CN1966537A - Isoolefin polymer or copolymer preparation method - Google Patents
Isoolefin polymer or copolymer preparation method Download PDFInfo
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- CN1966537A CN1966537A CN 200510123423 CN200510123423A CN1966537A CN 1966537 A CN1966537 A CN 1966537A CN 200510123423 CN200510123423 CN 200510123423 CN 200510123423 A CN200510123423 A CN 200510123423A CN 1966537 A CN1966537 A CN 1966537A
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Abstract
The invention provides a preparation method for isoolefine copolymer with excellent mechanical properties and processing properties through cationic polymerization. The said method includes carrying out homopolymerization of C4-C7 isoolefine monomers or copolymerization of C4-C7 isoolefine monomers with other monomers in the hydrocarbons or halohydrocarbons diluents with composite catalyst solution. The referred composite catalyst solution is the reaction product of Lewis acid and additive, wherein the additive is selected from at least one of phenols, amides, amines, pyridines, carboxylic acids, or ketones and esters. The addition amount of Lewis acids is 10-4-10-2 mole/L based on the concentration of slurry or solution, and the molar ratio of Lewis acid to additive is at 0.01-1.0.
Description
Technical field
The present invention relates to the preparation method of a kind of isoolefin polymer or multipolymer, more particularly, relate to a kind of method that adopts cationoid polymerisation prepared isoolefin polymer or multipolymer.Can directly prepare by this method and to have the excellent mechanical property and the polyisobutene and the isoprene-isobutylene rubber product of processing characteristics concurrently.
Background technology
" isoolefin homopolymer " described in this specification sheets is meant and comprises C
4～C
7The polymkeric substance, particularly polyisobutene of isoolefine, when molecular weight was enough big, it had certain elasticity.Isoprene-isobutylene rubber is the multipolymer of iso-butylene and a small amount of isoprene or p-methylstyrene normally, and wherein isoprene chain link or p-methylstyrene chain link are random distribution on macromolecular chain.Usually, the main commercially available prod of polyisobutene or isoprene-isobutylene rubber is to use Lewis acid (being typically with aluminum chloride and boron trifluoride) by the cationic polymerization process synthetic at low temperatures.Ethyl aluminum dichloride and aluminium diethyl monochloride also are considered to can be used in this type of polymerization.Isoprene-isobutylene rubber is one of important rubber clone, has extremely excellent resistance to air loss and watertightness, is mainly used in the production air tube.
In the tire manufacturing is used, need rubber to possess stress relaxation rate fast usually, make the stress that in making the course of processing, is applied to discharge rapidly, make rubber can slowly not be out of shape because of dissipative stress not or peel off.In general, stress relaxation rate is the function of molecular weight, and along with molecular weight increases, stress relaxation rate is slack-off.Simultaneously, rubber must possess sufficiently high mechanical property again when using as material, as higher green strength.It is generally acknowledged that the molecular weight of green strength and its rubber is closely related, molecular weight is high more, and green strength is high more.Molecular weight is high more also will to cause the polymer processing difficulty.So mechanical property is just in time opposite to the requirement of molecular weight with stress relaxation rate.Therefore, in the practical application and processing of isoprene-isobutylene rubber, just need consider and coordinate high green strength and fast two aspects of stress relaxation rate simultaneously, thereby be necessary the molecular weight and the molecular weight distribution of rubber are controlled, promptly need to be used in the high molecular weight block that improves green strength and reach certain balance with the low molecular weight fraction that is used to improve stress relaxation rate, thus all very good elastomeric material of the mechanical property of obtaining and processing characteristics.
In the prior art, adopt following two kinds of methods to regulate or control the molecular weight and the molecular weight distribution of elastomeric material usually: the one, the physical blending method; The 2nd, the polyreaction method.
The physical blending method is that the isobutene polymer product with high, medium and low different molecular weight mixes by a certain percentage and obtains a kind of particular molecular weight distribution, realize combining of green strength and stress relaxation with this, preparation mechanical property and the good isoprene-isobutylene rubber mixture of processing characteristics.But because the method for this physical blending is very difficult the microtexture and the homodisperse of elastomeric material inside are effectively controlled, and the technical process complexity, so the performance of gained material awaits further to improve after its blend.
