis and described monomer carry out low-temp reaction, complex reaction is carried out containing magnesium and the solid ingredient A of titanium, described organo-aluminium compound B and described silicoorganic compound C by described, the temperature of described complex reaction is 0 DEG C to 50 DEG C, the time of described complex reaction is 0.1-30 minute, and the pressure of described complex reaction is normal pressure; The temperature of preferred described complex reaction is 10-30 DEG C, and the time of described complex reaction is 0.1-10 minute, and the pressure of described complex reaction is 0.1-0.2MPa.Method of the present invention comprises described complex reaction, the polymerization activity of olefin high-temperature polymerization can be improved further, make at high temperature to be polymerized and can obtain polymeric articles with higher output, and be more conducive to obtaining melting index and the high and polymeric articles that molecular weight distributing index is wide of degree of isotacticity.
In the preferred embodiment of the present invention, preferably olefin high-temperature polymerization is carried out with following method: olefin polymerization catalysis contains the solid ingredient A of magnesium prepared by particular step and titanium; Solid ingredient A, the organo-aluminium compound B of magnesium and titanium and silicoorganic compound C are carried out complex reaction; The complex reaction product obtained and olefinic monomer carry out low-temp reaction; The low-temp reaction product of certain extent of polymerization that has obtained is carried out high temperature polymerization reaction.This preferred implementation can obtain higher polymerization activity, is more conducive to obtaining melting index and the high and polymeric articles that molecular weight distributing index is wide of degree of isotacticity.
Present invention also offers the olefin polymer prepared by method provided by the invention.
In the present invention, described olefin polymer can be by general formula CH
2the olefinic monomer that=CHR represents obtains through polyreaction, and wherein R can be hydrogen or C1-C6 alkyl.Under preferable case, described olefinic monomer is at least one in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; Preferred described olefinic monomer is at least one in ethene, propylene and 1-butylene; Further preferred described olefinic monomer is propylene.
According to the present invention, under preferable case, the melting index of described olefin polymer is 1-300g/10min, and degree of isotacticity is 94-99.8%, and molecular weight distributing index is 4-15; Preferably, melting index be 4-150g/10min, degree of isotacticity is 95-99.5%, and molecular weight distributing index is 5.5-10.
Below will be described the present invention by embodiment.In following examples, melt index measures according to GB/T3682-2000.
Polymkeric substance degree of isotacticity adopts heptane extraction process to measure, be specially: 2 grams of dry polymer samples, be placed on the heptane extracting after 6 hours with boiling in extractor, residuum be dried to polymer weight (g) and the 2(g of constant weight gained) ratio be degree of isotacticity.
Molecular weight distribution index M WD(MWD=Mw/Mn) mensuration adopt the PL-GPC220 instrument of Waters company, be that solvent carries out measuring (standard specimen: polystyrene at 150 DEG C with trichlorobenzene, flow velocity: 1.0ml/min, pillar: 3xPlgel10um MlxED-B300x7.5nm).
In following preparation example, embodiment and comparative example, calculate by charging capacity containing the content of each component in the solid ingredient A of magnesium and titanium, in the olefin polymerization catalysis obtained, the content of each component calculates by charging capacity.
Polymerization activity is obtained by the ratio calculation of polymerization resulting polymers quality and used catalyst quality.
The compound that following examples use is commercially available chemical pure commodity.
Preparation example 1
The preparation containing the solid ingredient A of magnesium and titanium that this preparation example uses for illustration of the present invention.
