CN101585891B - Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same - Google Patents
Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same Download PDFInfo
- Publication number
- CN101585891B CN101585891B CN2008101118147A CN200810111814A CN101585891B CN 101585891 B CN101585891 B CN 101585891B CN 2008101118147 A CN2008101118147 A CN 2008101118147A CN 200810111814 A CN200810111814 A CN 200810111814A CN 101585891 B CN101585891 B CN 101585891B
- Authority
- CN
- China
- Prior art keywords
- tin
- dichloride
- component
- initiator system
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a Lewis acid-carbon cationic-polymerization initiator system for preparing isoolefine polymers or copolymers, and a method for preparing high-molecular-weight isoolefine polymers or copolymers by adopting cationic polymerization. The method comprises the steps of using a Lewis acid-carbon cationic initiator system to perform homopolymerization of isoolefine monomers or copolymerization of the isoolefine monomers and other polyene hydrocarbon, and ensuring that obtained polymers have the characteristic of adjustable molecular weight distribution in a certain range by introducing organic tin compounds.
Description
Technical field
The present invention relates to a kind of initiator system that is used to prepare isoolefin homopolymer or multipolymer; Particularly in-100 ℃ to+20 ℃ polymerization temperature scope, be used for the Lewis acid carbon cation polymerization initiator system that iso-butylene homopolymerization, iso-butylene and isoprene copolymer close, and a kind of method for preparing the isoolefin polymer with controllable molecular weight distribution (MWD).
Background technology
Butyl rubber is the multipolymer of typical isoolefine and one or more conjugated polyene hydrocarbon.The butyl rubber that is purchased comprises the isoolefine of main part and the conjugated polyene hydrocarbon of less content, and preferred isoolefine is an iso-butylene.Conjugated polyene hydrocarbon commonly used comprises isoprene, divinyl, dimethylbutadiene, 1,3-pentadiene etc., wherein preferred isoprene.
The thirties in last century, the breadboard Michael Otto of German I.G.Farben finds at BF
3Under the existence condition, can obtain buttery polymkeric substance-low-molecular-weight polyisobutylene by isobutene polymerisation.The Baton Rouge of first in the world cover butyl rubber production equipment of nineteen forty-three in U.S. Louisiana state is constructed and put into operation, and wherein adopts AlCl down at-90 ℃～-100 ℃
3Cause iso-butylene and isoprene altogether and in the methyl chloride medium, carry out the incompatible preparation butyl rubber of cationic copolymerization.
Butyl rubber is a kind of elastomerics of odorless, tasteless, has characteristic and good insulation performance performance and resistances to tearing such as excellent resistance to air loss, watertightness, anti-ozone, antioxidant, ageing-resistant, heat-resisting, cold-resistant, weathering resistance, chemicals-resistant.Butyl rubber (comprising its halogenation modified product) is widely used in tube, tubeless tyre; Airbag, balloon, bladders, sealring, sealing agent, coating, vibroshock, adhesive plaster coating, Medical bottle stopper, capsule, curing bag, chewing gum glue; Insulating material; Automobile and flexible mechanical parts, tackiness agent, putty, Foldable container, storage tank liner, sebific duct, water-tight corrosion-proof building materials, smoke mask, sports goods, plastic asphalt blending modification etc.At present, butyl rubber becomes in the world
Being the fourth-largest synthetical glue kind, is the indispensable rubber raw materials of tire industry department.Butyl rubber is a best glue kind of making tube, also is the essential raw material of good radial-ply tyre.
