CN101007860A - Method for synthesizing vinyl solution-polymerization butadiene-isoprene rubber adopting composite regulation system - Google Patents
Method for synthesizing vinyl solution-polymerization butadiene-isoprene rubber adopting composite regulation system Download PDFInfo
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Abstract
The invention relates to a polymerization process for preparing solution polymerized butadiene-isoprene rubber, comprising carrying out copolymerization with butadiene and isoprene at 0- 130 Deg. C by taking organolithium as initiating agent and with existence of compound structure moderating system, and then carrying out coupling reaction with ploy degree of functionality of coupling agent after polymerization. The invention employs 1G/THF, 1G/Et3N or 2G/TMEDA compound structure moderating agent to get 1, 2- solution polymerized butadiene-isoprene rubber with construction content being 30- 50%. The invention is characterized by quality- stable product, easy- to- controlable process, and especial suitability for industrial production for medium ethenyl solution polymerized butadiene-isoprene rubber.
Description
Technical field
The present invention relates to the polymerization process of a kind of soluble polybutaamyl-rubber (IBR), more particularly, relate to a kind of employing 1G/THF, 1G/Et
3The soluble polybutaamyl-rubber of the polymerization process of the soluble polybutaamyl-rubber of the synthetic middle contents of ethylene of the compound regulation system of N or 2G/TMEDA and the middle contents of ethylene that obtains thus.
Background technology
Bibliographical information, glycol dimethyl ether (1G) be as conditioning agent, can regulate that contents of ethylene reaches 63.7% in the polyhutadiene.But this alcohol ether has two big shortcomings as conditioning agent: the one, can not from hexane, directly separate; The 2nd, coupling efficiency is near 0.Therefore ethylene glycol diethyl ether and the ethylene glycol dibutyl ether in this compounds can not satisfy test requirements document.
US 4,523, mentioned in 618 making coupling agent such as polyhalogenide or dicarboxylic diester and " reactive polymer " reaction, and the star structure rubber of preparation more has superiority than linear rubber.
US 4,577, and 002 discloses a kind of use formula R
1-O-CH
2-CH
2-O-R
2(R wherein
1And R
2Be identical or different C
2-18The method of alcohol ether synthetic aroma family's vinyl compound alkyl) and the elastomer copolymer of conjugated diene.Obtained contents of ethylene and be at least 30 weight %, the top of polymeric chain and terminal mostly are the multipolymer of aromatic base, because molecular structure and effect such as sterically hindered cause coupling efficiency not high.
US 4,530, mention in 985 and use diethyl carbitol (2G) when preparing wide distribution polyisoprene,, prove when adding coupling agent not had the active centre in the system owing to cross the early stopping polyreaction and/or disturb linked reaction can not obtain star polymer as conditioning agent.This patent has been set forth all conditioning agents in the past, confirms that they had the early stopping polymerization and/or disturbed the link coupled effect.This patent is found can be with a kind of new ether, i.e. formula R
1-O-CH
2-CH (R
2)-O-C (R
3) (R
4)-O-R
5(R wherein
1Alkyl for 2-18 carbon atom; R
2And R
3Alkyl for hydrogen or 1-4 carbon atom; R
4Alkyl for hydrogen or 1-6 carbon atom; R
5Alkyl for 1-18 carbon atom) ether replaces conventional alcohol ether, has improved the coupling situation, but compound itself is difficult to obtain.
US 5,008,343 disclose a kind of method for preparing no block polymer, comprise be selected from least two kinds of compounds in divinyl, isoprene and the vinylbenzene in inert organic solvents at organolithium compound as the ethylene glycol bisthioglycolate alkyl oxide of catalyzer and following formula as anionoid polymerization in the presence of the promotor:
R
1-O-CH
2-CH(R
3)-O-R
2
R wherein
3Be hydrogen, methyl or ethyl, R
1And R
2For having the alkyl of different carbonatomss, be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, and the total number of carbon atoms in the alkyl is 5-7.According to this patent, obtained no block polymer than high-vinyl-content by a large amount of use promotors.