A () is repeating in the reactor of replacing through high pure nitrogen, add 0.05 mole of Magnesium Chloride Anhydrous, 0.75 mole toluene, 0.1 moles of epichlorohydrin, 0.033 mole of phosphoric acid tri-n-butyl successively, under mixing speed 450rpm, temperature are the condition of 60 DEG C, react 1.5 hours, add 1.9 mmole diethyl phthalates (DEP) again, react 1.0 hours to obtain solution;
B solution that (a) obtains by () is cooled to-28 DEG C, drip titanium tetrachloride 0.51 mole, then add 1.4 mmole 3,5 heptanediol dibenzoates and the 4.4 mmole dimethoxydiphenylsilanes (DDS) of 0.1 mole toluene dilution, continue reaction and form mixture in 1 hour;
C mixture that (b) is formed by () is warming up to 85 DEG C gradually, separates out solid particulate matter in temperature-rise period.Add 2.6 mmole diethyl phthalates (DEP) to 85 DEG C, constant temperature one hour, elimination mother liquor, repeatedly washs after filtering liquid through inert diluent toluene, obtains the solids containing magnesium and titanium;
The d solids containing magnesium and titanium that (c) obtains by () adds titanium tetrachloride 0.44 mole and toluene 0.7 mole 110 DEG C of constant temperature 2 hours, re-treatment twice again after filtration, then use hexanes wash 5 times, remaining solid product obtains the solid ingredient A1 containing magnesium and titanium through vacuum-drying.
Preparation example 2
According to the method for preparation example 1, unlike:
Substitute " 1.9 mmole diethyl phthalate (DEP) " with " 1.9 mmole n-butyl phthalate (DNBP) " in (a);
C in (), " 2.6 mmole n-butyl phthalate (DNBP) " substitutes " 2.6 mmole diethyl phthalate (DEP) ".Obtain the solid ingredient A2 containing magnesium and titanium.
Preparation example 3
This preparation example is for illustration of the preparation of the solid ingredient of prior art.
By 0.05 mole of Magnesium Chloride Anhydrous, 0.88 mole toluene, 0.05 moles of epichlorohydrin, 0.05 mole of phosphoric acid tri-n-butyl joins in reactor, at mixing speed 450rpm, temperature is under the condition of 60 DEG C, react 2 hours, add 0.01 mole of Tetra hydro Phthalic anhydride, continue reaction one hour, be cooled to-28 DEG C, drip titanium tetrachloride 0.51 mole, be warming up to 85 DEG C gradually, 8.0 mmole n-butyl phthalates are added at 80 DEG C, constant temperature 1 hour after 85 DEG C to temperature, elimination mother liquor, wash twice with 0.95 mole toluene, toluene 0.57 mole is added after filtration, titanium tetrachloride 0.36 mole, 110 DEG C of constant temperature 2 hours, after filtration, re-treatment is once again, and it is dry after hexane 5 washings, obtain solid ingredient B1.
Preparation example 4
This preparation example is for illustration of the preparation of the solid ingredient of prior art.
Repeating in the reactor of replacing through High Purity Nitrogen, add 52.5mmol Magnesium Chloride Anhydrous, 328mmol toluene, 140mmol2-ethylhexanol successively, under mixing speed 450rpm, temperature are the condition of 110 DEG C, react 3.0 hours, obtain the alcohol adduct solution of stable and uniform; Add 3,5-heptanediol dibenzoate 0.8mmol again, diisobutyl phthalate 5.6mmol, tetrabutyl titanate 2.2mmol, stir 60 minutes, be cooled to room temperature.
3 are added with by above-mentioned, 5-heptanediol dibenzoate 0.8mmol, diisobutyl phthalate 5.6mmol, the alcohol adduct homogeneous solution of tetrabutyl titanate 2.2mmol joins fully replaces through nitrogen, be equipped with in the reactor of the 1.0mol titanium tetrachloride of-20 DEG C and 190mmol toluene, them are made fully to contact at-20 DEG C by stirring, after 5 hours, be warming up to 110 DEG C, solid precipitation is separated out in temperature-rise period, add n-butyl phthalate 5.6mmol, react 1 hour, after reaction terminates, filter out liquid, and then solid is contacted 1 hour with 680mmol toluene and 437mmol titanium tetrachloride at 110 DEG C, repeat again after filtration to react once with this Solids At Low Temperatures at 110 DEG C with 680mmol toluene and 437mmol titanium tetrachloride.By the solids 919mmol hexanes wash that obtains 5 times, then dry, obtain solid ingredient B2.
Preparation example 5
This preparation example is for illustration of the preparation of the solid ingredient of prior art.