Canadian patent application 2,252,295 disclose the method that catalyst system that a kind of use contains halogenation aluminum dialkyl, halogenation one aluminum alkyls and aikyiaiurnirsoxan beta or water prepares butyl rubber.It is that catalyst component carries out the isobutene polymerisation reaction-15 ℃ of direct down addings in the hydrocarbon polymer that Germany BASF AG (DE3300155) proposes to adopt ethylaluminum dichloride, tert-butyl chloride, and the molecular weight of product that obtains is 59000, and MWD is 4.5.The initiator system that patent WO0185810, US2003166809, US2002151663 and CN 1427851A adopt the aikyiaiurnirsoxan beta of the aluminum dialkyl monohalide of main quantity, a spot of dihalide one aluminum alkyls and trace to form; Be used to prepare the butyl rubber polymer of wide molecular weight distribution; MWD in about 4.0～10.0 scope, most preferably 5.0～8.0.Patent GB1094728 discloses a kind of butyl rubber catalyst system, and this system is by Al (M)
2(wherein M is C to R
1-C
12The straight or branched alkyl, and R can be M, hydrogen or halogen) and the Organohalogen compounds composition.The ratio of Primary Catalysts and promotor is 0.0001: 1 to 30: 1.This invention relates to is the rubber of producing high-molecular weight butyl type, and for example the multipolymer of iso-butylene carries out under far above the temperature that is adopted so far, for example-50 ℃.Generally speaking, its polymerization temperature can change in 0～-100 ℃ scope, and modal be between-27 ℃～-78 ℃.Patent US5448001 mentions the method for U.S. Queen ' s university invention with the metallocene catalysts butyl rubber.Under anhydrous and anaerobic condition, temperature is-100 ℃～-20 ℃, by CpMXX
1X
2And BRR
1R
2The initiator of forming-coinitiator system exists down, and iso-butylene and the isoprene copolyreaction speed in organic solvent (like toluene) is very fast.CpMXX
1X
2In Cp for leaning on the cyclopentadienyl moiety or the substituted cyclopentadienyl ligand of π key bonding, M represents Ti, Zr or Hf, X, X
1And X
2For including the identical or different anionic group of 1～20 non-hydrogen group; BRR
1R
2In B represent boron, R, R
1And R
2For including the identical or different anionic group of 1～30 non-hydrogen group.Explanation Polysar company uses by R among the patent US5194538
1[CR
2R
3(OH)]
n(R
1, R
2And R
3Be alkyl, aryl and aralkyl, n=2～6), the ternary complex catalyst system formed of certain catalyst component and certain Lewis acid with diamantane core, will be by the C of massfraction 95%～99.5% iso-butylene and massfraction 5%～0.5%
4～C
8The mix monomer that conjugated diene is formed is polymerized to the butyl rubber with bimodal molecular weight distribution under-120 ℃～50 ℃ conditions in inert organic solvents.For example, with CH
3Cl is a solvent, 1, and 4-two (2-hydroxyl-2-propyl group) benzene or 1,3,5-three (2-hydroxyl-2-propyl group) benzene and AlCl
3Exist down, make iso-butylene and isoprene, can obtain the butyl rubber that MWD is bimodal shape in-90 ℃ of following copolymerization.
Summary of the invention
The invention provides a kind of method for preparing isoolefin polymer, the especially butyl rubber of controllable molecular weight distribution through the proportioning that changes initiator system.
Particularly; The present invention relates to a kind of initiator system that adopts carbon cation polymerization prepared in reaction isoolefin homopolymer or isoolefine and conjugated polyene hydrocarbon copolymer, the Lewis acid carbon cation polymerization initiator system that closes especially for iso-butylene homopolymerization, iso-butylene and isoprene copolymer.This initiator system can prepare the isoolefin polymer with adjustable MWD (MWD).
The initiator system that technology of the present invention provides is at TiCl
4, AlCl
3Or AlR
mX
3-mOn the basis of conventional coinitiator; Organo-tin compound through introducing an amount of chemical structures is as additive; This type organo-tin compound can not be total to initiated polymerization separately, reaches the purpose of regulating the butyl rubber MWD, MWD is narrowed down or widens; This depends on chemical structure that contains tin organic compound and the consumption that is added; When for example adding an amount of chlorination tri-n-butyl tin or dichloro di-n-butyl tin, the MWD of polymerisate is between the 1.9-3.5, and the MWD (～4.5) of resulting polymers obviously narrows down when not adding chlorination tri-n-butyl tin or dichloro di-n-butyl tin; And when additive is tri-chlorination normal-butyl tin, MWD is regulated between 3.4-5.2 according to its consumption.In addition, adopt the present invention's technology, also can under the high conversion condition, synthesize high-molecular weight butyl rubber product, of embodiment 6, polymerisation conversion is 61% o'clock, the weight-average molecular weight Gao Keda 860,000 of butyl rubber.