At last, mentioned in the Chinese patent 92114800.3 and a kind ofly adopted the Lewis base of two or more opposed polarity to fit in by force/regulation system of strong, strong/weak, weak/low-pole, controlled the method for contents of ethylene Bv in the homopolymer of divinyl anionoid polymerization and the multipolymer.But only mention in this patent and be applicable to the industrial production of carrying out medium vinyl polybutadiene MVPB, high vinyl polybutadiene HVPB, random solution styrene butadiene rubber S-SBR and polystyrene-poly divinyl-products such as thermoplastic polystyrene elastomer SBS, do not mention and be used for the synthetic of soluble polybutaamyl-rubber, more do not disclose relevant link coupled situation.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the anionoid polymerization field of conjugated diene, in the hope of developing a kind of preparation vinyl, promptly 1,2-structural content stable and controllable and polymerization process that can successful link coupled soluble polybutaamyl-rubber.The result is unexpected to be found by adopting 1G/ tetrahydrofuran (THF) (THF), 1G/ triethylamine (Et
3N) or 2G/ Tetramethyl Ethylene Diamine (TMEDA) as compound regulation system divinyl and isoprene are carried out solution polymerization, can fully regulate the contents of ethylene in the gained multipolymer, and be easy to control, simultaneously can be with high coupling efficiency success coupling in the polymerization later stage.For example under certain conditioning agent consumption, can in 30～50% scopes, regulate arbitrarily contents of ethylene, and very little to the coupling effectiveness affects.
The purpose of this invention is to provide a kind of technology simple, be suitable for implementing and can satisfying stable control 1, the preparation method of the soluble polybutaamyl-rubber of 2-structural content on a large scale.
Therefore, the present invention relates to a kind of polymerization process of producing soluble polybutaamyl-rubber, be included under 0～130 ℃ the temperature at organolithium as initiator and 1G/THF, 1G/Et
3N or 2G/TMEDA are compound, and the copolymerization of divinyl and isoprene is carried out in the regulation system existence down in varsol, and carries out coupling at the basic adding of back fully of polymerization coupling agent.
The present invention relates to soluble polybutaamyl-rubber obtained by the method for the present invention in addition, and its contents of ethylene is 30～50%.
This and other purposes, feature and advantage of the present invention will become cheer and bright read the application's detailed description at the reference accompanying drawing after.
Description of drawings
Fig. 1 is the GPC spectrogram according to the multipolymer IBR54031 of the embodiment of the invention 1 acquisition;
Fig. 2 is the graphic representation according to monomer conversion and time relation among the multipolymer IBR54062 of the embodiment of the invention 1 acquisition;
Fig. 3 is according to the graphic representation of molecular weight growth among the multipolymer IBR54031 of the embodiment of the invention 1 acquisition with time relation;
Fig. 4 is in the multipolymer that obtains according to the embodiment of the invention 11, the graphic representation of 2-structural content and compound conditioning agent usefulness magnitude relation;
Fig. 5 is in the multipolymer that obtains according to the embodiment of the invention 21, the graphic representation of 2-structural content and compound conditioning agent usefulness magnitude relation;
Embodiment
In the method for the invention, used polymerization single polymerization monomer is the mixture of divinyl and isoprene, and wherein isoprene content is 10～50% based on the monomer total mass, and butadiene content correspondingly is 90～50%.
In the method for the invention, used varsol is hexanaphthene, raffinate oil or the mixed solvent (content of normal hexane in mixed solvent is 5～30 weight %) of hexanaphthene and normal hexane, and it is 10～20 weight % that the consumption of described solvent should make monomeric concentration.