Repeating in the reactor of replacing through High Purity Nitrogen, add 52.5mmol Magnesium Chloride Anhydrous, 328mmol toluene, 140mmol2-ethylhexanol successively, under mixing speed 450rpm, temperature are the condition of 110 DEG C, react 3.0 hours, obtain the alcohol adduct solution of stable and uniform; Add 3,5-heptanediol dibenzoate 0.8mmol again, 2-sec.-propyl-2-(3-methyl butyl)-1,3-Propanal dimethyl acetal 0.6mmol, diisobutyl phthalate 5.6mmol, tetrabutyl titanate 2.2mmol, stir 60 minutes, be cooled to room temperature.
3 are added with by above-mentioned, 5 heptanediol dibenzoate 0.8mmol, 2-sec.-propyl-2-(3-methyl butyl)-1, 3-Propanal dimethyl acetal 0.6mmol, diisobutyl phthalate 5.6mmol, the alcohol adduct homogeneous solution of tetrabutyl titanate 2.2mmol joins fully replaces through nitrogen, be equipped with in the reactor of the 1.0mol titanium tetrachloride of-20 DEG C and 190mmol toluene, them are made fully to contact at-20 DEG C by stirring, after 5 hours, be warming up to 110 DEG C, separate out in temperature-rise period in solid precipitation temperature-rise period and separate out solid precipitation, add n-butyl phthalate 5.6mmol, react after 1 hour, filter out liquid, then solid is contacted 1 hour with 680mmol toluene and 437mmol titanium tetrachloride at 110 DEG C, repeat again after filtration to react once with this Solids At Low Temperatures at 110 DEG C with 680mmol toluene and 437mmol titanium tetrachloride.By the solids 919mmol hexanes wash that obtains 5 times, then dry, obtain solid constituent B3.
Embodiment 1
The present embodiment is for illustration of the method for olefinic polymerization of the present invention.
(1) pre-complexing.The 3.5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are fully replaced.In catalyst feeder, the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, the hexane solution (concentration of DCPMS is 0.1mol/L) of 1mL dicyclopentyl dimethoxyl silane (DCPMS), 10mL anhydrous hexane and the 12mg solid ingredient A1 containing magnesium and titanium is added under room temperature, mix 2 minutes, obtain catalyzer Cat-1.
(2) prepolymerization.Catalyzer Cat-1 is joined autoclave.Close autoclave, introduce the liquid propene that 1 standard rises hydrogen and 2.4L; Stirring reaction 10 minutes at 15 DEG C; Multiplying power through measuring and calculating low-temp reaction is 200g polymkeric substance/g catalyzer.
(3) be polymerized.Be warming up to 95 DEG C and carry out polyreaction after 1 hour, stop stirring, remove unpolymerized propylene monomer, collect and obtain polymkeric substance.
Measure polymerization activity, the melting index (MI) of polymkeric substance, degree of isotacticity (II), the molecular weight distributing index (MWD) of polyreaction.Result is as shown in table 1.
Embodiment 2
The present embodiment is for illustration of the method for olefinic polymerization of the present invention.
According to the method for embodiment 1, unlike:
(2), in, substitute " at 15 DEG C stirring reaction 10 minutes " with " at 10 DEG C stirring reaction 15 minutes "; Multiplying power through measuring and calculating low-temp reaction is 150g polymkeric substance/g catalyzer;
(3), in, substitute " being warming up to 95 DEG C " with " being warming up to 110 DEG C ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 3
The present embodiment is for illustration of the method for olefinic polymerization of the present invention.
According to the method for embodiment 1, unlike:
(1), in, substitute " hexane solution (concentration of DCPMS is 0.1mol/L) of 1mL dicyclopentyl dimethoxyl silane (DCPMS) " with " hexane solution (concentration of TEOS is 0.1mol/L) of 1mL tetraethoxysilane (TEOS) ";
(2), in, substitute " at 15 DEG C stirring reaction 10 minutes " with " at 30 DEG C stirring reaction 5 minutes "; Multiplying power through measuring and calculating low-temp reaction is 500g polymkeric substance/g catalyzer.
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 4
The present embodiment is for illustration of the method for olefinic polymerization of the present invention.
According to the method for embodiment 1, unlike:
(1), in, substitute " hexane solution (concentration of DCPMS is 0.1mol/L) of 1mL dicyclopentyl dimethoxyl silane (DCPMS) " with " hexane solution (concentration of CHMMS is 0.1mol/L) of 1mL Cyclohexylmethyldimethoxysilane (CHMMS) ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 1
(1) pre-complexing.Nothing.