The polyreaction method is in the polymerization of isoolefine or copolymerization, in the copolyreaction process as iso-butylene and isoprene, by selectively, controllably changing initiator or branching agent kind or consumption, on purpose prepare the isoprene-isobutylene rubber that contains high molecular weight block and low molecular weight fraction of design.
United States Patent (USP) 5,194, disclose in 538 in polymerization process to add and had two, three or the initiator with special chemical structure of four-functional group, by strictness control initiator system and preparation process condition thereof, adopt and realize the synthetic isoprene-isobutylene rubber that contains high molecular and low-molecular-weight bimodal molecular weight distribution that has.But the initiator structure that adopts in this method is special, does not still have the industrialization commodity, needs the laboratory to prepare voluntarily and strict the purification, thereby increases preparation section and cost.
Disclose a kind of among WO 01/85810 A1 by changing lewis acidic chemical structure, promptly adopt the mixture of dialkylaluminum halides, alkyl dihalide aluminium and aluminum alkoxide (MAO) to cause iso-butylene and isoprene copolymer altogether, with the isoprene-isobutylene rubber product of synthetic wide molecular weight distribution.But, introduced the organo-aluminium compound that costs an arm and a leg with poor stability in this method, as MAO.
US 5,071,913 and EP 0678529 disclose and a kind ofly adjust and control molecular weight distribution to influence the desired performance of polymerisate by adding branching agent, promptly in polymerization process, introduce the multiple functionalized polymer branching agent of cation activity selectively, these branching agents can participate in the cationic polymerization of iso-butylene and isoprene, form high-molecular weight grafting or branched polymer, between polymerization period, generate simultaneously low-molecular-weight line polymer, thereby can directly prepare containing high molecular and low-molecular-weightly having an isoprene-isobutylene rubber product that suitable molecular weight distributes of design.These branching agents are selected from and have and can or generate the polymkeric substance or the multipolymer of the functional group of chemical bond with the polymerisate copolymerization that generates, and lyophilic, the soluble part of polymerisation diluent that this base polymer or multipolymer are preferably with, olefin copolymer, polyisoprene and hydrohalogenation product thereof, halogenated polystyrene, hydrohalogenation or the halogenated polyhutadiene and polystyrene block copolymer and poly-(1,3-pentadiene) etc. that contain the allyl halide structure as main chain.Must additional chemical structure functionalization in this method improve step or to the separation purification step of polymer branching agent strictness to the polymer branching agent.
Summary of the invention
The invention provides a kind of cationic polymerization that passes through, preparation has the method for the isoolefin polymer or the multipolymer of excellent mechanical property and processing characteristics.This method is included in halohydrocarbon or the hydrocarbon diluent, under the complex catalyst solution effect, carries out C
4-C
7The monomeric homopolymerization of isoolefine or with other monomeric copolyreaction, described complex catalyst solution is the reaction product of Lewis acid and additive, wherein additive is selected from least a in the following compound: by general formula R
1Alcohols that-OH represents or phenols, general formula N (R
2)
3The amine of expression or pyridines, general formula R
3COON (R
4)
2Amides, the general formula of expression are R
5COOR
6Carboxylic acid esters, the general formula of expression are R
7COR
8The ketone of expression, wherein R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be straight or branched alkyl, virtue (alkane) base, thiazolinyl, the alkyl of replacement, virtue (alkane) base of replacement or the thiazolinyl that replaces of 1～15 identical or different carbon atom, and lewis acidic add-on counts 10 with slurries or strength of solution
-4-10
-2Mol, additive and lewis acidic mol ratio are 0.01-1.0, preferred 0.02～0.5.
In above-mentioned polymerization process, described Lewis acid is selected from least a in aluminum chloride, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium, dichloro amyl group aluminium, sesquialter ethyl aluminum chloride, sesquialter propyl group aluminum chloride, sesquialter butyl aluminum chloride, sesquialter amyl group aluminum chloride, aluminium diethyl monochloride, a chlorine dipropyl aluminium, boron trichloride and the boron trifluoride.Be preferably aluminum chloride, alchlor or boron trifluoride.
