CN100387629C - Star high-vinyl-content poly-conjugated-diolefin rubber and preparing method - Google Patents
Star high-vinyl-content poly-conjugated-diolefin rubber and preparing method Download PDFInfo
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- CN100387629C CN100387629C CNB2005100522290A CN200510052229A CN100387629C CN 100387629 C CN100387629 C CN 100387629C CN B2005100522290 A CNB2005100522290 A CN B2005100522290A CN 200510052229 A CN200510052229 A CN 200510052229A CN 100387629 C CN100387629 C CN 100387629C
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Abstract
The present invention relates to star-shaped poly-conjugated dialkene comprising high vinyl content, and a preparation method thereof. In the present invention, raffinate oil is used as a solvent; organic lithium is used as an initiating agent; compound additive agents (the mixtures of Lewis base, anionic surface active agents and raffinate oil) are structure adjusting agents; conjugated dialkene generates homopolymerization reaction; products can be obtained through coupling reaction. The method of the present invention has the advantages of short reaction time for example, about 10 minutes, high production efficiency and high device utilization rate; the vinyl structure content of obtained products can be more than 70%, and simultaneously, the coupling efficiency can be more than 70%; the products are especially suitable for the modification of treads and plastic.
Description
Invention field
The present invention relates to a kind of method for preparing novel poly-conjugated-diolefin rubber, more particularly, relate to the new type rubber and the application thereof of a kind of method of the poly-conjugated-diolefin rubber for preparing star high-vinyl-content and preparation thus.
Background of invention
The polyhutadiene of high-vinyl-content is meant the polyhutadiene of vinyl (1, the 2-structure) content more than 55% (massfraction), is a kind of energy-saving tread rubber, also is a kind of good plastic modifier simultaneously.General polycoordination or the anionic polymerisation process of adopting synthesizes.For improving its over-all properties, synthesize the polybutadiene rubber of star high-vinyl-content by anionoid polymerization further again link coupled method after polymerization finishes in recent years.
As everyone knows, than divinyl and cinnamic copolyreaction, the characteristics of butadiene homopolymerization reaction are that speed is fast, and thermal discharge is big, and temperature rise is fast, and the temperature of reaction height is wayward, and cold condition helps the formation of vinyl structure.
US 4,397, and 994 show, Japan SYnthetic Rubber Co. Ltd is initiator with the butyllithium, and hexanaphthene is a solvent, tetrahydrofuran (THF) (THF) is a structure regulator, obtained contents of ethylene and be 70% high vinyl polybutadiene, use coupling agent SnCl again
4Carry out coupling and synthesized the polyhutadiene of star high-vinyl-content (S-HVBR).But what this patent was used is the low temperature system, and operation easier is big, is not easy to suitability for industrialized production.
US 5,008, and 343 mention, though adopt the strong structure regulators of ethers such as glycol dimethyl ether, diglyme can obviously improve vinyl structure content, the tin coupling efficiency is on the low side; And when adopting Tetramethyl Ethylene Diamine, make it be not easy to industrial applications because of seriously polluted.This patent is initiator with the butyllithium, and hexanaphthene is a solvent, and asymmetrical ether is a structure regulator, the solution polymerized butadiene styrene rubber that obtained contents of ethylene and be 58%, coupling efficiency is 75% star high-vinyl-content, but this asymmetrical ether is difficult to obtain, and the cost height is unfavorable for industrial applications.
US 5,654, and 384 show, with the butyllithium is initiator, and hexanaphthene is a solvent, and ethers or amine and alkali metal alcoholates are the composite structure conditioning agent, obtain contents of ethylene and be the polybutadiene rubber product more than 80%, but this patented method adopts isothermal reaction technology, is unfavorable for industrial applications.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the polybutadiene rubber field, in the hope of developing a kind of polybutadiene rubber that is suitable for making tire tread and modifying plastics.Found that by in the polymerization process of divinyl, using specific structure regulator and being used in combination to raffinate oil and be solvent, can at room temperature cause and carry out polyreaction, when reaction high temperature, need not remove reaction heat, and produce the polybutadiene rubber product of the star high-vinyl-content that satisfies above-mentioned performance requriements thus.The present invention just is being based on this discovery and is being accomplished.