(2) prepolymerization.The 3.5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are fully replaced.Under room temperature by catalyst feeder add the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, 1mL dicyclopentyl dimethoxyl silane (DCPMS) hexane solution (concentration of DCPMS is 0.1mol/L) to autoclave; The liquid propene that 1 standard rises hydrogen and 2.4L is introduced in autoclave; In autoclave, 10mL anhydrous hexane and 12mg solid ingredient A1 is added again by catalyst feeder.Close autoclave, stirring reaction 10 minutes at 15 DEG C; Multiplying power through measuring and calculating low-temp reaction is 180g polymkeric substance/g catalyzer.
(3) be polymerized.Be warming up to 95 DEG C and carry out polyreaction after 1 hour, stop stirring, remove unpolymerized propylene monomer, collect and obtain polymkeric substance.
Measure polymerization activity, the melting index (MI) of polymkeric substance, degree of isotacticity (II), the molecular weight distributing index (MWD) of polyreaction.Result is as shown in table 1.
Comparative example 2
(1) pre-complexing.The 3.5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are fully replaced.In catalyst feeder, add the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, the hexane solution (concentration of DCPMS is 0.1mol/L) of 1mL dicyclopentyl dimethoxyl silane (DCPMS), 10mL anhydrous hexane and 12mg solid ingredient A1 under room temperature, mix 2 minutes (pre-complexing); Obtain catalyzer Cat-1.
(2) prepolymerization.Nothing.
(3) be polymerized.Catalyzer Cat-1 is joined autoclave.Close autoclave, introduce the liquid propene that 1 standard rises hydrogen and 2.4L; In under agitation 20 minutes, temperature is risen to 95 DEG C and carry out polyreaction after 1 hour, stop stirring, remove unpolymerized propylene monomer, collect and obtain polymkeric substance.
Measure polymerization activity, the melting index (MI) of polymkeric substance, degree of isotacticity (II), the molecular weight distributing index (MWD) of polyreaction.Result is as shown in table 1.
Comparative example 3
According to the method for embodiment 1, unlike:
(3), in, substitute " being warming up to 95 DEG C " with " being warming up to 70 DEG C ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 4
According to the method for embodiment 3, unlike:
(3), in, substitute " being warming up to 95 DEG C " with " being warming up to 70 DEG C ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 5
According to the method for embodiment 1, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 6
According to the method for embodiment 2, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 7
According to the method for embodiment 3, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Embodiment 8
According to the method for embodiment 4, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 5
According to the method for comparative example 1, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 6
According to the method for comparative example 2, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 7
According to the method for comparative example 3, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 8
According to the method for comparative example 4, unlike:
(1) in, substitute with " the solid ingredient A2 containing magnesium and titanium " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 9
According to the method for embodiment 4, unlike:
(1) in, substitute with " solid ingredient B1 " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 10
According to the method for comparative example 9, unlike:
(1), in, substitute " being warming up to 95 DEG C " with " being warming up to 70 DEG C ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 11
According to the method for comparative example 9, unlike:
(1), in, substitute " being warming up to 95 DEG C " with " being warming up to 110 DEG C ".
Polymerization, measuring polymerization activity is zero, does not namely substantially react.
Comparative example 12
According to the method for embodiment 1, unlike:
(1) in, substitute with " solid ingredient B2 " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 13
According to the method for embodiment 1, unlike:
(1) in, substitute with " solid ingredient B3 " " the solid ingredient A1 containing magnesium and titanium ".
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 14
According to the method for comparative example 10, unlike: there is no (1) pre-complexing.
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
Comparative example 15
According to the method for comparative example 10, unlike: there is no (2) prepolymerization.
Polymerization, collects the polymkeric substance obtained.The polymerization activity measuring polyreaction, melting index (MI), degree of isotacticity (II), the molecular weight distributing index (MWD) of polymkeric substance that obtain.Result is as shown in table 1.