In above-mentioned polymerization process, the alcohols in the described additive includes but not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, n-hexyl alcohol, isohexyl alcohol, uncle's hexanol, phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol etc.Described phenols includes but not limited to phenol, methylphenol, xylenol, ethylphenol, diethyl phenol, propylphenol, dipropyl phenol, butylphenol, dibutyl phenol.
In above-mentioned polymerization process, the amine in the described additive includes but not limited to diethylamine, triethylamine, aniline, pentanoic, triphenylamine, N, dinethylformamide, N,N-dimethylacetamide, N, N-diethylformamide, N, N-diethyl acetamide etc.
In above-mentioned polymerization process, the pyridines in the described additive includes but not limited to pyridine, picoline, lutidine, vinyl pyridine, 3-methyl-2-phenylpyridine, phenmethyl pyridine, piperidines, N-methyl piperidine etc.
In above-mentioned polymerization process, in the described additive by R
5COOR
6The carboxylic acid esters of expression includes but not limited to methyl acetate, ethyl acetate, vinyl-acetic ester, propyl acetate, allyl acetate, jasmal, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the maleic dimethyl phthalate, the maleic diethyl phthalate, maleic acid dipropyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, the phenylformic acid allyl ester, phenylformic acid alkene butyl ester, peruscabin, phenylethyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diamyl phthalate, dihexyl phthalate, diheptyl phthalate or dioctyl phthalate (DOP) etc.
In above-mentioned polymerization process, the ketone in the described additive includes but not limited to acetone, butanone, pentanone, hexanone, pimelinketone, 2,4-hexanedione, methyl phenyl ketone, methyl ethyl diketone, acetonyl-acetone etc.
In polymerization process of the present invention, need usually at least a Lewis acid and at least a additive, in-110 ℃～25 ℃ temperature ranges, preferred-100 ℃～-20 ℃ contact reactss obtain a homogeneous complex catalyst solution.Be generally preferred 4min～4 hours the duration of contact of Lewis acid and additive 1 minute～10 hours.Additive and lewis acidic mol ratio are controlled at 0.01-1.0, are preferably 0.02～0.5.
Except that need under above-mentioned complex catalyst solution effect, causing the cationoid polymerisation of isoolefine,, can also in polymerization process, add above-mentioned Lewis acid in addition or/and at least a additive according to requirement to the polymerisate different performance.Wherein lewis acidic add-on counts 10 with slurries or strength of solution
-6-10
-3Mol, the add-on of additive counts 10 with slurries or strength of solution
-6-10
-3Mol.By in polymerization system, generating new active centre on the spot,, form the polymerisate of lower molecular weight fraction and higher molecular weight fraction respectively, to reach suitable molecular weight distribution with the common initiated polymerization in active centre that composite catalyst produces.
In polymerization process of the present invention, described C
4-C
7The preferred iso-butylene of isoolefine monomer, 2-methyl-1-butene alkene etc., the preferred isoprene of comonomer, pentadiene, p-methylstyrene etc.
Described cationic polymerization can adopt the form of slurry or solution polymerization, thinner that is adopted or solvent can adopt halohydrocarbon or hydrocarbon compound and their isomer, as hexane, heptane, isoheptane, octane, octane-iso, methylcyclohexane, methyl chloride, methylene dichloride, monochloroethane, ethylene dichloride and their mixture.Preferred monochloro methane, methylene dichloride, monochloroethane, monochloroethane, hexane and composition thereof.Their add-on is not particularly limited, as long as help the carrying out of polyreaction.
The inventive method is preferably carried out under-100～-10 ℃ of temperature.Preferably below-20 ℃.
Method of the present invention can be carried out under normal pressure, is applicable to continuously or the batchwise polymerization mode.