General purpose of the present invention is to provide a kind of novel method for preparing poly-conjugated-diolefin rubber, this method at room temperature causes and carries out polyreaction, reaction heat need not be removed during polyreaction high temperature, and technological process is simple, reaction times is short, production efficiency and plant factor height.
A comparatively concrete purpose of the present invention is to provide a kind of method for preparing the poly-conjugated-diolefin rubber of star high-vinyl-content, comprise making conjugated diene, carry out coupling and termination then as carrying out copolymerization at organic lithium initiator and Lewis base, anion surfactant and the mixture of raffinating oil in the presence of as composite additive in the raffinating oil of solvent.
Another object of the present invention is to provide the poly-conjugated-diolefin rubber product of the new star high-vinyl-content of a class, polybutadiene rubber product especially, and this series products is particularly suitable for making tire tread and modifying plastics.
Therefore, one aspect of the present invention provides a kind of method for preparing the poly-conjugated-diolefin rubber of star high-vinyl-content, comprises the steps:
1) adopting organolithium under inert gas environment is initiator, is composite additive with Lewis base, anion surfactant and the mixture of raffinating oil, as the equal polymerization of carrying out conjugated diene in the raffinating oil of solvent;
2) after finishing, polyreaction adds coupling agent; With
3) after linked reaction is finished, add terminator and anti-aging agent, condense in the usual way then and drying.
The present invention provides the poly-conjugated-diolefin rubber of the new star high-vinyl-content of a class on the other hand, and therein ethylene base content is 70% or higher.
Further aspect of the present invention provides the purposes of poly-conjugated-diolefin rubber in making tire and modified plastics of above-mentioned star high-vinyl-content.
Implement best mode of the present invention
In the preparation method of poly-conjugated-diolefin rubber of the present invention, operable conjugated diene is meant any monomer that has conjugated double bond in its molecule, as C
4～C
12Conjugated diene monomer, preferred C
4～C
8Conjugated diene monomer, its specific examples comprise 1,3-butadiene, isoprene, 1,3-pentadiene, 1, the 1,3-pentadiene of 3-hexadiene, replacement or the 1,3-butadiene of replacement, and as 2,3-dimethyl-1,3-butadiene or 1-phenyl-1,3-butadiene.Conjugated diene monomer can use separately, also can mix use.Preferably select 1,3-butadiene or isoprene for use, because these two kinds monomeric rate of polymerization height help suitability for industrialized production.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, should make monomer concentration as the consumption of raffinating oil of solvent is 2～70g total monomer/100ml solvent, preferred 5-50g/ total monomer/100ml solvent, most preferably 10-25g total monomer/100ml solvent.