As can be seen from Table 1, embodiment 1-8 and comparative example 1-8 is for using solid ingredient A1 of the present invention and A2.Comparative example 1-2,5-6 and comparative example 1-2,5-6, embodiment 1-2 uses solid ingredient A1, DCPMS, pre-complexing and low-temp reaction, can be polymerized under 95 DEG C and 110 DEG C of high temperature, and have high polymerization activity (AC), polymerisate better MI, II and MWD.Comparative example 1-2 uses A1 and DCPMS, but does not have pre-complexing or low-temp reaction, and AC, MI, II and MWD that at 95 DEG C, polyreaction obtains are poor; Embodiment 5-6 uses solid ingredient A2, DCPMS, pre-complexing and low-temp reaction, can be polymerized, and have high AC, polymerisate better MI, II and MWD under 95 DEG C and 110 DEG C of high temperature.Comparative example 5-6 uses A2 and DCPMS, but does not have pre-complexing or low-temp reaction, and AC, MI, II and MWD that at 95 DEG C, polyreaction obtains are poor.
Comparative example 1 and comparative example 3, only have and solid ingredient A1, DCPMS, pre-complexing and low-temp reaction condition matched with pyroreaction, could be polymerized to obtain polymkeric substance and have high MI, high II and wide MWD in addition.Same comparative example 5 and comparative example 7, only have and solid ingredient A2, DCPMS, pre-complexing and low-temp reaction condition matched with pyroreaction, under could having the prerequisite of high MI, also has high II and wide MWD being polymerized the polymkeric substance obtained.
Specific when selecting silicoorganic compound C to be TEOS in embodiment 3 and embodiment 7, polymerization can obtain the olefin polymer with high MI, and this polymkeric substance still has good II and MWD.
Comparative example 3 and comparative example 4, specific select silicoorganic compound C to be the condition of TEOS and solid ingredient A1, pre-complexing and low-temp reaction under, match with pyroreaction the olefin polymer that can be polymerized and obtain and have high MI, and this polymkeric substance still has good II and MWD.Same comparative example 7 and comparative example 8, the specific silicoorganic compound C that selects is TEOS, can be polymerized the olefin polymer obtaining high MI, and this polymkeric substance still has good II and MWD.
The solid ingredient B1-B3 that the polyreaction of carrying out in comparative example 9-13 uses prior art to obtain.Comparative example 4 and comparative example 9-11, although use CHMMS, pre-complexing and low-temp reaction, the B1 that comparative example 9-11 uses solid ingredient to obtain for prior art, therefore, when carrying out high temperature polymerization, polymerization activity is extremely low, does not even have polymerization activity, can only carry out low temperature polymerization.
In comparative example 12-13, when being used for polyreaction containing B2 and B3 solid ingredient in olefin polymerization catalysis, although activity can reach the requirement of industrial application, the polymkeric substance of isotactic index >99% can not be obtained under the same conditions.
Method provided by the invention can carry out alpha-olefine polymerizing under high temperature, can have high polymerization activity, and the olefin polymer of acquisition, when obtaining high fusion index, can also have high isotactic and wide molecular weight distribution index, have good industrial application value.
Claims (10)
1. prepare a method for olefin polymer, the method comprises the following steps:
(1) 'alpha '-olefin monomers and olefin polymerization catalysis are carried out low-temp reaction, the temperature of described low-temp reaction is for being more than or equal to 0 DEG C and being less than 50 DEG C, and the time of described low-temp reaction is 1-60 minute;
(2) the low-temp reaction product that step (1) obtains is carried out high temperature polymerization reaction, the temperature of described high temperature polymerization reaction is 80-120 DEG C;
Described olefin polymerization catalysis contains solid ingredient A containing magnesium and titanium and silicoorganic compound C;
The described solid ingredient A containing magnesium and titanium is prepared by following steps:
A magnesium halide is dissolved in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent by (), form homogeneous solution, optionally add internal electron donor compound c;
B (), at-30 DEG C at 60 DEG C, the solution mixing first titanium compound and step (a) obtained, then adds precipitation additive solution, forms mixture; Or first precipitation additive solution is joined in the solution that step (a) obtains, then at-30 DEG C at 60 DEG C, mix with titanium compound, form mixture;
C the mixture obtained in step (b) is warming up to 60-110 DEG C by (), optionally internal electron donor compound d is added at temperature-rise period or after temperature, after temperature, stir 0.5-8 hour, elimination mother liquor, after inert diluent washing, obtain the solids containing magnesium and titanium;
The d mixture process of solids containing titanium compound, inert diluent and optional internal electron donor compound e 1 time containing magnesium and titanium that () will obtain in step (c), again by the mixture process containing titanium compound and inert diluent 1-2 time, use inert diluent washes clean subsequently, the obtained solid ingredient A containing magnesium and titanium;
Wherein precipitation additive solution is the mixing solutions containing precipitation additive a and precipitation additive b; In every mole of magnesium halide, organic epoxy compound thing is 0.2-10 mole, organo phosphorous compounds is 0.1-3 mole, titanium compound is 0.5-50 mole, precipitation additive A is 0.001-0.3 mole, and precipitation additive B is 0.001-0.5 mole, internal electron donor compound c is 0-3 mole, internal electron donor compound d and e is respectively 0-5 mole, and c+d+e is 0-5 mole;
Described silicoorganic compound C is at least one in dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane and tetraethoxysilane.