In the method for the invention, used initiator is to be selected from the following compound any: C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium or C
3-C
6The cycloalkyl lithium, as lithium ethide, propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium etc., preferred n-Butyl Lithium or s-butyl lithium.The consumption of organic lithium initiator is selected according to the molecular weight size of required polymkeric substance.General initiator amount is that every 100g monomer need add 0.3～2.5mmol.
In the method for the invention, polyreaction is with 1G/THF, 1G/Et
3N or 2G/TMEDA be as compound regulation system, preferred 1G/THF.In the described compound regulation system, be 0.1: 1～10: 1 as 1G, the 2G of strong polar Lewis base and the mol ratio of TMEDA and organolithium, and as the THF and the Et of low-pole Lewis base
3The mol ratio of N and organolithium is 0.1: 1～160: 1.
In the method for the invention, the reaction later stage adopts the coupling agent of polyfunctionality to carry out coupling usually.The example of described coupling agent comprises Vinylstyrene, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, silicon tetrachloride or tin tetrachloride, preferred silicon tetrachloride.The mol ratio of described coupling agent and organic lithium initiator is 0.15: 1～0.20: 1.
Fourth penta multipolymer of the present invention can be by interrupter method and continuous processing production, preferably by interrupter method production., at first monomer and solvent are joined in the reactor for this reason, then compound conditioning agent and organic lithium initiator are joined respectively in the reactor, in 10～120 minutes reaction times, the back adds coupling agent again, and coupling time is 10～40 minutes.
Polymerization process of the present invention can be carried out in 0～130 ℃ temperature range, preferably carries out under 40～120 ℃, and it is liquid that polymerization pressure should keep polymerization system, generally at 0.05～1MPa, selects 0.1～0.3MPa usually.
When polymerization and linked reaction end, handle polymer fluid, to stop reactive polymer, avoid it to contact with airborne oxygen.Terminator commonly used is Virahol, water, ethanol etc.In addition, added a small amount of anti-aging agent usually before polymer precipitation, for example oxidation inhibitor such as 2,6 di tert butyl 4 methyl phenol etc. are precipitated out polymkeric substance then in excess ethyl alcohol.The consumption of terminator is generally the 1-5% that needs the trigger monomer quality, and the consumption of anti-aging agent is generally the 0.1-10% that needs the trigger monomer quality.
Polymerisate can obtain by the usual manner of this area, is added with the direct desolventizing of polymers soln of anti-aging agent after for example will stopping, or makes solvent and water form azeotrope with devaporation the above-mentioned polymers soln and be removed.Wet polymer drying and granulation and obtain product again.
The present invention passes through 1G/THF, 1G/Et
3N or 2G/TMEDA cooperate the adjustment of kick off temperature as the composite structure conditioning agent, obtain difference 1, fourth penta multipolymer of 2-structural content.The consumption of fixing a kind of conditioning agent, when adjusting the add-on of another conditioning agent, in the gained multipolymer 1, the 2-structural content changes little, the stable and controllable in having realized producing.
By adopting 1G/THF, 1G/Et
3N or 2G/TMEDA are as structure regulator and be used in combination coupling agent, can carry out successfully coupling in the polymerization later stage, obtain difference 1, the soluble polybutaamyl-rubber of 2-structural content, and this glue has excellent machinability, physical and mechanical properties and dynamic properties.
The present invention has following advantage:
1. the various raw materials of composite structure conditioning agent are taken conveniently, and its synthesis route is simple;
2. guaranteed the activity of spike in the polymerization process, and the successful coupling of energy;
3. different polymer solvent systems are used in reaction, as hexanaphthene, raffinate oil and hexanaphthene/hexane mixed solvent system, need not in the system adding other auxiliary adjustment agent, and polymeric reaction temperature can fix on 40～120 ℃, and the reaction times is 20～160 minutes;
4. polyreaction is by add-on and proportioning based on compound conditioning agent, and polymerization temperature is the adjustment means of assisting, and can obtain difference 1, the soluble polybutaamyl-rubber of 2-structural content, and its regulation range is 30～50%;
5. 1 in fourth penta multipolymer, the 2-Stability Analysis of Structures is easily controlled;
6. the adding of compound conditioning agent is little to the molecular weight and the molecular weight distribution influence of product.