It is worthy of note according to industry technician's generally understanding, obtain desirable polymeric articles and the coordinated balance that reaches green strength and stress relaxation, very high to the requirement of polymericular weight and molecular weight distribution.The Comprehensive Control of the kind by additive and phase application quantity, preparation of catalysts mode and polymeric reaction condition is in the hope of the gratifying polymkeric substance of obtained performance in the present invention.By the isoolefin polymer that the inventive method obtains, high molecular weight block accounts for about 5～25% (wt) in its polymkeric substance, preferred 8～20% (wt); Low molecular weight fraction accounts for about 5～25% (wt), preferred 8～20% (wt).Peak molecular weight is greater than 17 * 10
4, preferably 25 * 10
4～70 * 10
4Between.
In addition, among the present invention by in polymerization reaction system, quoting a kind of complex catalyst solution, can not only improve the effect of dispersion effect and stable slurry, and can reach the molecular weight and the molecular weight distribution of regulating polymerisate within the specific limits, and then reach the directly polymerisate of the synthetic expection of control in polymerization process, prepare polyisoolefines and multipolymer thereof, as isoprene-isobutylene rubber with excellent mechanical property and processing characteristics.
Embodiment
Following illustrative example illustrates in greater detail the present invention, but the present invention is not subjected to the restriction of these embodiment.
Testing method
1, adopt weighting method to measure the monomer polymerization transformation efficiency;
2, adopt the GPC method to measure weight-average molecular weight, peak molecular weight and the molecular weight distributing index of polymerisate, and obtain the content of different molecular weight fraction scope according to the original integration data that GPC gathers.
Embodiment
Embodiment 1
1, the preparation of complex catalyst solution:
Under the protection of-50 ℃ and high pure nitrogen, with the hexalin of 0.1mmol and the AlCl of 0.8mmol
3Be pre-mixed afterreaction 60min, to prepare homogeneous catalyst solution.Hexalin/AlCl wherein
3=0.125.
2, polyreaction:
Under the protection of-50 ℃ and high pure nitrogen, to 20mL monomer iso-butylene (IB) and CH are housed
2Cl
2The mixing solutions of/normal hexane (v/v=40/60) is (in [IB]=1.5mol/L), add the above-mentioned reacted in advance catalyst solution of 2.6mL and begin polyreaction, behind the polymerization 5min, add ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 98.8%.Weight-average molecular weight is 34.5 * 10
4Peak molecular weight is 26.6 * 10
4Molecular weight distributing index is 3.54.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 10%, be 46% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 16%.
Comparative Examples 1:
Raw material and operational condition are substantially with embodiment 1, but preparation method's difference.Under the protection of-50 ℃ and high pure nitrogen, in the polyreaction bottle, add hexalin and 20mL IB and the CH of 0.01mmol
2Cl
2([IB]=1.5mol/L) adds the AlCl of 0.08mmol to the mixing solutions of/n-hex (v/v=40/60) then
3The beginning polyreaction behind the 5min, adds ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.Monomer conversion is 99.4%, and weight-average molecular weight is 11.2 * 10
4Peak molecular weight is 10.7 * 10
4, molecular weight distributing index is 3.56.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 0, molecular weight is greater than 50 * 10
4Polymer content only be 2%, be 37% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 50%.
Embodiment 2
1, the preparation of complex catalyst solution:
Under the protection of-50 ℃ and high pure nitrogen, with the phenylcarbinol of 0.12mmol and the AlCl of 0.67mmol
3Be pre-mixed back ageing reaction 60min, to prepare homogeneous catalyst solution, wherein phenylcarbinol/AlCl
3=0.18.
2, polyreaction: with embodiment 1.The IB transformation efficiency is 64.3%, and weight-average molecular weight is 44.3 * 10
4Peak molecular weight M
p=34.6 * 10
4Molecular weight distributing index is 2.59.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 14%, be 46% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 8%.
Embodiment 3
Polyreaction: under the protection of-50 ℃ and high pure nitrogen, in the polyreaction bottle, add 2.12 * 10
-3The phenylcarbinol of mmol and 20mL IB and CH
2Cl
2([IB]=1.5mol/L) adds reacted in advance catalyst solution of 3.2mL embodiment 2 and 0.96mLAlCl to the mixing solutions of/n-hex (v/v=40/60) then
3Solution (concentration is 0.0176mol/L) beginning polyreaction behind the 5min, adds ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.Monomer conversion is 100%, and weight-average molecular weight is 24.5 * 10
4Peak molecular weight is 17.7 * 10
4, molecular weight distributing index is 2.77.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 5%, be 48% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 18%.
