CN100390213C - Star high-vinyl-content soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber, and preparing method - Google Patents
Star high-vinyl-content soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber, and preparing method Download PDFInfo
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Abstract
The present invention relates to star-shaped high-vinyl-content solution polymerized copolymer rubber of conjugated diolefin/single ethenyl arene and a preparation method thereof. A compound additive agent (a mixture of lewis base, an anionic surface active agent and raffinate oil) is used as a structure regulating agent, conjugated diene and single ethenyl arene have a copolymerization reaction, and through a coupling reaction, a product can be obtained. The present invention has the advantages that the reaction time of the preparation method is short, such as about 10 minutes; productive efficiency and equipment utilization rate are high; the vinyl structure content of the obtained product reaches more than 60%, and at the same time, coupling efficiency reaches more than 70%; the obtained product has high moisture and slip resistance and low rolling resistance, and is especially suitable for fabricating building tyre treads.
Description
Invention field
The present invention relates to a kind of method for preparing novel conjugated-diolefin/uni-vinyl-arene copolymer rubber, more particularly, relate to the new copolymer rubber and the application thereof of a kind of method of the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber for preparing star high-vinyl-content and preparation thus.
Background of invention
The current rubber of tread rubber of automobile tires that is applicable to not only will have good abrasion resistance, also will have high wet-sliding resistant and low-rolling-resistance, could satisfy demand energy-conservation and safety traffic like this.And these two kinds of performance demands of low-rolling-resistance and high wet-sliding resistant are conflicting, and the rubber of single variety is difficult to satisfy simultaneously this two kinds of requirements.Method with blend just makes two kinds of performances improve to some extent two kinds of blend rubbers that have low-rolling-resistance and high wet-sliding resistant respectively, is difficult to obtain the ideal product.For improving the anti-slippery and the rolling resistance of rubber item, attempt mainly to reach with divinyl rubber or the styrene-butadiene rubber(SBR) that organic lithium initiator obtains by modification.For example, by Molecular Structure Design, can synthesize multipolymer and homopolymer with low-rolling-resistance and high wet-sliding resistant.The rolling resistance of rubber item and anti-slippery can be characterized by the tan δ value of 60 ℃ and 0 ℃ in its viscoelastic spectra usually, and the value of the tan δ in the time of 60 ℃ is low more, and the rolling resistance of rubber is more little, and the tan δ value in the time of 0 ℃ is high, and the anti-slippery of rubber is good more.
US 4,367, and 325 and US4, mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic high-vinyl-content of anionoid polymerization in 139,690, it is the composite structure conditioning agent that this method adopts ethers and anion surfactant, because of initiation reaction at low temperatures, long reaction time.
US 5, also mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic star high-vinyl-content of anionoid polymerization in 008,343, this method is the activator and the structure regulator of reaction with the asymmetrical ether, because the complex ability of asymmetrical ether is poor, so long reaction time; And the method that this patent relates to will be carried out removing of reaction heat, polymerization technique complexity when reaction reaches a high temperature.
US 4,397, also mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic star high-vinyl-content of anionoid polymerization in 994, this method adopts cyclic ethers (THF) as structure regulator, initiation reaction at low temperatures, this method running cost height, long reaction time are unfavorable for suitability for industrialized production.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the styrene-butadiene rubber(SBR) field, a kind ofly not only has good abrasion resistance in the hope of developing, but also has the styrene-butadiene rubber(SBR) of high wet-sliding resistant and low-rolling-resistance.Found that by in divinyl and cinnamic polymerization process, 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 solution polymerized butadiene styrene 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 conjugated-diolefin/uni-vinyl-arene copolymer rubber, this method at room temperature causes and carries out polyreaction, reaction heat need not be removed during polyreaction high temperature, 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 soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of star high-vinyl-content, comprise making conjugated diene and monovinylarene, 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 soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber product of the new star high-vinyl-content of a class, especially styrene-butadiene rubber(SBR) product, this series products has high moisture resistance and low-rolling-resistance, be particularly suitable for making tire tread, can use separately, also can use with other rubber mix.
Therefore, one aspect of the present invention provides a kind of method for preparing the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer 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 copolymerization of carrying out conjugated diene and monovinylarene 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.
The present invention provides the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of the new star high-vinyl-content of a class on the other hand, and therein ethylene base content is 60% or higher.
Further aspect of the present invention provides the goods based on the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of above-mentioned star high-vinyl-content, as tire.