7. can carry out successfully coupling in the polymerization later stage, obtain difference 1, the star-shaped solution-polymerized butadiene-isoprene rubber of 2-structural content.
Embodiment
The following example is used to describe the present invention, but never means the present invention is constituted any restriction, and in contrast, the applicant only regards it as one of optimum implementation of the various technical solutions of the present invention.
In the following example, specifications of raw materials and treating process are as follows: divinyl is industrial polymerization-grade, directly uses; Isoprene is industrial polymerization-grade, under the high pure nitrogen protection, uses behind the adding gama-alumina drying and dehydrating; Hexanaphthene, raffinate oil or the mixed solvent of hexanaphthene and normal hexane is a technical grade, need to add the gama-alumina drying and dehydrating more than three days, feed the high pure nitrogen oxygen of half an hour before use may exist in the system of removing; Initiator is n-Butyl Lithium or s-butyl lithium; Structure regulator is 1G/THF, 1G/Et
3N or 2G/TMEDA, it is stand-by that process adds the sodium backflow, back feeding nitrogen bubble is handled in distillation.
It is the composite structure conditioning agent that embodiment 1 adopts 1G/THF, and hexanaphthene/normal hexane mixed solvent (=88/12, weight ratio) system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=70/30, weight ratio)
Be aggregated in 5 liters of stainless steel cauldrons and carry out, reactor finds time to fill nitrogen (high purity nitrogen) pump drainage three times after hexanaphthene/normal hexane embathes, and reactor adopts deep fat heating and cold oil cooling, and hot oil temperature is set at 50 ℃, and the cold oil temperature is set at 30 ℃.Hexanaphthene/normal hexane 2600g, divinyl 271.95g, isoprene 116.55g are made with extra care at first disposable adding.Add 1G and THF according to design flow then, with deep fat reacting by heating material, when the question response temperature in the kettle rises to 50 ℃, control deep fat and cold oil ratio, make temperature of charge keep stable, disposable then adding is killed assorted and is caused with n-Butyl Lithium 4.2mmol (with the polymer solvent dilution, concentration is 0.3M) initiated polymerization.Polyreaction adds the 0.65mmol silicon tetrachloride and carries out linked reaction after 40 minutes, coupling is disposable adding 0.5ml Virahol termination and 0.5g anti-aging agent 1520 (Switzerland vapour Bagong department product) after 30 minutes, synthesizes star-shaped solution-polymerized butadiene-isoprene rubber.The polyreaction original pressure is 0.1MPa, and the reactor mixing speed is set at 200rpm, and the gained glue adopts devaporation to remove solvent.The molecular weight of sample, molecular weight distribution and coupling efficiency adopt gel permeation chromatography (day island proper Tianjin Class-LC10A cohesion permeation chromatography) to measure, and microtexture adopts nuclear-magnetism wave of oscillation spectrometer (Switzerland Bruker 400MHz nuclear magnetic resonance analyser) to measure.
The molecular weight of polymerisate, molecular weight distribution, coupling efficiency and 1,2 structural content measurement result see Table 1 and Fig. 1.By table 1 as seen: the star-shaped solution-polymerized butadiene-isoprene rubber prepared according to the present invention can successfully carry out linked reaction, and 1 in the multipolymer, the stable easily control of 2-structural content.