Embodiment 4
1, the preparation of complex catalyst solution:
Under the protection of 20 ℃ and high pure nitrogen, with the methyl benzoate of 0.094mmol and the AlCl of 0.855mmol
3Be pre-mixed back ageing reaction 20min, to prepare the homogeneous catalyst solution.Methyl benzoate/AlCl
3=0.11.
2, polyreaction:
With embodiment 1, but the add-on of complex catalyst solution changes 3.8mL into.The IB transformation efficiency is 61.5%, and weight-average molecular weight (Mw) is 29.1 * 10
4Peak molecular weight is 24.0 * 10
4Molecular weight distributing index is 2.60.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 5%, be 45% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 13%.
Embodiment 5
1, the preparation of complex catalyst solution:
Under the protection of-50 ℃ and high pure nitrogen, with the methyl benzoate of 0.3mmol and the AlCl of 8.2mmol
3Be pre-mixed back ageing reaction 60min, to prepare homogeneous catalyst solution.Methyl benzoate/AlCl
3=0.039.
2, polyreaction:
With embodiment 1, but the add-on of complex catalyst solution changes 3.7mL into.The IB transformation efficiency is 100%, and weight-average molecular weight (Mw) is 29.2 * 10
4Peak molecular weight is 22.2 * 10
4Molecular weight distributing index is 3.85.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 7%, be 44% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 20%.
Comparative Examples 5
Under the protection of-50 ℃ and high pure nitrogen, in the polyreaction bottle, add methyl benzoate and 20mL IB and the CH of 0.002mmol
2Cl
2([IB]=1.5mol/L) adds the AlCl of 0.056mmol to the mixing solutions of/n-hex (v/v=40/60) then
3The beginning polyreaction behind the 5min, adds ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.Monomer conversion is 100%, and weight-average molecular weight (Mw) is 16.5 * 10
4Peak molecular weight is 14.1 * 10
4, molecular weight distributing index is 2.94.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 0%, be 43% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 29%.
Embodiment 6
1, the preparation of complex catalyst solution: under the protection of-60 ℃ and high pure nitrogen, with the AlCl of 0.088mmol pimelinketone and 0.88mmol
3Be pre-mixed afterreaction 60min, to prepare the homogeneous catalyst solution.Pimelinketone/AlCl wherein
3=0.1.
2, polyreaction:
Under the protection of-60 ℃ and high pure nitrogen, to 20mL IB and CH are housed
2Cl
2([IB]=1.5mol/L) adds the above-mentioned reacted in advance catalyst solution of 3.2mL and begins polyreaction the monomer mixture solution of/n-hex (v/v=40/60), behind the polymerization 5min, add ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 78.8%, and weight-average molecular weight (Mw) is 60.8 * 10
4Peak molecular weight is 50.1 * 10
4Molecular weight distributing index is 2.39.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 24%, be 45% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 5%.
Embodiment 7
1, the preparation of complex catalyst solution: with embodiment 6.
2, polyreaction:
Under the protection of-60 ℃ and high pure nitrogen, to being equipped with 1.1 * 10
-5mmolN, N-N,N-DIMETHYLACETAMIDE and 20mLIB and CH
2Cl
2([IB]=1.5mol/L) adds above-mentioned reacted in advance catalyst solution of 3.2mL and 0.32mL AlCl to the monomer mixture solution of/n-hex (v/v=40/60)
3Solution (concentration is 0.0176mol/L) beginning polyreaction behind the polymerization 5min, adds ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 82.6%, and weight-average molecular weight (Mw) is 42.0 * 10
4Peak molecular weight is 35.7 * 10
4Molecular weight distributing index is 3.38.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 13%, be 42% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 13%.