2. method according to claim 1, wherein, described olefin polymerization catalysis also includes machine aluminium compound B; Aluminium element in described organo-aluminium compound B and the described mol ratio containing the titanium elements in the solid ingredient A of magnesium and titanium are 5-5000:1, and the mol ratio of the aluminium element in described organo-aluminium compound B and described silicoorganic compound C is 0.1-500:1.
3. method according to claim 1 and 2, wherein, the multiplying power of described low-temp reaction is 10-500g polymkeric substance/g catalyzer, and the temperature of described low-temp reaction is 10 DEG C-50 DEG C, the time of described low-temp reaction is 0.5-20 minute, and the pressure of described low-temp reaction is 0.1-3MPa.
4. method according to claim 1 and 2, wherein, the temperature of described high temperature polymerization reaction is 85-110 DEG C, and the time of described high temperature polymerization reaction is 0.5-4 hour, and the pressure of described high temperature polymerization reaction is 0.5-5MPa.
5. method according to claim 1 and 2, wherein, the weight ratio of described monomer and described olefin polymerization catalysis is 50000-200000:1.
6. method according to claim 1 and 2, wherein, described monomer is at least one in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
7. method according to claim 1 and 2, wherein, described method is also included in before described olefin polymerization catalysis and described monomer carry out low-temp reaction, complex reaction is carried out containing magnesium and the solid ingredient A of titanium, described organo-aluminium compound B and described silicoorganic compound C by described, the temperature of described complex reaction is 0 DEG C-50 DEG C, and the time of described complex reaction is 0.1-30 minute.
8. method according to claim 7, wherein, the temperature of described complex reaction is 10-30 DEG C, and the time of described complex reaction is 0.1-10 minute.
9. the olefin polymer prepared by the method in claim 1-8 described in any one.
10. olefin polymer according to claim 9, wherein, the melting index of described olefin polymer is 1-300g/10min, and degree of isotacticity is 94-99.8%, and molecular weight distributing index is 4-15; Preferably, melting index be 4-150g/10min, degree of isotacticity is 95-99.5%, and molecular weight distributing index is 5.5-10.
Priority Applications (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109678995A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN109678994A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN109679005A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| JP2021502471A (en) * | 2017-11-13 | 2021-01-28 | ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ | Catalyst components for propylene polymerization |
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| CN1258683A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Catalyst for polymerization or copolymerization of propylene and its preparation and use |
| CN103087237A (en) * | 2011-10-29 | 2013-05-08 | 中国石油化工股份有限公司 | Preparation method of propylene random copolymer |
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| CN1258683A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Catalyst for polymerization or copolymerization of propylene and its preparation and use |
| CN103087237A (en) * | 2011-10-29 | 2013-05-08 | 中国石油化工股份有限公司 | Preparation method of propylene random copolymer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678995A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN109678994A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN109679005A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| JP2021502471A (en) * | 2017-11-13 | 2021-01-28 | ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ | Catalyst components for propylene polymerization |
| JP7366912B2 (en) | 2017-11-13 | 2023-10-23 | ダブリュー・アール・グレース・アンド・カンパニー－コーン | Catalyst components for propylene polymerization |
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