CN1283681C - Method for preparing isobutylene block copolymer by sequential initiation - Google Patents
Method for preparing isobutylene block copolymer by sequential initiation Download PDFInfo
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- CN1283681C CN1283681C CN 02148784 CN02148784A CN1283681C CN 1283681 C CN1283681 C CN 1283681C CN 02148784 CN02148784 CN 02148784 CN 02148784 A CN02148784 A CN 02148784A CN 1283681 C CN1283681 C CN 1283681C
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Abstract
The present invention provides a method for preparing isobutylene block copolymers by sequential initiation, which orderly comprises the following steps: (1) first stage polymerization: controllable or active cation homopolymerization or copolymerization is carried out on styrene monomers (monomers A); (2) second stage polymerization: isobutylene is used as the monomers, and the homopolymerization of the isobutylene is carried out under the conditions that the polymerisates of the first stage are used as macromolecule initiators, and a new lewis acid is added and used as coinitiators, or the copolymerization of the monomers and comonomers of the isobutylene is carried out under the conditions that the isobutylene is used as the monomers, the polymerisates of the first stage are used as the macromolecule initiators, and a new lewis acid is added and used as the coinitiators. Finally, the block polymer is obtained. The present invention also provides an isobutylene block polymer prepared by the method of the present invention and a derivative thereof, and applications.
Description
Technical field
The present invention relates to a kind of preparation method of segmented copolymer, more particularly, the present invention relates to prepare the cationic polymerization method of the segmented copolymer of styrene monomer and iso-butylene, iso-butylene segmented copolymer and its functional derivative of this method preparation.
Background technology
Segmented copolymer is that a class has definite sequential structure and the multipolymer that is different from the random copolymers performance.Each block has the physical and mechanical property similar to its homopolymer in the multipolymer.Segmented copolymer is widely used as dispersion agent, tensio-active agent, expanding material and thermoplastic elastomer.
Prepare segmented copolymer by active cationic polymerization, particularly contain polyisobutene segmental multipolymer and disclose following preparation method.
United States Patent (USP) 5,428 discloses a kind of method for preparing the iso-butylene segmented copolymer No. 111, and this method comprises: (1) is in the mixed solvent of hydrochloric ether and alkane, with organic uncle's chlorine compound, TiCl
4With 2, the 6-di-tert-butyl pyridine is an initiator system, carries out the living polymerization of iso-butylene; (2) in above-mentioned active polymerization system, add end-capping reagent; (3) add styrene monomer and carry out polymerization.The also open segmented copolymer of preparation as stated above of this patent is a kind of thermoplastic elastomer.
It is the active cationic polymerization method of the thermoplastic elastomer of rubber segments that Chinese patent 1204653A discloses the preparation polyisobutene, it is characterized in that with the hexahydropyridine being electron donor or nucleophilic reagent, with dicumyl chlorine/TiCl
4Being initiator system, is solvent with the mixture of methyl chloride and hexanaphthene.Preparation process is similarly the active cationic polymerization that at first carries out iso-butylene, adds end-capping reagent then, adds styrene monomer at last and obtains triblock copolymer.This triblock copolymer can be used as thermoplastic elastomer.
United States Patent (USP) 5,451,647 disclose a kind of initiator composition of being made up of organic uncle's halogen compound, dimethylaluminum chloride and the pyridine that is obstructed that is used for synthetic isobutylene homo, multipolymer and segmented copolymer.
Chinese patent 1332757 discloses a kind of new triblock copolymer and the method for preparation thereof.This segmented copolymer is characterised in that its middle soft section random copolymers for iso-butylene and vinyl aromatic monomers.Its method is carried out active cationic polymerization for being initiator system with organic uncle's chlorine compound/dimethylaluminum chloride in the mixed solvent of hydrochloric ether and alkane composition.
Yet, in the cationic polymerization method of disclosed preparation iso-butylene segmented copolymer, at first carry out the polymerization of low activity monomer iso-butylene usually.The cationic polymerization specific activity styrenic of iso-butylene low correspondingly needs stronger Lewis acid as coinitiator.This just produces the monomeric homopolymer of high reactivity inevitably when adding the high reactivity monomer, in order to address this problem, generally adopt following method: (1) uses end-capping reagent; (2) use proton capture agent and nucleophilic reagent (electron donor).In addition, because polyisobutene is insoluble under the cationic polymerization temperature in cationic polymerization the chlorinated hydrocarbon solvent methyl chloride and methylene dichloride commonly used, and (as straight-chain paraffin and aromatic hydrocarbons) can't realize living polymerization in the good solvent of polyisobutene, therefore must use mixed solvent.The existence of these problems has greatly increased cost, makes complex technical process simultaneously, especially reclaims and aftertreatment.Therefore, still need to seek a kind of new method for preparing the iso-butylene segmented copolymer.