According to the present invention, preferred raffinating oil of using is meant that boiling range is the hydrogenated gasoline that 60～90 ℃ platformate raffinate or boiling range are 60～90 ℃.Boiling range is that 60-90 ℃ platformate raffinate is meant from platformate raffinate and extracts remaining that part of oil behind the aromatic hydrocarbons, and main component is:
Component concentration (volume %)
2-methylpropane 0.43
Normal butane 0.10
2-methylbutane 4.55
Skellysolve A 7.10
Pentamethylene 4.24
2,3-methyl cyclobutane 3.84
2-methylpentane 14.94
3-methylpentane 11.30
Normal hexane 22.53
Methylcyclopentane 8.44
Benzene 0.38
Hexanaphthene 1.28
2-methyl hexane 6.38
1,1-dimethylcyclopentane 2.5
2,3-dimethylcyclopentane 2.5
3-methyl hexane 5.55
Suitable-1,2-dimethylcyclopentane 1.14
Instead-1,3-dimethylcyclopentane 0.46
3,3-dimethylpentane 0.72
Instead-1,2-dimethylcyclopentane 0.72
Normal heptane 0.79
C
8On a small quantity
Generally can be used for polymer solvent raffinate oil or the specification of hydrogenated gasoline as follows:
Boiling range: 60～140 ℃, be preferably 60～90 ℃
Iodine number :≤0.4g/100g
Water-content: do not have
Water-soluble soda acid: neutrality
In the preparation method of poly-conjugated-diolefin rubber of the present invention, used composite additive is Lewis base, anion surfactant and the mixture of raffinating oil in the polymerization process.Various Lewis base compounds can be selected for use, preferably select for use ether compound or tertiary amine compound as polar additive and structure regulator, can select tetrahydrofuran (THF), tetrahydropyrans or 1,4-dioxane for use as cyclic ether compounds; Aliphatic monoether can be selected Anaesthetie Ether or dibutyl ether for use; The optional spent glycol dme of aliphatic polyether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol or diethylene glycol dibutyl ether; Aromatic oxide can be selected diphenyl ether, methyl-phenoxide or similar ether for use; Tertiary amine compound can be selected triethylamine, tripropyl amine, Tributylamine or other compound such as N, N, N ' for use, N '-Tetramethyl Ethylene Diamine, N, N-two basic aniline, pyridine or quinoline etc., its consumption is 10～30% weight based on the composite additive total amount, preferred 15～25% weight; Anion surfactant is selected the Sulfonates compound of the alkyl that contains 4～20 carbon atoms for use, and as Sodium dodecylbenzene sulfonate or Potassium dodecylbenzenesulfonate, its consumption is 3～15% weight based on the composite additive total amount, preferred 5～12% weight; Raffinating oil and selecting boiling range for use is the hydrogenated gasoline that 60～90 ℃ platformate raffinate or boiling range are 60～90 ℃, and wherein boiling range is that 60-90 ℃ platformate raffinate is meant from platformate raffinate and extracts remaining that part of oil behind the aromatic hydrocarbons.In composite additive, the consumption of raffinating oil is 55～87% weight based on the composite additive total amount, preferred 65～80% weight.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, the consumption of composite additive should make that the weight ratio of itself and organic lithium initiator is 1～40, preferred 10～30.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, used organic lithium initiator preferably uses organic single-lithium for commonly used those in anionoid polymerization field in the polymerization process, those shown in the formula RLi for example, and wherein R is the C of straight or branched
1-C
7Alkyl, C
3-C
6Cycloalkyl or C
6-C
12Aryl 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., but is preferably selected n-Butyl Lithium or s-butyl lithium for use.The consumption of initiator depends on the size of design molecular weight in the polymerization process.General initiator amount is that every 100g monomer need add 0.3～2.5mmol.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, operable rare gas element is commonly used those in this area, as nitrogen, argon gas or helium etc.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, operable coupling agent is many vinyl compounds, halogenide, ether, aldehyde, ketone, ester etc.As Vinylstyrene, tetrem thiazolinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate (DMT) etc.Coupling agent is Vinylstyrene, silicon tetrachloride or tin tetrachloride etc. preferably.It is 0.1～2 that the consumption of coupling agent should make the mol ratio of coupling agent and organic lithium initiator.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, operable terminator is water or alcohols, as being methyl alcohol, ethanol, Virahol etc., preferably selects Virahol for use.It is 0.1～1 that the consumption of terminator should make the mol ratio of terminator and organic lithium initiator.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, operable anti-aging agent can be normally used phenols or amine, be preferably 2,6-ditertbutylparacresol (abbreviation antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol) (abbreviation antioxidant 2246) etc.The add-on of anti-aging agent is generally 0.5～2% weight of amount of polymers.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, the polymeric reaction temperature in step 1) is generally 0～150 ℃, and preferred 20～110 ℃, most preferably 30～90 ℃.