The molecular weight of the star-shaped solution-polymerized butadiene-isoprene rubber of table 1, molecular weight distribution and coupling efficiency
| The experiment number | IBR54052 | IBR54032 | IBR54054 | IBR54011 |
| 1G/THF/Li(mol/mol) | 0.1/30/1.0 | 0.3/30/1.0 | 0.5/30/1.0 | 0.8/30/1.0 |
| Mp | 178,314 | 167,685 | 188,699 | 163,657 |
| Mw/Mn | 1.36267 | 1.84682 | 1.43722 | 1.50261 |
| S(％) | 79.302 | 74.568 | 65.399 | 84.736 |
| 1，2-(％) | 43.34 | 43.88 | 44.13 | 44.46 |
Table 1 (continuing)
| The experiment number | IBR54062 | IBR54071 | IBR54072 | IBR54031 |
| 1G/THF/Li(mol/mol) | 1.0/30/1.0 | 1.5/30/1.0 | 2.0/30/1.0 | 1.0/10/1.0 |
| Mp | 185,657 | 139,172 | 158,029 | 150,676 |
| Mw/Mn | 1.47451 | 1.45580 | 1.46887 | 1.42868 |
| S(％) | 62.418 | 73.064 | 64.740 | 72.907 |
| 1，2-(％) | 44.57 | 44.91 | 45.00 | 42.34 |
Annotate:
Li: n-Butyl Lithium;
Mp: peak molecular weight;
Mw/Mn: molecular weight distribution;
S (%): coupling efficiency;
1,2-(%): contents of ethylene in the multipolymer.
As can be seen from Table 1: the adding of 1G/THF is little to the molecular weight and the molecular weight distribution influence of multipolymer, control THF consumption, adjust the add-on of 1G, in the multipolymer 1, the 2-structural content changes little, stable easily control, polymerization reaction late stage can be carried out linked reaction smoothly, and coupling efficiency can reach more than 60%.
In addition, copolymer sample IBR54062 and the IBR54031 that obtains in the present embodiment measured monomer conversion and molecular weight growth and time relation respectively, the result is shown in respectively in Fig. 2 and 3.
Fig. 4 shows that at kick off temperature be 50 ℃, and fixedly under the THF consumption condition, the 1G add-on is in the product 1, and the influence of 2-structural content is less, in conjunction with Fig. 5 as can be known, according to design requirements, by the adjustment of kick off temperature, can regulate in 30～50% scope.
Polymerization result shows: carry out the synthetic of soluble polybutaamyl-rubber, the radial copolymer of contents of ethylene in can obtaining with 1G/THF as the composite structure conditioning agent.
Butylaml random copolymer is carried out physical and mechanical properties measure, the result is as shown in table 2.By table 2 as seen, the star butadiene-isoprene rubber that synthesizes and common rare earth butadiene-isoprene rubber (Sinopec Qilu Petroleum Chemistry Co. Inst. development, with reference to " rare earth butadiene-isoprene rubber performance and the research of in tread rubber, using ", Jiao Zhimin etc., " rubber industry " the 49th the 8th phase of volume) relatively, has more excellent physical and mechanical performance.
The physical and mechanical properties of the star-shaped solution-polymerized butadiene-isoprene rubber of table 2
Comparative Examples 1Adopting the 2G/ ether is the composite structure conditioning agent, and hexanaphthene/normal hexane mixed solvent (=88/12, weight ratio) system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=70/30, weight ratio)
The coupling efficiency test is identical with embodiment 1 in copolymer method and the polymkeric substance, difference is that the composite structure conditioning agent changes the 2G/ ether into, the coupling efficiency measurement result of polymerisate sees Table 3, by table 3 as seen: under this condition, the a large amount of inactivations of reaction later stage spike, coupling efficiency is lower, is difficult to synthetic star-shaped solution-polymerized butadiene-isoprene rubber.