Summary of the invention
The purpose of this invention is to provide a kind of cationic polymerization method for preparing the iso-butylene segmented copolymer.
Another object of the present invention provides the segmented copolymer and the functional derivative thereof of described method preparation.
Alleged segmented copolymer is meant one section random copolymers for polyisobutene or iso-butylene and p-methylstyrene among the application, or the random copolymers of iso-butylene and Vinylstyrene, and another section is the homopolymer or the multipolymer segment of styrene monomer.
Alleged styrene monomer is meant having on cinnamic α-C and has substituent vinylbenzene and derivative thereof on substituting group or the phenyl ring among the application, include but not limited to vinylbenzene, p-methylstyrene, alpha-methyl styrene, the vinylbenzene that various alkyl replace, as to t-butyl styrene, palkoxy benzene ethene.
The preparation method of a kind of iso-butylene segmented copolymer of the present invention comprises step successively:
(1) fs polymerization: styrene monomer carries out " controlled " or " activity " cationic polymerization in reactor, and the transformation efficiency that makes polyreaction proceed to styrene monomer continuously is more than the 95 weight %;
(2) subordinate phase polymerization: the homopolymer or the multipolymer of styrene monomer with (1) preparation is macromole evocating agent, add the second monomer iso-butylene, the adding coinitiator causes the polymerization of the second monomer iso-butylene, and successive polymerization is more than the 90 weight % to isobutene conversion.
The preparation method of above-mentioned iso-butylene segmented copolymer is characterized in that styrene monomer is vinylbenzene or is having substituent derivative on cinnamic α-C or on the phenyl ring, and described substituting group is C
1To C
15Aliphatics and/or aromatic substituents.
The preparation method of above-mentioned iso-butylene segmented copolymer, the comonomer of its isobutene polymerisation can be p-methylstyrene and/or Vinylstyrene.
The preparation method of above-mentioned iso-butylene segmented copolymer, its described macromole evocating agent can be that terminal group is the homopolymer or the multipolymer of the styrene monomer of halogen.
The preparation method of above-mentioned iso-butylene segmented copolymer, its described coinitiator can be Lewis acid, is selected from the group of being made up of halogenide, alkyl halide, alkoxy halide or its mixture of boron, tin, zinc, aluminium, titanium one or more; Preferred coinitiator is dialkylaluminum chloride or dialkyl group boron chloride.
The cationic polymerization method of the application's preparation iso-butylene segmented copolymer comprises step successively:
(1) fs polymerization: styrene monomer carries out " controlled " or " activity " cationic polymerization or copolymerization in reactor, and the selection of polymerization initiation system and polymeric reaction condition should make this polymerization or copolymerization be combined into " controlled " or " activity " polymerization.
(2) subordinate phase polymerization: when above-mentioned polyreaction is finished or when finishing, or the transformation efficiency of styrene monomer is that 95 weight % are when above, polymkeric substance with preparation in (1) is a macromole evocating agent, the mix monomer that adds low activity monomer iso-butylene and/or p-methylstyrene or Vinylstyrene, add stronger Lewis acid as coinitiator, above-mentioned reactant is mixed, and the mix monomer that causes iso-butylene and/or p-methylstyrene or Vinylstyrene carries out polymerization.The transformation efficiency of isobutylene monomer is that 90 weight % stop polyreaction when above, reclaims copolymerization product, and its number-average molecular weight is 5000-200000, molecular weight distribution 1.0-2.5.
The cationic polymerization of iso-butylene or iso-butylene and p-methylstyrene or iso-butylene and Vinylstyrene can be " controlled " or " activity " cationic polymerization, also can be traditional cationic polymerization.
The present invention relates to a kind of preparation contains the order initiation of polyisobutene or poly-(iso-butylene-co-p-methylstyrene) or poly-(iso-butylene-co-Vinylstyrene) segmental segmented copolymer and adds the cationic polymerization method that monomer combines in proper order.