In the preparation method of poly-conjugated-diolefin rubber of the present invention, the polymerization pressure in step 1) is generally 0.1～0.8MPa, preferred 0.1～0.4MPa, most preferably 0.1～0.30MPa.
According to the present invention, carry out the equal polymerization of conjugated diene as solvent by using specific composite additive also to use to raffinate oil as structure regulator, can be at short notice, for example in 5-30 minute, especially in 7-20 minute, finish polyreaction, so production efficiency and plant factor are all very high.In addition, it is 70% or higher homopolymer rubber that the method according to this invention can obtain contents of ethylene, and coupling efficiency reaches more than 70% simultaneously, and described homopolymer rubber is particularly suitable for making tire and modified plastics.
Embodiment
Describe the present invention in detail by embodiment and Comparative Examples below, but scope of the present invention is not limited to these embodiment.
Initiator concentration records with two volumetrys in an embodiment; The molecular weight of polymkeric substance and coupling efficiency are tested with gel permeation chromatograph (mobile phase solvent is THF for day island proper Tianjin LC-10Atvp of company series, normal temperature mensuration); Vinyl structure content, 1 in the divinyl chain, and 4-structural content infrared spectrometer (U.S. FTS3000 of BIO-RAD company type infrared spectrometer, normal temperature is measured, the liquid pool method, solvent is CS
2, scanning times 32 times) and test.
Embodiment 1
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60-90 ℃ a platformate raffinate) 7000ml, composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60-90 ℃ a platformate raffinate) of raffinating oil successively; weight ratio is 20: 10: 70) 19g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, add n-Butyl Lithium 0.64g when temperature is 30 ℃, reaction pressure is 0.1～0.3MPa.After the polyreaction 10 minutes, transformation efficiency reaches 100%, adds tin tetrachloride 0.65g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The molecular weight and the coupling efficiency of product are tested with gel permeation chromatograph, vinyl, 1, and the 4-structural content is tested with the infrared light spectrum instrument, and the test result of product sees Table 1.
Embodiment 2
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60-90 ℃ a platformate raffinate) 7000ml, composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60-90 ℃ a platformate raffinate) of raffinating oil successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, n-Butyl Lithium 0.64g, carry out polyreaction.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 10 minutes, transformation efficiency reaches 100%, adds tin tetrachloride 0.65g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
Embodiment 3
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60-90 ℃ a platformate raffinate) 7000ml, composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60-90 ℃ a platformate raffinate) of raffinating oil successively; weight ratio is 25: 10: 65) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, n-Butyl Lithium 0.64g, carry out polyreaction.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 10 minutes, transformation efficiency reaches 100%, adds tin tetrachloride 0.50g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
Embodiment 4
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60-90 ℃ a platformate raffinate) 7000ml, composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60-90 ℃ a platformate raffinate) of raffinating oil successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, n-Butyl Lithium 0.64g, carry out polyreaction.The polymerization kick off temperature is 40 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 7 minutes, transformation efficiency reaches 100%, adds tin tetrachloride 0.65g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
Embodiment 5
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60-90 ℃ a platformate raffinate) 7000ml, composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60-90 ℃ a platformate raffinate) of raffinating oil successively; weight ratio is 20: 5: 75) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, n-Butyl Lithium 0.64g, carry out polyreaction.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 10 minutes, transformation efficiency reaches 100%, adds silicon tetrachloride 0.45g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
Comparative Examples 6
Test is carried out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds hexanaphthene 7000ml, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, n-Butyl Lithium 0.64g, carry out polyreaction.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 3 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.65g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
Comparative Examples 7
Test is carried out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, volume ratio 9: 1) 7000ml, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 1000 grams, reacting liquid temperature reduced to 0 ℃, add n-Butyl Lithium 0.64g, carry out polyreaction by cooling.Reaction pressure is 0.1～0.3MPa.After the polyreaction 5 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.65g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.6g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the polybutadiene rubber product of star high-vinyl-content.The test result of product sees Table 1.