The coupling efficiency of table 3 soluble polybutaamyl-rubber
| The experiment number | IBR56011 | IBR56012 | IBR56021 | IBR56022 |
| 2G/ ether/Li (mol/mol) | 0.1/30/1.0 | 0.3/30/1.0 | 0.5/30/1.0 | 0.8/3 0/1.0 |
| S(％) | 39.354 | 24.682 | 25.374 | 24.648 |
Table 3 (continuing)
| The experiment number | IBR56061 | IBR56062 | IBR56113 |
| 2G/ ether/Li (mol/mol) | 1.0/30/1.0 | 1.5/30/1.0 | 2.0/30/1.0 |
| S(％) | 22.196 | 23.568 | 24.704 |
The coupling efficiency test is identical with embodiment 1 in copolymer method and the polymkeric substance, difference is that the composite structure conditioning agent changes 1G/2G into, the coupling efficiency measurement result of polymerisate sees Table 4, by table 4 as seen: under this condition, the a large amount of inactivations of reaction later stage spike, coupling efficiency is lower, is difficult to synthetic star-shaped solution-polymerized butadiene-isoprene rubber.
The coupling efficiency of table 4 soluble polybutaamyl-rubber
| The experiment number | IBR56131 | | IBR56151 | IBR56162 | |
| 1G/2 G/Li(mol/mol) | 0.1/0.8/1.0 | 0.3/0.8/1.0 | 0.5/0.8/1.0 | 0.8/0.8/1.0 | |
| S(％) | 28.147 | 21.473 | 18.064 | 14.438 |
Table 4 (continuing)
| The experiment number | | IBR56182 | IBR56183 | |
| 1G/2G/Li(mol/mol) | 1.0/0.8/1.0 | 1.5/0.8/1.0 | 2.0/0.8/1.0 | |
| S(％) | 16.356 | 12.548 | 10.631 |
Embodiment 2(the 1G/THF/Li mol ratio: 0.8/30/1) be the composite structure conditioning agent, hexanaphthene/normal hexane mixed solvent (=88/12, weight ratio) system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=70/30, weight ratio) to adopt 1G/THF
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that kick off temperature is 70 ℃.In the product 1, the relation of 2-structure and 1G/THF add-on is seen Fig. 5.The coupling efficiency and the physical and mechanical properties of product see Table 5.
The coupling efficiency of the star-shaped solution-polymerized butadiene-isoprene rubber of table 5 and physical and mechanical properties
Embodiment 3(the 1G/THF/Li mol ratio: 0.8/30/1) be the composite structure conditioning agent, hexanaphthene/normal hexane mixed solvent (=88/12, weight ratio) system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=50/50, weight ratio) to adopt 1G/THF
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that the raw material add-on should be hexanaphthene/normal hexane 2600g, divinyl 194.25g, isoprene 194.25g mutually.The coupling efficiency and the physical and mechanical properties of product see Table 6.
The coupling efficiency of the star-shaped solution-polymerized butadiene-isoprene rubber of table 6 and physical and mechanical properties
Embodiment 4(the 1G/THF/Li mol ratio: 0.8/30/1) be the composite structure conditioning agent, the hexanaphthene system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=70/30, weight ratio) to adopt 1G/THF
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that the polymer solvent system changes hexanaphthene 2600g into.The coupling efficiency and the physical and mechanical properties of product see Table 7.
The coupling efficiency of the star-shaped solution-polymerized butadiene-isoprene rubber of table 7 and physical and mechanical properties
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is 1G/Et
3N is the composite structure conditioning agent.The coupling efficiency and the physical and mechanical properties of product see Table 8.
The coupling efficiency of the star-shaped solution-polymerized butadiene-isoprene rubber of table 8 and physical and mechanical properties
Embodiment 6(the 2G/TMEDA/Li mol ratio: 0.5/1/1) be the composite structure conditioning agent, hexanaphthene/normal hexane mixed solvent (=88/12, weight ratio) system is synthesized star-shaped solution-polymerized butadiene-isoprene rubber (BD/IP=70/30, weight ratio) to adopt 2G/TMEDA
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that 2G/TMEDA is the composite structure conditioning agent.The coupling efficiency and the physical and mechanical properties of product see Table 9.