Method of the present invention is at first to carry out " controlled " or " activity " polymerization of styrene monomer.The realization that can in all sorts of ways of " controlled " of styrene monomer or " activity " cationic polymerization, these methods are described in the various documents, as " the monomeric active cationic polymerization of resonance stabilization " (Puskas, J.E.; Kaszas, G.Progress in Polymer Science.2000,25,403), " HI/ZnX
2The active cationic polymerization of the p-methylstyrene that causes " (K.Kojima, M.Sawamoto, Jouranal of PolymerScience:Part A, Polymer Chemistry, Vol 28,3007 (1990)), etc.In this application, " controlled " or " activity " cationic polymerization is defined as: the relative molecular mass of (1) polymerisate can be pressed
Determine (wherein
Be the number average relative molecular mass of poly-and thing, [M]
0Be monomeric starting point concentration, [I]
0Be the starting point concentration of initiator, FW is the molecular weight of monomer M); (2) terminal group of polymerisate can be controlled; (3) there are not irreversible chain termination and chain transfer reaction in the polymerization process basically.The general condition that styrene monomer carries out " controlled " or " activity " cationic polymerization comprises:
(1) initiator is selected from the (X=Cl by HX, Br, I), aryl halide such as benzyl chloride, cumyl chlorine, 1-phenyl-chloride ethane, 1-phenyl-bromide ethane, cumyl bromine, bromotoluene, tertiary alkyl halogenide, tert-alkyl ether, tertiary alkyl ester, aralkyl ethers, aralkyl ester and composition thereof form in one or more compound in the group.
(2) Lewis acid coinitiator is selected from by in halogenide, alkyl halide or the alkoxy halide of boron, tin, zinc, aluminium, titanium one or more.
(3) the electron donor additive is or/and homo-ion salt additives, as ethers, for example ether, methyl tertiary butyl ether etc.; Ester class such as ethyl acetate, ethyl benzoate etc.; Amides is N for example, dinethylformamide, N,N-dimethylacetamide etc.; Quaternary ammonium salt, tetrabutylammonium chloride, Tetrabutyl amonium bromide etc.(4) solvent is chosen according to initiator, coinitiator, monomeric characteristic, commonly used is hydrochloric ether such as methyl chloride, methylene dichloride, trichloromethane, monochloroethane, chloropropane etc.; Alkane such as hexanaphthene, substituted cyclohexane, aromatic hydrocarbons such as toluene, benzene etc.
(5) monomer or comonomer.
Knownly can be used for styrene monomer " controlled " or any initiator system of " activity " polymeric can be applicable to the present invention, be not particularly limited, for example the property summarized document " the monomeric active cationic polymerization of resonance stabilization " (Puskas, J.E.; Kaszas, G.Progress in Polymer Science.2000,25,403) in cited polymerization system (but being not limited to these systems).But preferred in the present invention initiator system is: (1) aryl halide such as benzyl chloride, cumyl chlorine, 1-phenyl-chloride ethane, 1-phenyl-bromide ethane, cumyl bromine, bromotoluene; (2) coinitiator is a tin halides, halogenation boron, and zinc halide, aluminum alkyls or boron alkyl, wherein alkyl is the straight or branched alkyl that contains 1-15 carbon atom; (3) additive is homo-ion salt, as various quaternary ammonium salts; (4) solvent is a hydrochloric ether, as methyl chloride, and methylene dichloride, trichloromethane, monochloroethane, chloropropane etc.
The consumption of initiator depends on the relative molecular mass of prepared multipolymer.Usually in 0.0001 mol-0.02 mol scope, preferably in 0.0001 mol-0.015 mol scope, more preferably in 0.0005 mol-0.02 mol scope, particularly preferably in 0.0001 mol-0.01 mol scope.The consumption of coinitiator is 1-5 times (mole) of initiator amount, is preferably 1-4.5 doubly (mole), and more preferably 1.5-5 times (mole) is preferably 1-4 (mole) especially.The consumption of the homo-ion salt of additive is generally 0.1-5 times (mole) of initiator, is preferably 0.5-5 doubly (mole), and more preferably 1.0-5 times (mole) is preferably 1-4.5 doubly (mole) especially.