The test result of table 1 product
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Mn (ten thousand) | 10.0 | 10.2 | 10.0 | 9.8 | 10.1 | 10.3 | 10.1 |
| CE％ | 75 | 76 | 70 | 76 | 80 | 55 | 56 |
| Bv％ | 86 | 83 | 82 | 72 | 81 | 50 | 55 |
| Ct％ | 9 | 11 | 12 | 17 | 12 | 30 | 32 |
| Cc％ | 5 | 6 | 6 | 11 | 7 | 20 | 13 |
Annotate: Mn (ten thousand) is basic number-average molecular weight; CE% is a coupling efficiency; Bv% is 1, the 2-structural content; Cc% is suitable-1,4 structural content; Ct% is anti--1,4 structural content.
Claims (24)
1. a method for preparing the poly-conjugated-diolefin rubber of star high-vinyl-content comprises the steps:
1) adopting organolithium under inert gas environment is initiator, is composite additive with Lewis base, anion surfactant and the mixture of raffinating oil, as the equal polymerization of carrying out conjugated diene in the raffinating oil of solvent;
2) after finishing, polyreaction adds coupling agent;
3) after linked reaction is finished, add terminator and anti-aging agent, condense in the usual way then and drying;
Wherein should make monomer concentration as the consumption of raffinating oil of solvent in step 1) is 2～70g total monomer/100ml solvent; The consumption of organic lithium initiator is that every 100g monomer need add 0.3～2.5mmol; Described composite additive is lewis' base, anion surfactant and the mixture of raffinating oil, and the weight ratio of composite additive and organic lithium initiator is 1～40.
2. be 5～50g total monomer/100ml solvent according to the process of claim 1 wherein that in step 1) the consumption of raffinating oil as solvent should make monomer concentration.
3. according to the process of claim 1 wherein that the weight ratio of composite additive and organic lithium initiator is 10～30.
4. according to the method for claim 1, wherein in described composite additive, described Lewis base is a cyclic ether compounds, aliphatic monoether, aliphatic polyether, aromatic oxide, tertiary amine compound or be selected from N, N, N ', N '-Tetramethyl Ethylene Diamine, N, other compound of N-Diethyl Aniline, pyridine or quinoline, its consumption is 10～30% weight based on the composite additive total amount; Described anion surfactant is the Sulfonates compound that contains the alkyl of 4～20 carbon atoms, and its consumption is 3～15% weight based on the composite additive total amount; Described raffinating oil to boiling range is the hydrogenated gasoline that 60～90 ℃ platformate raffinate or boiling range are 60～90 ℃, its consumption is 55～87% weight based on the composite additive total amount.
5. according to the method for claim 4, wherein cyclic ether compounds is selected from tetrahydrofuran (THF), tetrahydropyrans or 1, the 4-dioxane, aliphatic monoether is selected from Anaesthetie Ether or dibutyl ether, aliphatic polyether is selected from glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol or diethylene glycol dibutyl ether, aromatic oxide is selected from diphenyl ether, methyl-phenoxide or similar ether, and tertiary amine compound is selected from triethylamine, tripropyl amine or Tributylamine.
6. according to the method for claim 4, the consumption of wherein said Lewis base is 15～25% weight based on the composite additive total amount.
7. according to the method for claim 4, wherein said anion surfactant is that Sodium dodecylbenzene sulfonate or Potassium dodecylbenzenesulfonate and its consumption are 5～12% weight based on the composite additive total amount.
8. according to the method for claim 4, wherein said consumption of raffinating oil is 65～80% weight based on the composite additive total amount.
9. according to the process of claim 1 wherein that the polymerization reaction time of step 1) is 5-30 minute.