Embodiment 8
1, the preparation of complex catalyst solution: under the protection of-60 ℃ and high pure nitrogen, with the AlCl of 0.88mmol pimelinketone and 8.8mmol
3Be pre-mixed back ageing reaction 60min, to prepare the homogeneous catalyst solution.
2, polyreaction:
Under the protection of-60 ℃ and high pure nitrogen, to being equipped with 1.70 * 10
-3Mmol pimelinketone and 20mL IB and CH
2Cl
2([IB]=1.5mol/L) adds above-mentioned reacted in advance catalyst solution of 3.2mL and 0.48mL AlCl to the monomer mixture solution of/n-hex (v/v=40/60)
3Solution (concentration is 0.0176mol/L) beginning polyreaction behind the polymerization 5min, adds ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 84.2%, and weight-average molecular weight is 37.9 * 10
4Peak molecular weight is 29.4 * 10
4Molecular weight distributing index is 2.98.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 11%, be 45% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 11%.
Embodiment 9
1, the preparation of complex catalyst solution:
Under the protection of-80 ℃ and high pure nitrogen, with the AlCl of 2.2mmol phenylcarbinol and 17.6mmol
3Be pre-mixed back ageing reaction 110min, to prepare the homogeneous catalyst solution.Phenylcarbinol/AlCl wherein
3=0.1.
2, polyreaction:
Under the protection of-100 ℃ and high pure nitrogen, to 0.02mmol hexalin and 60mL iso-butylene IB, isoprene IP and CH are housed
3The monomer mixture solution of Cl ([IB]=4.0mol/L, IP/IB=0.025) add the reacted catalyst solution of the above-mentioned ageing in advance of 12mL and begin polyreaction, behind the polymerization 5min, add ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 84.2%, and weight-average molecular weight (Mw) is 47.0 * 10
4Peak molecular weight is 52.2 * 10
4Molecular weight distributing index is 2.10.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 15%, be 35% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 8%.
Embodiment 10
1, the preparation of complex catalyst solution:
Under the protection of-80 ℃ and high pure nitrogen, with the AlCl of 0.5mmol triethylamine and 17.6mmol
3Be pre-mixed back ageing reaction 5min, to prepare the homogeneous catalyst solution.Triethylamine/AlCl wherein
3=0.03.
2, polyreaction:
Under the protection of-100 ℃ and high pure nitrogen, to 150mL iso-butylene IB, isoprene IP and CH are housed
3The monomer mixture solution of Cl ([IB]=4.0mol/L, IP/IB=0.025) add the reacted catalyst solution of the above-mentioned ageing in advance of 20mL and begin polyreaction, behind the polymerization 5min, add ethanol/water (V/V=50/50) the mixing solutions termination polymerization that 2mL contains 1wt%NaOH.After polymerisate removed solvent and unreacted IB, after repeatedly washing purifying, 40 ℃ of following vacuum-dryings were to constant weight.The IB transformation efficiency is 85%, and weight-average molecular weight (Mw) is 33.8 * 10
4Peak molecular weight is 36.0 * 10
4Molecular weight distributing index is 2.0.Molecular weight is greater than 80 * 10 in polymerisate
4Polymer content be 7%, be 43% greater than the polymer content of peak molecular weight, and molecular weight is less than 7 * 10
4Polymer content be 10%.