Detailed Description Of The Invention
Initiator system of the present invention comprises component A and B component.
Wherein, component A is that structural formula is M
1X
nCompound (M
1Be V, Ti, Zr, Hf, Sn or Sb, X is a halogen, and n is a metal M
1Valency), or structural formula is M
2R
1 3-mX
mCompound (M
2Be Al or B; R
1Be the identical or different straight or branched alkyl with 1-8 carbon atom, m=1,1.5,2 or 3, X are identical or different halogen), or aikyiaiurnirsoxan beta, perhaps two or more mixture in them.The specific examples of component A is titanium tetrachloride, tin tetrachloride, aluminum chloride, alchlor, boron trichloride, boron trifluoride, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium, diisobutyl aluminum chloride, isobutyl-al dichloride, octyl group al dichloride, sesquialter propyl group aluminum chloride, sesquialter butyl aluminum chloride, sesquialter amyl group aluminum chloride, aluminium diethyl monochloride, a chlorine dipropyl aluminium, a chlorine dibutyl aluminium, a chlorine diamyl aluminium, MAO, modified methylaluminoxane, or two or more mixture in them.Most preferred composition A is an ethyl aluminum dichloride.
According to the present invention, preferred ingredient A is formula M
2R
1 3-mX
mCompound, M wherein
2, R
1, X and m as above define.More preferably R wherein
1Formula M for identical or different straight or branched alkyl with 1-4 carbon atom
2R
1 3-mX
mCompound.Preferred in addition wherein m is 1,1.5 or 2 formula M
2R
1 3-mX
mCompound.
B component is that structural formula is (R
2)
4-ySnX
yCompound, R wherein
2Be the identical or different straight or branched alkyl with 1-10 carbon atom, X is a halogen, and y is from 1 to 3 integer.For example; Trimethyltin chloride, dichloride tin methide, methyl tin chloride, triethyltin chloride, tin diethyl dichloride, tri-chlorination ethyl tin, chlorination tri-n-butyl tin, dichloro di-n-butyl tin, tri-chlorination normal-butyl tin; Or two or more mixture in them, be preferably the dichloro di-n-butyl tin.
Initiator system of the present invention can directly or use behind the wiring solution-forming in thinner, preferably in thinner, uses behind the wiring solution-forming.Employed thinner is that the person skilled in the art is for butyl rubber polyreaction known inert solvent of institute or reaction medium; Comprise alkane, naphthenic hydrocarbon and their halogen monobasic or polynary substituent; Or the mixture of alkane/halogenated alkane, or the mixture of multiple halogenated alkane.The preferred chloroparaffin that uses, like monochloro methane, methylene dichloride etc., or the mixture of their mixture itself or they and alkane, like hexane/chloroparaffin mixture.Most preferably use methylene dichloride.It is 0.001-10mol/L that the concentration of initiator system is carried out scope, preferred 0.01-1mol/L.
Polymerization method of the present invention carries out in the presence of thinner, and wherein employed thinner can be identical or different with the top thinner that is used to prepare initiator solution.Specific examples comprises alkane, naphthenic hydrocarbon and their halogen monobasic or polynary substituent, or the mixture of alkane/halogenated alkane, or the mixture of multiple halogenated alkane.The preferred chloroparaffin that uses, like methyl chloride, methylene dichloride, or the mixture of their mixture itself or they and alkane are like hexane/chloroparaffin mixture.Here preferably use monochloro methane.Monomeric concentration range is 10～40 weight % during polyreaction, is preferably 15～35 weight %.
Polymerization method of the present invention is preferred for C
4-C
8The homopolymerization of monoolefine or C
4-C
8Monoolefine and C
4-C
14The copolymerization of conjugated diene.According to the present invention, C
4-C
8Monoolefine is preferably isomery monoolefine, most preferably iso-butylene.According to the present invention, C
4-C
14The preferred C of conjugated diene
4-C
10Conjugated diene, most preferably isoprene.
According to the present invention, the usage quantity of initiator system accounts for the 0.01-4.0% of reaction monomers gross weight, and preferable range is 0.5-1.5%.