Implement best mode of the present invention
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable mono vinyl arenes monomer is meant the aromatic monomer that has a vinyl substituted base on its aromatic ring, as contains C
8～C
20Monovinylarene, preferred C
8-C
12Monovinylarene, its specific examples comprises vinylbenzene, C
1-C
6The vinylbenzene that alkyl replaces, as-vinyl toluene, p-methylstyrene or right-t-butyl styrene, or have substituent styrene derivatives on the vinyl, as alpha-methyl styrene.Mono vinyl arenes monomer can use separately, also can mix use.Consider from obtaining the complexity aspect, preferably use vinylbenzene and p-methylstyrene, most preferably use vinylbenzene.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the consumption of conjugated diene monomer is a 25-95% weight based on the monomer total amount, preferred 50-90% weight; Correspondingly, the consumption of mono vinyl arenes monomer is a 5-75% weight based on the monomer total amount, preferred 10-50% weight.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer 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-Diethyl 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 conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, used organic lithium initiator is commonly used those in anionoid polymerization field in the polymerization process, the preferred organic single-lithium that uses, those shown in the formula RLi for example, 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 conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer 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 0.5～2% weight based on polymkeric substance generally.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer 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 conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the polymerization pressure in step 1) is generally 0.1～0.8MPa, preferred 0.1～0.4MPa, most preferably 0.1～0.3MPa.
According to the present invention, carry out the copolymerization of conjugated diene and monovinylarene 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 60% or higher copolymer rubber that the method according to this invention can obtain contents of ethylene, and coupling efficiency reaches more than 70% simultaneously, and described copolymer rubber has high wet-sliding resistant and low-rolling-resistance, is particularly suitable for making tire tread.
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 infrared spectrometer in styrene content and the divinyl chain (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; (measure by U.S. TA-DMA2980 viscoelastic spectrometer with viscoelastic spectrometer for the tan δ value of rubber unvulcanizate.Frequency 2Hz, 5 ℃/min of temperature rise rate ,-120 ℃～+ 100 ℃, batten size: 40mm*5mm*1mm) 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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see 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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 250 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 750 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see 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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 150 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 850 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see 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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 40 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see 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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 5: 75) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds silicon tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Comparative Examples 6
Test is carried out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds hexanaphthene 7000ml, vinylbenzene 200 grams, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.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 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see 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, vinylbenzene 200 grams, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, reacting liquid temperature reduced to 10 ℃, add n-Butyl Lithium 0.53g, carry out copolyreaction then by cooling.Reaction pressure is 0.1～0.3MPa.After the polyreaction 5 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Comparative Examples 8
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 the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 250 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and hexanaphthene/normal hexane (volume ratio is 90: 1) successively; weight ratio is 20: 10: 70) 16g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 750 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 1.5 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
The structure of table 1 copolymer product and performance data
| Embodiment number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Mn (ten thousand) | 12.0 | 11.9 | 12.0 | 12.1 | 11.8 | 12.3 | 12.1 | 14.2 |
| CE％ | 75 | 76 | 75 | 76 | 80 | 55 | 50 | 55 |
| St％ | 20 | 25 | 15 | 20 | 20 | 20 | 20 | 25 |
| Bv％ | 70 | 69 | 70 | 60 | 69 | 50 | 54 | 65 |
| Ct％ | 20 | 19 | 19 | 26 | 20 | 33 | 32 | 18 |
| Cc％ | 10 | 12 | 11 | 14 | 11 | 17 | 14 | 17 |
| tanδ(0℃) | 1.012 | 1.083 | 0.9665 | 0.8141 | 0.8199 | 0.4007 | 0.4431 | 0.8350 |
| Tanδ(60 ℃) | 0.1060 | 0.1035 | 0.1096 | 0.1101 | 0.0986 | 0.1114 | 0.1082 | 0.1128 |
Annotate:
Mn (ten thousand) is basic number-average molecular weight; CE% is a coupling efficiency; St% is a styrene content; Bv% is 1, the 2-structural content; Cc% is suitable-1,4 structural content; Ct% is anti--1,4 structural content; Cure conditions:
Rubber: 200g; SULPHUR POWDER: 3.4g; Stearic acid: 4g; Anti-aging agent (N-Phenyl beta naphthylamine): 2g; Carbon black: 90g; Promotor (N-cyclohexyl-2-[4-morpholinodithio base sulphenamide): 2g; Zinc oxide: 10g; Curing time: 50 minutes; Curing temperature: 145～150 ℃.