In the method for the invention, utilize the homopolymer or the multipolymer of the styrene monomer of method for preparing to be macromole evocating agent, add the monomer of the common monomer of iso-butylene or iso-butylene and p-methylstyrene or Vinylstyrene composition then for another block, add a kind of new coinitiator, carry out homopolymerization of isobutene or copolymerization.The polymerization process of polyisobutene or poly-(iso-butylene-co-p-methylstyrene) or poly-(iso-butylene-co-Vinylstyrene) block can be " controlled " or " activity " cationic polymerization, also can be traditional cationic polymerization.Therefore, anyly can become the coinitiator of isobutene polymerisation or iso-butylene and p-methylstyrene or Vinylstyrene copolymerization to may be used to the present invention with the homopolymer or the copolymer in combination of styrene monomer of preparation as stated above.These coinitiators include but not limited to: the halogenide of boron and alkyl halide, the halogenide of aluminium and alkyl halide, the halogenide of titanium, VCl
4, SbF
5Deng.Wherein the alkyl chloride of the alkyl chloride of boron and aluminium preferably is more preferably dialkylaluminum chloride or dialkyl group boron chloride.The consumption that is used for the coinitiator of isobutene polymerisation or copolymerization is 1-5 times (mole) of styrene monomer polymerization starter consumption.In the polymerization process of subordinate phase, can add solvent or not add solvent.The solvent of adding can with the used solvent phase of fs polymerization with, also can be different.
The temperature of the polyreaction that is adopted among the present invention should be lower than 0 ℃, preferably-10 ℃～-115 ℃, the selected multipolymer that should be enough to prepare desired relative molecular mass of polymerization temperature and polymerization time, these selections are that those skilled in the art are known.Polyreaction can be carried out in the reactor of routine or container, for example produces the conversion unit of isoprene-isobutylene rubber and polyisobutene.
Example according to the segmented copolymer of the present invention preparation includes, but is not limited to: polystyrene-b-polyisobutene, poly-p-methylstyrene-b-polyisobutene, polystyrene-b-gathers (iso-butylene-co-p-methylstyrene), polystyrene-b-gathers (iso-butylene-co-is to Vinylstyrene), poly-(vinylbenzene-co-p-methylstyrene)-b-polyisobutene, poly-(vinylbenzene-co-p-methylstyrene)-b-poly-(iso-butylene-co-p-methylstyrene), poly-(vinylbenzene-co-p-methylstyrene)-b-poly-(iso-butylene-co-Vinylstyrene), poly-(vinylbenzene-co-Vinylstyrene)-b-poly-(iso-butylene-co-p-methylstyrene), poly-(p-methylstyrene-co-Vinylstyrene)-b-poly-(iso-butylene-co-p-methylstyrene), poly-(alpha-methyl styrene)-b-poly-(iso-butylene-co-p-methylstyrene), poly-(alpha-methyl styrene)-b-polyisobutene, poly-(alpha-methyl styrene)-b-poly-(iso-butylene-co-p-methylstyrene) and poly-(alpha-methyl styrene)-b-poly-(iso-butylene-co-Vinylstyrene) etc.
In addition, for the multipolymer that contains the p-methylstyrene structural unit, can prepare derivative by halogenation known in the art, functionalized or grafting.With not functionalized polymer phase ratio, these functionalized segmented copolymers can provide improved binding property, consistency, lyophily and dispersiveness, and multiple crosslinking reaction mode, comprise ultraviolet light cross-linking, electron beam irradiation, free radical and carbonium ion chemically crosslinked.The functionalized block Copolymers of these modifications can be with the composition of tackiness agent, coating, moulded parts, polymer blend be used for the dispersion polymerization of letex polymerization and non-aqueous system as emulsifying agent.
Description of drawings
Fig. 1 is the technological process synoptic diagram of preparation segmented copolymer of the present invention.
Embodiment
The technological process that the present invention prepares segmented copolymer is as shown in Figure 1:
The fs polymerization reaction time should guarantee that fs polymeric monomer conversion is greater than 95% weight, concrete polymerization reaction time and styrene monomer and monomer, initiator, coinitiator, polymeric reaction temperature are relevant with solvent altogether should be selected according to the character of system.The polymerization reaction time of subordinate phase also should guarantee the monomeric together polymerization conversion of isobutylene monomer or iso-butylene greater than 95% weight, and concrete polymerization reaction time is relevant with the character of monomer and common monomer and coinitiator.
Use method of the present invention, can prepare the segmented copolymer with following properties: (1) relative molecular mass distributes about 1.0 to 2.5; (2) molecular weight about 5000 to 200000; (3) in the polyisobutene block, contain the p-methylstyrene monomer structure unit of 0% to 50% (weight), and the Vinylstyrene structural unit of 0% to 2.5% (weight).As known in this area, the copolymerization of segmented copolymer is formed, and comprises that copolymerization composition and crosslinking degree depend on the purposes of polymkeric substance and required performance in the molecular weight of each block and the different block.Equally, functional group's character of functionalized block Copolymers and degree of functionalization depend on the purposes of polymkeric substance and required performance equally.