The molar ratio of component A and B component preferably 100: 1～1: 10 is more preferably 50: 1～1: 5, most preferably at 20: 1～1: 1.
Monomer is normally in-100 ℃～+ 20 ℃ scopes, preferably under the temperature in-100 ℃～-20 ℃ scopes and carry out polymerization of the present invention under the pressure in 0.1～4Mpa scope.
Polyreaction is carried out under inert atmosphere usually, for example under argon gas, helium, nitrogen etc., carries out.After polyreaction finishes, stop with alcohols usually and wash, then polymkeric substance is dried to constant weight in stink cupboard or vacuum drying oven.
Utilize the inventive method to prepare to have the distribute butyl rubber polymer of (MWD) of controllable molecular weight.According to the present invention, MWD preferably in 1.5～10.0 scope, most preferably 2.0～6.0.
Embodiment of the present invention will explain that they should not be used to explain or limit scope of the present invention with reference to following examples.
Embodiment
Molecular weight of product adopts the U.S. Maxims of Waters company 820 type gel permeation chromatographies (GPC) to detect, and solvent and moving phase are THF (THF), and RI (refractive index detector) detects, room temperature.
The product degree of unsaturation adopts the Switzerland AVANCE 400MHz NMR of Bruker company spectrometer to detect, magneticstrength 9.40 teslas, and sample hose diameter 5mm, sample with the deuterochloroform dissolving, are interior mark with TMS at normal temperatures, test under the room temperature.Utilize
1The H-NMR spectrum is carried out the calculating of the degree of unsaturation (being isoprene content) of butyl rubber.
The calculation formula of the degree of unsaturation of butyl rubber (representing with U) is following:
Abbreviation promptly gets:
In the formula: A represents the area at chemical shift peak in 5.01～5.15ppm scope;
B represents the area at chemical shift peak in 4.90～4.98ppm scope;
C represents the area at chemical shift peak in 0.25～2.20ppm scope.
Comparative Examples 1
In 2 liters of reaction kettles, add monochloro methane 161.3 grams down successively in high pure nitrogen protection, iso-butylene 40.0 grams and isoprene 1.26 restrain ,-90 ℃ of following constant temperature 0.5 hour.The about 0.1MPa of polymerization pressure; Adding 10mL 0.1mol/L Dichloroethyl aluminum solutions begins initiated polymerization to reaction kettle under the high pure nitrogen protection, reacts to add the about 20ml termination reaction of ethanol (95% analytical pure), discharging after 60 seconds; With washing with alcohol three times, obtain white product.With this product stink cupboard inner drying 24 hours, in vacuum drying oven dry 48 hours then, obtain product 31.60 grams, reaction conversion ratio is 79%, degree of unsaturation is 1.1%, weight-average molecular weight (M
w) be 454000, MWD (M
w/ M
n) be 4.42.
Embodiment 1
By ethyl aluminum dichloride and chlorination tri-n-butyl tin mol ratio is 8: 1, and compound concentration is the dichloromethane solution X of 0.1mol/L.
Like Comparative Examples 1 said method; The mixing solutions X that under the high pure nitrogen protection, adds aforesaid ethyl aluminum dichloride of 10ml and chlorination tri-n-butyl tin begins initiated polymerization to reaction kettle; React and add the about 20ml termination reaction of ethanol (95% analytical pure) after 60 seconds; Discharging with washing with alcohol three times, obtains white product.With this product stink cupboard inner drying 24 hours, in vacuum drying oven dry 48 hours then, obtain product 35.15 grams, transformation efficiency is 87.8%, degree of unsaturation is 1.15%, M
wBe 579700, M
w/ M
nBe 3.5.
Embodiment 2
Like embodiment 1 said method, only ethyl aluminum dichloride and chlorination tri-n-butyl tin mol ratio are changed into 4: 1.Polymerisation conversion is 48%, and degree of unsaturation is 0.9%, M
wBe 462000, M
w/ M
nBe 2.5.