Claims (25)
1. a method for preparing the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer 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 copolymerization of carrying out conjugated diene and monovinylarene 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 conjugated diene is a 25-95% weight based on the monomer total amount in step 1), and monovinylarene is a 5-75% weight based on the monomer total amount; Should make monomer concentration as the consumption of raffinating oil of solvent 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 that the weight ratio of lewis' base, anion surfactant and the mixture of raffinating oil and composite additive and organic lithium initiator is 1～40.
2. according to the process of claim 1 wherein that conjugated diene is a 50-90% weight based on the monomer total amount in step 1), and monovinylarene is a 10-50% weight based on the monomer total amount.
3. be 5～50g total monomer/100ml solvent according to the process of claim 1 wherein that the consumption of raffinating oil as solvent should make monomer concentration.
4. according to the process of claim 1 wherein that the weight ratio of composite additive and organic lithium initiator is 10～30.
5. according to the method for claim 1, wherein said 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 5587% weight based on the composite additive total amount.
6. according to the method for claim 5, 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.
7. according to the method for claim 5, the consumption of wherein said Lewis base is 15～25% weight based on the composite additive total amount.
8. according to the method for claim 5, 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.
9. according to the method for claim 5, wherein said consumption of raffinating oil is 65～80% weight based on the composite additive total amount.
10. according to the process of claim 1 wherein that the polymerization reaction time of step 1) is 5-30 minute.
11. according to each method among the claim 1-10, wherein said raffinating oil is that boiling range is 60～90 ℃ a platformate raffinate.
12. according to each method among the claim 1-10, 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; Described mono vinyl arenes monomer is selected from vinylbenzene, C
1-C
6The vinylbenzene that alkyl replaces, or have substituent styrene derivatives or its mixture on the vinyl.
13. according to the method for claim 12, wherein the 1,3-butadiene of Qu Daiing is 2,3-dimethyl-1,3-butadiene or 1-phenyl-1,3-butadiene, C
1-C
6The vinylbenzene that alkyl replaces be between-vinyl toluene, p-methylstyrene or right-t-butyl styrene, having substituent styrene derivatives on the vinyl is alpha-methyl styrene.
14. according to the method for claim 12, wherein said conjugated diene is that 1,3-butadiene or isoprene and described mono vinyl arenes monomer are vinylbenzene or p-methylstyrene.
15. according to the method for claim 14, wherein said conjugated diene is that 1,3-butadiene and described mono vinyl arenes monomer are vinylbenzene.
16. according to each method among the claim 1-10, wherein said organic lithium initiator is n-Butyl Lithium or s-butyl lithium.
17. according to each method among the claim 1-10, 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.
18. according to each method among the claim 1-10, wherein said terminator is water, methyl alcohol, Virahol, and the mol ratio of terminator and organic lithium initiator is 0.1～1.
19. according to each method among the claim 1-10, wherein said anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), and its consumption is 0.5～2% weight based on polymkeric substance.
20. according to each method among the claim 1-10, wherein polymeric reaction temperature is 0～150 ℃.
21. according to the method for claim 20, wherein polymeric reaction temperature is 20～110 ℃.
22. according to each method among the claim 1-10, wherein polymerization pressure is 0.1～0.8MPa.
23. according to the method for claim 22, wherein polymerization pressure is 0.1～0.4MPa.
24. one kind by the star-like soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber that obtains according to each method among the claim 1-22, it is characterized in that vinyl structure content is 60% or higher.
25. one kind based on the tire according to the star-like soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of claim 24.
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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 |
| US20150065647A1 (en) * | 2013-08-28 | 2015-03-05 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| CN106632928B (en) * | 2015-10-28 | 2019-04-19 | 中国石油化工股份有限公司 | Star-like butadiene-styrene block copolymer and its preparation method and application |
| JP7273623B2 (en) * | 2019-06-13 | 2023-05-15 | 株式会社ブリヂストン | Rubber composition and tire |
| CN113583197B (en) * | 2020-04-30 | 2024-02-13 | 中国石油化工股份有限公司 | Low-heat-generation integrated rubber and synthetic method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367325A (en) * | 1980-04-22 | 1983-01-04 | Japan Synthetic Rubber Co., Ltd. | Styrene-butadiene random copolymer and process for the production thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367325A (en) * | 1980-04-22 | 1983-01-04 | Japan Synthetic Rubber Co., Ltd. | Styrene-butadiene random copolymer and process for the production thereof |
| 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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