The coupling efficiency of the star-shaped solution-polymerized butadiene-isoprene rubber of table 9 and physical and mechanical properties
Claims (12)
1. polymerization process of producing soluble polybutaamyl-rubber is included under 0～130 ℃ the temperature at organolithium as initiator and 1G/THF, 1G/Et
3The compound regulation system of N or 2G/TMEDA exists carries out the copolymerization of divinyl and isoprene down in varsol, and the coupling agent that adds polyfunctionality in the basic back fully of polymerization carries out linked reaction, vinyl solution polymerized butadiene-isoprene rubber in obtaining.
2. according to the method for claim 1, it is characterized in that organolithium is to be selected from the following compound any: C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium, C
3-C
6The cycloalkyl lithium.
3. according to the method for claim 2, it is characterized in that organolithium is n-Butyl Lithium or s-butyl lithium.
4. according to the method for claim 1, it is characterized in that varsol is a hexanaphthene, the mixed solvent system of raffinating oil or being made up of hexanaphthene and normal hexane, wherein the content of normal hexane in mixed solvent is 5～30 weight %.
5. according to the method for claim 1, it is characterized in that isoprene content is 10～50% based on the monomer total mass, butadiene content is 90～50% based on the monomer total mass.
6. according to the method for claim 1, it is 10～20 weight % that the consumption that it is characterized in that varsol should make monomer concentration.
7. according to the method for claim 1, it is characterized in that temperature of reaction is 40～120 ℃.
8. according to the method for claim 1, it is characterized in that the preferred 1G/THF of compound regulation system.
9. according to the method for claim 1, it is characterized in that in the compound regulation system, is 0.1: 1～10: 1 as 1G, the 2G of strong polar Lewis base and the mol ratio of TMEDA and organolithium, and as the THF and the Et of low-pole Lewis base
3The mol ratio of N and organolithium is 0.1: 1～160: 1.
10. according to the method for claim 1, it is characterized in that coupling agent is to be selected from any of following compound: Vinylstyrene, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, silicon tetrachloride, tin tetrachloride, preferred silicon tetrachloride.
11. according to the method for claim 10, the mol ratio that it is characterized in that coupling agent and organolithium is 0.15: 1～0.20: 1.
12., it is characterized in that contents of ethylene is 30～50% in the gained multipolymer according to the method for claim 1.
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| CN102558441A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Synthetic method of solution polymerized butadiene-isoprene rubber |
| CN102863576A (en) * | 2012-08-23 | 2013-01-09 | 辽宁和运合成橡胶研究院有限公司 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
| CN104558410A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Structure modifier for anionic polymerization and anionic polymerization method |
| CN114716598A (en) * | 2021-01-04 | 2022-07-08 | 北京化工大学 | Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber |
| CN117567686A (en) * | 2024-01-16 | 2024-02-20 | 新***山子石油化工有限公司 | Solution polymerized styrene-butadiene rubber with fixed block styrene content, and preparation method and application thereof |
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2006
- 2006-01-28 CN CNB200610002958XA patent/CN100487009C/en active Active
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| CN101638450B (en) * | 2008-07-29 | 2011-01-19 | 中国石油化工股份有限公司 | Method for preparing solution-polymerized conjugated diene homopolymer or conjugated diene/monovinyl aromatic hydrocarbon copolymer with high vinyl content |
| CN102558441A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Synthetic method of solution polymerized butadiene-isoprene rubber |
| CN102863576A (en) * | 2012-08-23 | 2013-01-09 | 辽宁和运合成橡胶研究院有限公司 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
| CN102863576B (en) * | 2012-08-23 | 2014-11-19 | 辽宁和运合成橡胶研究院有限公司 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
| CN104558410A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Structure modifier for anionic polymerization and anionic polymerization method |
| CN114716598A (en) * | 2021-01-04 | 2022-07-08 | 北京化工大学 | Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber |
| CN117567686A (en) * | 2024-01-16 | 2024-02-20 | 新***山子石油化工有限公司 | Solution polymerized styrene-butadiene rubber with fixed block styrene content, and preparation method and application thereof |
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