Embodiment 3
Like embodiment 1 said method, only ethyl aluminum dichloride and chlorination tri-n-butyl tin mol ratio are changed into 2: 1.Polymerisation conversion is 13%, and degree of unsaturation is 0.8%, M
wBe 472000, M
w/ M
nBe 2.1.
Embodiment 4
By ethyl aluminum dichloride and dichloride di-n-butyl tin mol ratio is 10: 1, and compound concentration is the dichloromethane solution Y of 0.1mol/L.
Like Comparative Examples 1 said method, in 2 liters of reaction kettles, add monochloro methane 169.8 grams down successively in high pure nitrogen protection, iso-butylene 30.2 grams and isoprene 0.94 restrain ,-90 ℃ of following constant temperature 0.5 hour.The mixing solutions Y that under the high pure nitrogen protection, adds aforesaid ethyl aluminum dichloride of 10ml and dichloride di-n-butyl tin begins initiated polymerization to reaction kettle; React and add the about 20ml termination reaction of ethanol (95% analytical pure) after 60 seconds; Discharging with washing with alcohol three times, obtains white product.Stink cupboard inner drying 24 hours, in vacuum drying oven dry 48 hours then, polymerisation conversion was 70% with this product, and degree of unsaturation is 1.3%, M
wBe 714000, M
w/ M
nBe 2.4.
Embodiment 5
Like embodiment 4 said methods, only ethyl aluminum dichloride and dichloride di-n-butyl tin mol ratio are changed into 5: 1.Polymerisation conversion is 61%, and degree of unsaturation is 1.4%, M
wBe 860000, M
w/ M
nBe 2.2.
Embodiment 6
By ethyl aluminum dichloride and normal-butyl tin trichloride mol ratio is 8: 1, and compound concentration is the dichloromethane solution Z of 0.1mol/L.
Like Comparative Examples 1 said method, in 2 liters of reaction kettles, add monochloro methane 169.8 grams down successively in high pure nitrogen protection, iso-butylene 31.5 grams and isoprene 0.96 restrain ,-90 ℃ of following constant temperature 0.5 hour.The mixing solutions Z that under the high pure nitrogen protection, adds aforesaid ethyl aluminum dichloride of 10ml and normal-butyl tin trichloride begins initiated polymerization to reaction kettle; React and add the about 20ml termination reaction of ethanol (95% analytical pure) after 60 seconds; Discharging with washing with alcohol three times, obtains white product.Stink cupboard inner drying 24 hours, in vacuum drying oven dry 48 hours then, polymerisation conversion was 87% with this product, and degree of unsaturation is 1.0%, M
wBe 358000, M
w/ M
nBe 5.2.
Embodiment 7
Like embodiment 6 said methods, only ethyl aluminum dichloride and normal-butyl tin trichloride mol ratio are changed into 4: 1.Polymerisation conversion is 85%, and degree of unsaturation is 1.7%, M
wBe 494000, M
w/ M
nBe 5.1.
Embodiment 8
Like embodiment 6 said methods, only ethyl aluminum dichloride and chlorination tri-n-butyl tin mol ratio are changed into 2: 1.Polymerisation conversion is 79%, and degree of unsaturation is 1.2%, M
wBe 687000, M
w/ M
nBe 4.5.
Embodiment 9
Like embodiment 6 said methods, only ethyl aluminum dichloride and chlorination tri-n-butyl tin mol ratio are changed into 1: 1.Polymerisation conversion is 55%, and degree of unsaturation is 1.0%, M
wBe 495000, M
w/ M
nBe 3.4.
Embodiment 10
By aluminum chloride and chlorination tri-n-butyl tin mol ratio is 10: 1, and compound concentration is the dichloromethane solution M of 0.02mol/L.
Like Comparative Examples 1 said method, in 2 liters of reaction kettles, add monochloro methane 170.2 grams down successively in high pure nitrogen protection, iso-butylene 29.3 grams and isoprene 0.96 restrain ,-90 ℃ of following constant temperature 0.5 hour.The mixing solutions M that under the high pure nitrogen protection, adds aforesaid aluminum chloride of 10ml and chlorination tri-n-butyl tin begins initiated polymerization to reaction kettle; React and add the about 20ml termination reaction of ethanol (95% analytical pure) after 60 seconds; Discharging with washing with alcohol three times, obtains white product.Stink cupboard inner drying 24 hours, in vacuum drying oven dry 48 hours then, polymerisation conversion was 68% with this product, and degree of unsaturation is 1.8%, M
wBe 494000, M
w/ M
nBe 2.7.