Table 1
| Numbering | IB transformation efficiency (%) | Weight-average molecular weight * 10 4 | Peak molecular weight * 10 4 | Molecular weight distributing index | Content in the polymerisate (wt%) | ||
| Molecular weight is greater than 80 * 10 4 | Greater than peak molecular weight | Molecular weight is less than 7 * 10 4 | |||||
| Example 1 | 98.8 | 34.5 | 26.6 | 3.54 | 10 | 46 | 16 |
| Contrast 1 | 99.4 | 11.2 | 10.7 | 3.56 | 0 | 37 | 50 |
| Example 2 | 64.3 | 44.3 | 34.6 | 2.59 | 14 | 46 | 8 |
| Example 3 | 100 | 24.5 | 17.7 | 2.77 | 5 | 48 | 18 |
| Example 4 | 61.5 | 29.1 | 24.0 | 2.6 | 5 | 45 | 13 |
| Example 5 | 100 | 29.2 | 22.2 | 3.85 | 7 | 44 | 20 |
| Contrast 5 | 100 | 16.5 | 14.1 | 2.94 | 0 | 43 | 29 |
| Example 6 | 78.8 | 60.8 | 50.1 | 2.39 | 24 | 45 | 5 |
| Example 7 | 82.6 | 42.0 | 35.7 | 3.38 | 13 | 42 | 13 |
| Example 8 | 84.2 | 37.9 | 29.4 | 2.98 | 11 | 45 | 11 |
| Example 9 | 84.2 | 47.0 | 52.2 | 2.10 | 15 | 35 | 8 |
| Example 10 | 85.0 | 33.8 | 36.0 | 2.50 | 7 | 43 | 10 |
By the contrast of above-mentioned data as can be seen, the present invention adopts additive and catalyzer reacted in advance and makes composite catalyst, can obviously improve high molecular weight block content in the polymkeric substance, reduces low molecular weight fraction content, adjusts molecular weight distribution.In addition, except adding composite catalyst, in polymerization process, also can add identical or different additive and/or Lewis acid, also can suitably increase high molecular weight block content and low molecular weight fraction content simultaneously, adjust molecular weight distribution.Thereby prepare the isoolefin polymer and the multipolymer thereof of specified molecular weight and molecular weight distribution, reach the overall equilbrium of its mechanical property and processing characteristics, had the polyisoolefines and the multipolymer thereof of excellent mechanical property and processing characteristics simultaneously, as isoprene-isobutylene rubber.
Claims (10)
1, the preparation method of a kind of isoolefin polymer or multipolymer, it is included in halohydrocarbon or the hydrocarbon diluent, under the complex catalyst solution effect, carries out C
4-C
7The equal polymerization of the monomeric positively charged ion of isoolefine reaction or with other monomeric cationic copolymerizations reactions, described complex catalyst solution is the reaction product of Lewis acid and additive, wherein additive is selected from least a in the following compound: by general formula R
1Alcohols that-OH represents or phenols, general formula N (R
2)
3The amine of expression or pyridines, general formula R
3COON (R
4)
2Amides, the general formula of expression are R
5COOR
6Carboxylic acid esters, the general formula of expression are R
7COR
8The ketone of expression, wherein R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be straight or branched alkyl, virtue (alkane) base, thiazolinyl, the alkyl of replacement, virtue (alkane) base of replacement or the thiazolinyl that replaces of 1～15 identical or different carbon atom, and lewis acidic add-on counts 10 with slurries or strength of solution
-4-10
-2Mol, additive and lewis acidic mol ratio are 0.01-1.0.
2, by the preparation method of described isoolefin polymer of claim 1 or multipolymer, it is characterized in that additive and lewis acidic mol ratio are 0.02～0.5.
3, by the preparation method of described isoolefin polymer of claim 1 or multipolymer, it is characterized in that can also adding at least a Lewis acid in described polyreaction, its add-on counts 10 with slurries or strength of solution
-6-10
-3Mol.
4, by the preparation method of described isoolefin polymer of claim 1 or multipolymer, it is characterized in that adding the described additive of at least a claim 1 in described polyreaction, its add-on counts 10 with slurries or strength of solution
-6-10
-3Mol.
5,, it is characterized in that described Lewis acid is to be selected from least a by in aluminum chloride, alchlor, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium, sesquialter ethyl aluminum chloride, sesquialter propyl group aluminum chloride, sesquialter butyl aluminum chloride, sesquialter amyl group aluminum chloride, aluminium diethyl monochloride, a chlorine dipropyl aluminium, boron trichloride and the boron trifluoride by the preparation method of claim 1 or 3 described isoolefin polymers or multipolymer.
6, by the preparation method of claim 1 or 4 described isoolefin polymers or multipolymer, it is characterized in that described additive is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, n-hexyl alcohol, isohexyl alcohol, uncle's hexanol, phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol etc.Described phenols includes but not limited at least a in phenol, methylphenol, xylenol, ethylphenol, diethyl phenol, propylphenol, dipropyl phenol, butylphenol and the dibutyl phenol.
7, press the preparation method of claim 1 or 4 described isoolefin polymers or multipolymer, it is characterized in that described additive is selected from diethylamine, triethylamine, aniline, pentanoic, triphenylamine, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethylformamide and N, at least a in the N-diethyl acetamide.
8,, it is characterized in that described additive is selected from least a in pyridine, picoline, lutidine, vinyl pyridine, 3-methyl-2-phenylpyridine, phenmethyl pyridine, piperidines and the N-methyl piperidine by the preparation method of claim 1 or 4 described isoolefin polymers or multipolymer.
9, preparation method by claim 1 or 4 described isoolefin polymers or multipolymer is characterized in that described additive is selected from methyl acetate, ethyl acetate, vinyl-acetic ester, propyl acetate, allyl acetate, jasmal, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the maleic dimethyl phthalate, the maleic diethyl phthalate, maleic acid dipropyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, the phenylformic acid allyl ester, phenylformic acid alkene butyl ester, peruscabin, phenylethyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diamyl phthalate, dihexyl phthalate, at least a in diheptyl phthalate and the dioctyl phthalate (DOP).
10, press the preparation method of claim 1 or 4 described isoolefin polymers or multipolymer, it is characterized in that described additive is selected from acetone, butanone, pentanone, hexanone, pimelinketone, 2, at least a in 4-hexanedione, methyl phenyl ketone, methyl ethyl diketone and the acetonyl-acetone.
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| CNB2005101234233A CN100523018C (en) | 2005-11-18 | 2005-11-18 | Isoolefin polymer or copolymer preparation method |
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|---|---|---|---|
| CNB2005101234233A CN100523018C (en) | 2005-11-18 | 2005-11-18 | Isoolefin polymer or copolymer preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613427B (en) * | 2008-06-27 | 2011-04-20 | 北京化工大学 | Method for preparing polyisobutylene with high reaction activity |
| CN101781377B (en) * | 2009-01-16 | 2011-07-20 | 北京化工大学 | Initiation system for preparing high-reactivity polyisobutene |
| CN101955558B (en) * | 2009-07-15 | 2013-03-13 | 北京化工大学 | Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene |
| CN108264597A (en) * | 2018-02-11 | 2018-07-10 | 山东齐鲁石化工程有限公司 | Butyl rubber liquid catalyst paradigmatic system |
| DE112017004476T5 (en) | 2016-09-07 | 2019-05-23 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | Butyl rubber and its manufacturing process, rubber product and composition and use, as well as airtight layer of the car tire, hose and vulcanized capsule |
| CN111303551A (en) * | 2018-12-12 | 2020-06-19 | 北京化工大学 | Vinyl chloride resin compound and preparation method thereof |
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2005
- 2005-11-18 CN CNB2005101234233A patent/CN100523018C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613427B (en) * | 2008-06-27 | 2011-04-20 | 北京化工大学 | Method for preparing polyisobutylene with high reaction activity |
| CN101781377B (en) * | 2009-01-16 | 2011-07-20 | 北京化工大学 | Initiation system for preparing high-reactivity polyisobutene |
| CN101955558B (en) * | 2009-07-15 | 2013-03-13 | 北京化工大学 | Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene |
| DE112017004476T5 (en) | 2016-09-07 | 2019-05-23 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | Butyl rubber and its manufacturing process, rubber product and composition and use, as well as airtight layer of the car tire, hose and vulcanized capsule |
| US10894881B2 (en) | 2016-09-07 | 2021-01-19 | China Petroleum & Chemical Corporation | Product, composition and application thereof, and automobile tire inner liner, tube and curing bladder |
| CN108264597A (en) * | 2018-02-11 | 2018-07-10 | 山东齐鲁石化工程有限公司 | Butyl rubber liquid catalyst paradigmatic system |
| CN111303551A (en) * | 2018-12-12 | 2020-06-19 | 北京化工大学 | Vinyl chloride resin compound and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100523018C (en) | 2009-08-05 |
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