Segmented copolymer with the present invention's preparation can be used for a lot of fields, comprise tackiness agent, dispersion agent, the dispersion polymerization of non-aqueous system (as the production that is used for isoprene-isobutylene rubber makes the polymer slurries stabilization), the emulsifying agent of letex polymerization, the compatilizer of polymer blend compositions, moulded parts, dynamic perduren etc.
The present invention may be better understood with reference to the following examples, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
The adding of 30ml methyl chloride is filled in the reactor of nitrogen with exsiccant, add about 60mgn-Bu then
4N
+Cl
-, the 2.06g p-methylstyrene, 18 microlitre 1-phenylethyl chlorine are cooled to reaction mixture-40 ℃, add 50 microlitre SnCl then
4The polymerization of beginning fs.After the polyreaction 1 hour, the sample that takes a morsel is used to measure the relative molecular mass of poly-p-methylstyrene.Then add the 2.04g iso-butylene, be cooled to-80 ℃, add 0.2mlAlEt
2Cl (10M hexane solution) carries out the polymerization of subordinate phase.Polyreaction adds 2 milliliters methyl alcohol termination polyreaction after 30 minutes, use the methanol extraction polymkeric substance, gets about 4.0 grams of polymkeric substance after the drying.The number average relative molecular mass of measuring with GPC is poly-p-methylstyrene 19200 (MWD=1.46), and poly-p-methylstyrene-the b-polyisobutene is 36600 (MWD=1.42).
Embodiment 2
The adding of 20ml methyl chloride is filled in the reactor of nitrogen with exsiccant, add about 25mg n-Bu then
4N
+Cl
-, the 1.5g p-methylstyrene, 15 microlitre 1-phenylethyl chlorine are cooled to reaction mixture-40 ℃, add 50 microlitre SnCl then
4The polymerization of beginning fs, polyreaction 1 hour.Then add 1.8g iso-butylene and 18 milligrams of Vinylstyrenes, be cooled to-80 ℃, add 0.1mlAlEt
2Cl (10M hexane solution) carries out the polymerization of subordinate phase.Polyreaction adds 2 milliliters methyl alcohol termination polyreaction after 30 minutes, use the methanol extraction polymkeric substance, gets about 3.2 grams of polymkeric substance after the drying.10% hexanaphthene insolubles is arranged in the polymerisate approximately, and the number average relative molecular mass of the soluble part of measuring with GPC is 25300 (MWD=4.13), and the GPC spectrogram is bimodal.This shows that crosslinking reaction has taken place poly-(iso-butylene-co-Vinylstyrene) part.
Embodiment 3
The adding of 30ml methylene dichloride is filled in the reactor of nitrogen with exsiccant, add about 25mgn-Bu then
4N
+Cl
-, 1.8g vinylbenzene, 15 microlitre 1-phenylethyl chlorine are cooled to reaction mixture-40 ℃, add 200 microlitre SnCl then
4The polymerization of beginning fs, polyreaction 4 hours.Then add 1.8g iso-butylene and 100 milligrams of p-methylstyrenes, be cooled to-80 ℃, add 0.1mlAlEt
2Cl (10M hexane solution) carries out the polymerization of subordinate phase.Polyreaction adds 2 milliliters methyl alcohol termination polyreaction after 30 minutes, use the methanol extraction polymkeric substance, gets about 3.67 grams of polymkeric substance after the drying.The number average relative molecular mass of measuring with GPC is 35300 (MWD=1.65),
1The content of p-methylstyrene is about 5.2% (weight) in the polyisobutene block that H-NMR measures.
Embodiment 4
With the poly-p-methylstyrene of 10 grams-b-polyisobutene (the number average relative molecular mass of poly-p-methylstyrene section is 24000, MWD=1.42, the number average relative molecular mass of di-block copolymer is 46000, MWD=1.45) is dissolved in 80 milliliters of CCl
4In, adding 2 milliliters of bromines, 100 milligrams AIBN reacted 3 hours down at 60 ℃, used water precipitation then, must gather after the drying and about 12 grams of thing.
1Methyl in the poly-p-methylstyrene block that H-NMR measures in the p-methylstyrene structural unit of about 76.3% (mole) is by bromo.
Embodiment 5
Take by weighing about 6 grams of poly-p-methylstyrene-b-polyisobutene of bromo, add 40 milliliters of dissolvings of toluene.3 milliliters of triethylamines are dissolved in 10 milliliters of Virahols, under agitation join in the toluene solution of poly-p-methylstyrene-b-polyisobutene.Reacted 3 hours down at about 86 ℃ then.Products therefrom precipitates in Virahol, and dry back is used
1The result that H-NMR records shows that the brominated p-methylstyrene structural unit near 100% (mol ratio) has generated quaternary ammonium salt.Quaternised poly-p-methylstyrene-b-polyisobutene is dissolved in trichloromethane, methylene dichloride, and normal hexane forms milky solution in the toluene, vinylbenzene etc.Can form stable emulsion with adding entry in the above-mentioned milky solution.
Embodiment 6
The poly-p-methylstyrene of about 0.2 gram-b-polyisobutene of embodiment 1 preparation is dissolved in the batch mixing that 100 milliliters of isoprene-isobutylene rubbers produce [content of iso-butylene and isoprene is 31.8% (weight), and all the other are methyl chloride].This mixture is cooled to-100 ℃ then, under agitation adds 10 milliliters of AlCl
3Methyl chloride solution (wherein contain AlCl
3About 25 milligrams).The polymerisate milk sap that is white in color under agitation is warming up to-50 ℃ naturally and still keeps emulsion form.Add ethanol sedimentation, get polymerisate 25 grams.
As mentioned above, the present invention has done clear and has intactly described, and these all are the explanations to the present invention program's enumerative.But fully aware of, under the situation that does not deviate from spirit of the present invention, those skilled in the art can make various improvement or modification to the present invention, and these all should comprise within the scope of the invention.Scope of the present invention will propose in the appended claims.
Claims (5)
1. the preparation method of an iso-butylene segmented copolymer, this method comprises step successively:
(1) fs polymerization: styrene monomer carries out " controlled " or " activity " cationic polymerization in reactor, and the transformation efficiency that makes polyreaction proceed to styrene monomer continuously is more than the 95 weight %;
(2) subordinate phase polymerization: the homopolymer or the multipolymer of styrene monomer with (1) preparation is macromole evocating agent, add the second monomer iso-butylene, the adding coinitiator causes the polymerization of the second monomer iso-butylene, and successive polymerization is more than the 90 weight % to isobutene conversion; Described coinitiator is Lewis acid, is selected from the group of being made up of halogenide, alkyl halide, alkoxy halide or its mixture of boron, tin, zinc, aluminium, titanium one or more.
2. the preparation method of the iso-butylene segmented copolymer of putting down in writing by claim 1 is characterized in that styrene monomer is vinylbenzene or is having substituent derivative on cinnamic α-C or on the phenyl ring, and described substituting group is C
1To C
15Aliphatics and/or aromatic substituents.
3. the preparation method of the iso-butylene segmented copolymer of putting down in writing by claim 1, the comonomer that it is characterized in that isobutene polymerisation is p-methylstyrene and/or Vinylstyrene.
4. the preparation method of the iso-butylene segmented copolymer of putting down in writing by claim 1 is characterized in that described macromole evocating agent is meant that terminal group is the homopolymer or the multipolymer of the styrene monomer of halogen.
5. the preparation method of the iso-butylene segmented copolymer of putting down in writing by claim 1 is characterized in that described coinitiator is dialkylaluminum chloride or dialkyl group boron chloride.
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| CN100429252C (en) * | 2005-12-15 | 2008-10-29 | 北京化工大学 | Production of soft-segment total saturated block copolymer |
| CN101353403B (en) * | 2007-07-27 | 2012-02-08 | 中国石油化工股份有限公司 | Preparation of star-branched polyisobutene or isobutene-diene rubber |
| CN105669882B (en) * | 2014-11-18 | 2018-02-23 | 北京化工大学 | A kind of poly- (styrene b isobutene b styrene) triblock copolymer of Nitrogen ionization and preparation method thereof |
| JP6827919B2 (en) * | 2015-05-26 | 2021-02-10 | 株式会社カネカ | Manufacturing method of thermoplastic elastomer and thermoplastic elastomer |
| CN106317349B (en) * | 2015-07-08 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of styrene-isomonoolefin-styrene triblock copolymer and preparation method thereof |
| CN106947039A (en) * | 2017-03-31 | 2017-07-14 | 安徽同心化工有限公司 | A kind of isobutene isoprene Petropols and preparation method |
| CN116425930A (en) * | 2021-09-30 | 2023-07-14 | 北京石油化工学院 | Poly (isomonoolefin) copolymer, initiator system and application |
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