Embodiment 11
Like embodiment 10 said methods, only the chlorination tri-n-butyl tin is replaced with the dichloride di-n-butyl tin.Polymerisation conversion is 77%, and degree of unsaturation is 1.4%, M
wBe 498000, M
w/ M
nBe 2.7.
Embodiment 12
Like embodiment 10 said methods, only aluminum chloride and dichloride di-n-butyl tin mol ratio are changed into 4: 1.Polymerisation conversion is 50%, and degree of unsaturation is 1.4%, M
wBe 481000, M
w/ M
nBe 2.6.
Claims (13)
1. initiator system that is used to prepare adjustable isoolefin homopolymer of MWD or multipolymer, form by following component:
Be selected from following component A: aluminum chloride, alchlor, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium, diisobutyl aluminum chloride, isobutyl-al dichloride, octyl group al dichloride, sesquialter propyl group aluminum chloride, sesquialter butyl aluminum chloride, sesquialter amyl group aluminum chloride, aluminium diethyl monochloride, a chlorine dipropyl aluminium, a chlorine dibutyl aluminium, a chlorine diamyl aluminium, or two or more mixture in them;
And
B component, this B component are formula (R
2)
4-ySnX
yCompound, R wherein
2For having the straight or branched alkyl of 1-10 carbon atom, X is that halogen and y are from 1 to 3 integers independently of one another,
Wherein the mol ratio of component A and B component is 20: 1～2: 1.
2. initiator system as claimed in claim 1; Wherein B component is selected from trimethyltin chloride, dichloride tin methide, methyl tin chloride, triethyltin chloride, tin diethyl dichloride, tri-chlorination ethyl tin, chlorination tri-n-butyl tin, dichloro di-n-butyl tin, tri-chlorination normal-butyl tin, or two or more mixture in them.
3. according to claim 1 or claim 2 initiator system, wherein component A is that ethyl aluminum dichloride and B component are the dichloro di-n-butyl tin.
4. method for preparing isoolefin homopolymer and multipolymer, this method are included in-100 ℃ to+20 ℃ polymerization temperature, make C
4-C
8Monoolefine monomer itself perhaps makes C
4-C
8Monoolefine monomer and C
4-C
14Conjugated diene monomer carries out polymerization in the presence of each described initiator system and the thinner in like claim 1-3.
5. method as claimed in claim 4, wherein thinner is alkane, naphthenic hydrocarbon and their halogen monobasic or polynary substituent, or the mixture of alkane/halogenated alkane, or the mixture of multiple halogenated alkane.
6. method as claimed in claim 4, wherein thinner is a monochloro methane.
7. method as claimed in claim 4, wherein C
4-C
8Monoolefine is the isomery monoolefine.
8. method as claimed in claim 4, wherein C
4-C
8Monoolefine is an iso-butylene.
9. method as claimed in claim 4, wherein C
4-C
14Conjugated diene is C
4-C
10Conjugated diolefine.
10. method as claimed in claim 4, wherein C
4-C
14Conjugated diene is an isoprene.
11. method as claimed in claim 4, wherein the usage quantity of initiator system accounts for the 0.01-4.0% of total monomer weight.
12. method as claimed in claim 4, wherein the MWD of isoolefin homopolymer or multipolymer is 1.5-10.0.