10. according to each method among the claim 1-9, wherein said raffinating oil is that boiling range is 60～90 ℃ a platformate raffinate.
11. according to each method among the claim 1-9, wherein said conjugated diene is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 1, the 1,3-pentadiene of 3-hexadiene, replacement or the 1,3-butadiene of replacement, or its mixture.
12. according to the method for claim 11, wherein the 1,3-butadiene of Qu Daiing is 2,3-dimethyl-1,3-butadiene or 1-phenyl-1,3-butadiene.
13. according to the method for claim 11, wherein said conjugated diene is 1,3-butadiene or isoprene.
14. according to the method for claim 13, wherein said conjugated diene is a 1,3-butadiene.
15. according to each method among the claim 1-9, wherein said organic lithium initiator is n-Butyl Lithium or s-butyl lithium.
16. according to each method among the claim 1-9, wherein in step 2) in use the coupling agent that is selected from tin tetrachloride, silicon tetrachloride, Vinylstyrene, and the mol ratio of coupling agent and organic lithium initiator is 0.1～2.
17. according to each method among the claim 1-9, wherein said terminator is water, methyl alcohol or Virahol, and the mol ratio of terminator and organic lithium initiator is 0.1～1.
18. according to each method among the claim 1-9, wherein said anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol or 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), and its consumption is 0.5～2% weight based on polymkeric substance.
19. according to each method among the claim 1-9, wherein polymeric reaction temperature is 0～150 ℃.
20. according to the method for claim 19, wherein polymeric reaction temperature is 20～110 ℃.
21. according to each method among the claim 1-9, wherein polymerization pressure is 0.1～0.8MPa.
22. according to the method for claim 21, wherein polymerization pressure is 0.1～0.4MPa.
23. one kind by the star-like poly-conjugated-diolefin rubber that obtains according to each method among the claim 1-21, it is characterized in that vinyl structure content is 70% or higher.
24. the purposes of star-like poly-conjugated-diolefin rubber in making tire tread and modified plastics according to claim 23.
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| CN103374101B (en) * | 2012-04-18 | 2015-11-25 | 中国石油化工股份有限公司 | The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) |
| CN103804603B (en) * | 2012-11-07 | 2016-03-02 | 中国石油化工股份有限公司 | The application of a kind of solution polymerized butadiene styrene rubber and synthetic method and acid anhydrides |
| CN103804736B (en) * | 2012-11-14 | 2016-06-08 | 中国石油天然气股份有限公司 | A kind of preparation method of the oil-filled solution polymerized butadiene styrene rubber of environment-friendly type |
| CN114044838A (en) * | 2021-11-26 | 2022-02-15 | 瑞易德新材料股份有限公司 | Chlorinated butadiene rubber material, preparation method and application |
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| US4139690A (en) * | 1976-02-20 | 1979-02-13 | Japan Synthetic Rubber Co., Ltd. | Process for preparing conjugated diene polymers |
| CN1039036A (en) * | 1989-08-17 | 1990-01-24 | 北京燕山石油化工公司研究院 | The manufacture method of atactic butadiene styrene copolymer |
| CN1089272A (en) * | 1992-12-26 | 1994-07-13 | 中国石油化工总公司 | The method of contents of ethylene in control dienite and the multipolymer |
-
2005
- 2005-01-31 CN CNB2005100522290A patent/CN100387629C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139690A (en) * | 1976-02-20 | 1979-02-13 | Japan Synthetic Rubber Co., Ltd. | Process for preparing conjugated diene polymers |
| CN1039036A (en) * | 1989-08-17 | 1990-01-24 | 北京燕山石油化工公司研究院 | The manufacture method of atactic butadiene styrene copolymer |
| CN1089272A (en) * | 1992-12-26 | 1994-07-13 | 中国石油化工总公司 | The method of contents of ethylene in control dienite and the multipolymer |
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