13. method as claimed in claim 4, wherein the MWD of isoolefin homopolymer or multipolymer is 2.0-6.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101118147A CN101585891B (en) | 2008-05-19 | 2008-05-19 | Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101118147A CN101585891B (en) | 2008-05-19 | 2008-05-19 | Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101585891A CN101585891A (en) | 2009-11-25 |
| CN101585891B true CN101585891B (en) | 2012-02-29 |
Family
ID=41370338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101118147A Active CN101585891B (en) | 2008-05-19 | 2008-05-19 | Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101585891B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453183B (en) * | 2010-10-14 | 2013-09-04 | 中国石油天然气股份有限公司 | Method for preparing isoolefine copolymer |
| CN115109189B (en) * | 2022-06-15 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107417A (en) * | 1971-11-26 | 1978-08-15 | Snamprogetti, S.P.A. | Process for the production of polymers and copolymers of isobutylene |
| US4379899A (en) * | 1977-09-14 | 1983-04-12 | Bp Chemicals Limited | Process for producing polyisobutenes |
| CN1302820A (en) * | 1999-12-27 | 2001-07-11 | 住友化学工业株式会社 | Modified particles and preparation method of olefine polymerization catalyst and olefine polymer using said particle |
| CN1813010A (en) * | 2003-06-25 | 2006-08-02 | 株式会社普利司通 | Butadiene polymer and process for producing the same, and rubber composition and tire comprising or made from the same |
-
2008
- 2008-05-19 CN CN2008101118147A patent/CN101585891B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107417A (en) * | 1971-11-26 | 1978-08-15 | Snamprogetti, S.P.A. | Process for the production of polymers and copolymers of isobutylene |
| US4379899A (en) * | 1977-09-14 | 1983-04-12 | Bp Chemicals Limited | Process for producing polyisobutenes |
| CN1302820A (en) * | 1999-12-27 | 2001-07-11 | 住友化学工业株式会社 | Modified particles and preparation method of olefine polymerization catalyst and olefine polymer using said particle |
| CN1813010A (en) * | 2003-06-25 | 2006-08-02 | 株式会社普利司通 | Butadiene polymer and process for producing the same, and rubber composition and tire comprising or made from the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101585891A (en) | 2009-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4109071A (en) | Process for the polymerization of olefins | |
| Quirk et al. | Anionic synthesis of polystyrene and polybutadiene heteroarm star polymers | |
| JP2005534771A (en) | Fluorinated polymer | |
| AU706514B2 (en) | A process for making graft block copolymers by grafting anionic polymer chains onto functionalized polyolefins | |
| JPH04337308A (en) | Production of block copolymer | |
| US20080269440A1 (en) | Polymerization of Olefins | |
| EP3747916A1 (en) | Ethylene/alpha-olefin copolymer and method for preparing same | |
| CN105646757A (en) | Cationic polymerization system and preparation method of high-unsaturation-degree isoolefin copolymer | |
| CA1057732A (en) | Process of polymerizing or copolymerizing olefines by using a new catalytic composition | |
| EP0166536B1 (en) | Block copolymer | |
| CN114402002A (en) | Terpolymer of ethylene and 1, 3-diene | |
| CN101585891B (en) | Initiator system for preparing isoolefine homopolymers or copolymers, and method for preparing isoolefine homopolymers or copolymers by using same | |
| AU654238B2 (en) | Polymers having stable anhydride rings | |
| JPS59117510A (en) | Manufacture of catalyst for olefin polymerization and polymerization of olefin | |
| Bogaert et al. | Chlorolanthanocene‐dialkylmagnesium systems for styrene bulk polymerization and styrene‐ethylene block copolymerization | |
| CN101987876A (en) | Controllable cation polymerizing method of vinyl monomers | |
| Mays et al. | Synthesis of high molecular weight near-monodisperse poly (4-methylstyrene) by anionic polymerization | |
| CN110283279A (en) | Copolymer, preparation method and the rubber composition of 1,3- butadiene and 1- butylene | |
| Masuda et al. | Polymerization of silicon‐containing acetylenes. 5. Polymerization of 1‐silyl‐1‐propynes by TaCl5‐based catalysts | |
| US6100337A (en) | Functionalized thermoplastic elastomer | |
| EP1355953A1 (en) | Process for making high molecular weight isobutylene polymers | |
| JP2000191714A (en) | Catalyst for polymerization and production of isobutylene-styrene copolymer using the same | |
| EP1834970B1 (en) | A process for producing polyolefin-polyvinylaromatic-block copolymers | |
| JP2002526612A (en) | Random isomonoolefin / allyl styrene copolymers and their functionalized derivatives | |
| CN104277159A (en) | Catalyst for production of polyethylene with narrow molecular weight distribution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |