CN1495208A - Method for preparing conjugated diolefine/monovinyl aromatic hydrocarbon copolymer rubber by means of solution polymeriaztion - Google Patents
Method for preparing conjugated diolefine/monovinyl aromatic hydrocarbon copolymer rubber by means of solution polymeriaztion Download PDFInfo
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Abstract
The present invention relates to a method for synthesizing conjugated diolefine/mono-vinyl aromatic copolymer rubber by using organic dilithium compound as initiator through the process of solution polymerization, and relates to the product based on said copolymer rubber, for example type. The compolymer rubber obtained by said invented method has improved lagging property.
Description
Technical field
The present invention relates to a kind of novel conjugated-diolefin/uni-vinyl-arene copolymer rubber and its production and application.More particularly, the present invention relates to a kind of use organic stannic dilithium compound as initiator by the method for solution polymerization conjugated-diolefin/uni-vinyl-arene copolymer rubber, the copolymer rubber that obtains thus and based on the goods of described copolymer rubber, as tire.
Background technology
In recent years, along with the raising of people's awareness of saving energy with to the concern of tire safe capability, the requirement with glue improves constantly to tire, mainly shows under the prerequisite that guarantees anti-slippery to reduce rolling resistance as much as possible.
Tire tread glue experiment shows, a kind of effective ways that reduce the rolling resistance of solution polymerized butadiene styrene rubber and reduce its hysteresis loss are exactly to introduce to contain tin group in polymer molecule.At present general technology is to be initiator with the lithium alkylide, causes vinylbenzene in varsol, butadiene copolymer closes, obtain the random butylbenzene copolymer of line style of required microtexture after, add tin tetrachloride again and carry out coupling.But because the death of part spike takes place in polymerization process inevitably, causing the molecule of this part terminal spike death to participate in the coupling process goes, linked reaction is to betide between macromolecular chain and the small molecules coupling agent in addition, and big and curling form sterically hindered of macromolecular chain all can have influence on coupling effect owing to the viscosity of system like this.For overcoming this problem, research and propose in initiator to introduce and contain tin group, can guarantee that like this each macromole all contains at least one tin atom in the product.For example United States Patent (USP) 5,502, and 129 have introduced a kind of method of using the tributyl tin lithium as synthetic divinyl of initiator and styrol copolymer.Found that although polymer architecture is closely similar, the tributyl tin lithium causes, I-PrOH stops (65 ℃ time tan δ be 0.0938) to be caused than n-Butyl Lithium, and tributyl tin chlorine end-blocking (65 ℃ time tan δ be 0.1073) more can reduce hysteresis loss; And α, the hysteresis loss of the functionalized SBR of ω-two (tributyl tin lithium) (65 ℃ time tan δ be 0.0773) has reduced by 51.4% than tri-n-butyl tin lithium initiator products obtained therefrom.It is the method for the synthetic star-like solution polymerized butylbenzene of polyfunctional group stanniferous organic alkali metal initiator between 2.5～6.5 that the open CN 1148050A of Chinese patent application has introduced a kind of functionality of using, and found that the star-like SSBR of institute's synthetic (50 ℃ time tan δ be 0.092) is lower than the rolling resistance of Japanese tin coupling product SL-557 (50 ℃ time tan δ be 0.12).But use the disclosed initiator of this patent application can only prepare star-type polymer.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor is carrying out research extensively and profoundly by solution polymerization conjugated-diolefin/uni-vinyl-arene copolymer rubber field, found that to use a kind of special organic stannic dilithium compound can prepare the copolymer rubber of the rolling resistance with excellent wet-sliding resistant performance and reduction as initiator.The present invention just is being based on this discovery and is being accomplished.
Therefore, the purpose of this invention is to provide a kind of novel method by solution polymerization synthesis of conjugate diolefine/uni-vinyl-arene copolymer rubber, this method uses a kind of special organic stannic dilithium compound as initiator, makes the gained copolymer rubber have the excellent wet-sliding resistant performance and the rolling resistance of reduction.
Another object of the present invention provides a kind of copolymer rubber that is obtained by aforesaid method.
A further object of the present invention provides a kind of goods based on above-mentioned copolymer rubber, as tire.
One aspect of the present invention provides a kind of method by solution polymerization synthesis of conjugate diolefine/uni-vinyl-arene copolymer rubber, and this method comprises the steps:
1) adopting organic stannic dilithium compound under inert gas environment is initiator, is randomizer and structure regulator with the Lewis base, carries out the random copolymerization of conjugated diene monomer and mono vinyl arenes monomer in one or more varsols; With
2) directly stop polyreaction or use sn-containing compound that step 1) gained living polymer chains is carried out end-blocking or coupling.
The present invention provides a kind of copolymer rubber that is synthesized by aforesaid method on the other hand.
Further aspect of the present invention provides a kind of goods based on copolymer rubber of the present invention, as tire.
Implement best mode of the present invention
In conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic, operable conjugated diene monomer is meant any monomer that has conjugated double bond in its molecule, as C
4～C
6Conjugated diene monomer, its object lesson comprise divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof, more preferably divinyl and isoprene.
In conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic, operable mono vinyl arenes monomer is meant the aromatic monomer that has a vinyl substituted base on its aromatic ring, its object lesson comprises the vinylbenzene that vinylbenzene or alkyl replace, as Vinyl toluene (all isomer), alpha-methyl styrene, the 4-t-butyl styrene, the 4-vinyl toluene, 3,5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene, 4-dodecyl vinylbenzene etc., and composition thereof, preferred mono vinyl arenes monomer comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene and composition thereof, most preferably vinylbenzene.
The organic stannic dilithium compound that is used as initiator in conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic can be represented with following general formula (1):
R
2Sn (Y
a-Z
m-Y
b-Li)
2(1) wherein R is C
1～C
20Alkyl, C
3～C
20Cycloalkyl or C
6～C
20The aryl of aryl or replacement; Z is C
1～C
20Straight chain or branched bivalent hydrocarbon radical, C
6～C
20Arylidene or replacement arylidene; Y is the group that is derived from the multipolymer of conjugated dienes homopolymer, monovinylarene homopolymer or conjugated dienes and monovinylarene; M is 0 or 1; A is 06, and b is 0～6, and a+b is 0～6.
In above-mentioned general formula (1), R is preferably C
1～C
10Alkyl, C
3～C
10Cycloalkyl or C
6～C
10Aryl or substituted aryl, wherein alkyl can be methyl, ethyl, sec.-propyl, normal-butyl, sec-butyl, n-hexyl, n-octyl etc., cycloalkyl can be a cyclohexyl, aryl or substituted aryl can be phenyl, neighbour-,-or p-methylphenyl etc.; Conjugated dienes described in the definition of Y is preferably divinyl, isoprene or derivatives thereof, and described monovinylarene is preferably vinylbenzene, alpha-methyl styrene; Z is preferably straight chain or branched C
2～C
10Bivalent hydrocarbon radical, C
6～C
20Arylidene or replacement arylidene.Wherein straight chain or branched C
2～C
10Bivalent hydrocarbon radical is preferably straight chain or branched α, ω-C
2-C
10Bivalent hydrocarbon radical, α more preferably, ω-divalence butyl or α, ω-divalence amyl group; Arylidene or replace arylidene be preferably have the following formula (a) and (b), (c), (d), (e) or arylidene (f) or replace arylidene:
The preparation method of the organic stannic dilithium compound of general formula (1) is with a, b, the difference of the value of m and slightly variant.The statement of hereinafter will itemizing.
1. when a, b and m equaled 0 in the general formula (1), the compound of general formula (1) was corresponding to the compound of following general formula (1a):
R
2SnLi
2(1a) wherein R is as defined above.
Compound shown in the general formula (1a) can be by making the halogenide of following general formula (2)
R
2SnX
2????????(2)
Wherein X is the halogen that is selected from F, Cl, Br and I, preferred Cl or Br;
Direct and metallic lithium reacts in solvent and obtains.
Halogenide shown in the general formula (2) can be dibutyltin chloride, dihexyl tin chloride, dioctyl tin chloride etc., and these compounds are the commercial compound.
The metallic lithium that is used for above-mentioned reaction is preferably the lithium sand that particle diameter is 10～300 μ m.
Above-mentioned reaction is preferably carried out under rare gas element such as argon gas or nitrogen protection.
The solvent that is used for above-mentioned reaction can be ether solvent such as tetrahydrofuran (THF), dme or ether, or aromatic solvent such as benzene or toluene, wherein preferred tetrahydrofuran (THF).Except using solvent, in above-mentioned reaction, can also use varsol such as hexane or heptane as thinner, so that more effectively remove the LiX that generates in the reaction process.
Above-mentioned reaction is carried out under 0～70 ℃ temperature usually, preferred 5～35 ℃.
In above-mentioned reaction, the mol ratio of halogenide and metallic lithium is 1: 4～1: 7 shown in the general formula (2), preferred 1: 4.5～1: 6.
2. a and b equal 0 and during m=1 in the general formula (1), and the compound of general formula (1) is corresponding to the compound of following general formula (1b):
R
2Sn(ZLi)
2?????????(1b)
Wherein R and Z are as defined above.
The compound of general formula (1b) can prepare with the method that comprises the steps:
I) be prepared as follows the two-lithium compound shown in the general formula (3):
LiZLi????????????????(3)
Wherein Z such as general formula (1) definition,
Ii) in step I) add as defined above halogenide shown in the general formula (2) in the products therefrom and make it to react.
In the aforesaid method step I) in, two-lithium compound can be α shown in the general formula (3), ω-C
2-C
10The adducts of the adducts of the adducts of diolefine and single lithium compound, divinyl benzene-like compounds and single lithium compound or two (1, the 1-toluylene) compounds and single lithium compound.The disclosed two-lithium compound of prior art all can be used for the present invention, and its object lesson is the two-lithium compound shown in the following structure:
(a) Li-(CH
2)
4-Li (referring to US3,886,089)
(b) Li-(CH
2)
5-Li (referring to US3,886,089)
(referring to Friedhelm Bandermann, Hans-Dieter Speikamp and LudwigWeigel, Makromol.Chem., 1985,186,2017-2024);
(referring to Jiang Shuojian, Liu Huaibing, Zhao Zhong, elastomerics, 1992,2 (2), 33-37);
(referring to H.Uytterhoeven, M.Fontanille and P.Sigwalt, Polymer, 1981,22 (12), 1724-1728);
(referring to H.Uytterhoeven, M.Fontanille and P.Sigwalt, Polymer, 1981,22 (12), 1724-1728).
Above-mentioned reaction is equally preferably carried out under rare gas element such as argon gas or nitrogen protection.
The solvent of halide reaction can be ether solvent such as tetrahydrofuran (THF), dme or ether shown in two-lithium compound shown in the general formula (3) and the general formula (2), or varsol such as benzene, toluene, hexanaphthene, hexane, pentane, heptane or raffinate oil.These solvents can use separately or use with two or more mixture.
Above-mentioned reaction is carried out under 0～60 ℃ temperature usually, preferred 5～35 ℃.
In above-mentioned reaction, halid mol ratio is 2: 1 shown in two-lithium compound shown in the general formula (3) and the general formula (2).
3. a equals 0 in the general formula (1), b is not equal to 0 and during m=1, and the compound of general formula (1) is corresponding to the compound of general formula (1c):
R
2Sn(ZY
bLi)
2????(1c)
Wherein R, Z and b are as defined above.
The compound of general formula (1c) can prepare with the method that comprises the steps:
I) prepare two-lithium compound shown in the general formula (3) as defined above;
Ii) make two-lithium compound shown in the general formula (3) and halide reaction shown in the general formula (2) as defined above, obtain compound shown in the general formula (1b) as defined above;
Be the polymerization that initiator causes conjugated dienes monomer, mono vinyl arenes monomer or its mixture iii) with compound shown in the general formula (1b).
Halogenide preferably reacts in solvent shown in two-lithium compound shown in the general formula (3) and the general formula (2).Operable solvent for example is an ether solvent, as tetrahydrofuran (THF), dme, ether, or varsol such as benzene, toluene, hexanaphthene, hexane, pentane, heptane, raffinates oil.These solvents can use separately, and perhaps the mixture with two or more uses.
The temperature of halide reaction is preferably 0～60 ℃ shown in two-lithium compound shown in the general formula (3) and the general formula (2), more preferably 5～35 ℃.
Halid reinforced mol ratio is 2: 1 shown in two-lithium compound shown in the general formula (3) and the general formula (2).
Conjugated dienes monomer used in this method can be divinyl, isoprene or derivatives thereof; Mono vinyl arenes monomer is vinylbenzene, alpha-methyl styrene.
Above-mentioned polyreaction is preferably carried out in solvent, and described solvent can be varsol, and aromatic solvent for example as benzene, toluene, aliphatic hydrocarbon solvent such as hexanaphthene, hexane, pentane, heptane, is raffinated oil.These solvents can use separately, and perhaps the mixture with two or more uses.
Polymerization temperature is 10～60 ℃.
Step I ii) compound shown in the formula of (1b) changes with the different of designed molecular weight with monomeric usage ratio, and promptly the difference according to described b value changes.
4. m=0 and a in the general formula (1), b is not 0 o'clock simultaneously, the compound of general formula (1) is corresponding to the compound of following general formula (1d):
R
2Sn(Y
a+b-Li)
2???????(1d)
Wherein R, Y, a and b are as defined above.
The compound of general formula (1d) can prepare with the method that comprises the steps:
I) be initiator causes the mixture of conjugated dienes monomer, mono vinyl arenes monomer or conjugated dienes monomer and mono vinyl arenes monomer in varsol polymerization with the lithium aryl, obtain the low-molecular-weight oligomer that the molecular chain two ends shown in the following general formula (3 ') all have the active centre:
Li-Y
a+b-Li??????(3’)
Wherein Y, a and b are as defined above;
Ii) adding as defined above, halogenide shown in the general formula (2) makes it and step I) reaction of gained oligopolymer.
The lithium aryl initiator that can be used for this reaction is the reaction product of condensed-nuclei aromatics such as naphthalene, alpha-methyl-naphthalene, anthracene, biphenyl, trans-stilbene and metallic lithium, is best with the naphthalene lithium wherein.
The conjugated dienes monomer that can be used for this reaction is divinyl, isoprene or derivatives thereof etc.; Mono vinyl arenes monomer is vinylbenzene, alpha-methyl styrene etc.
The varsol that can be used for this method can be aromatic solvent such as benzene, toluene etc., aliphatic hydrocarbon solvent such as hexanaphthene, hexane, pentane, heptane, raffinates oil etc.These solvents can use separately or use with two or more mixture.
Polymeric reaction temperature for example is 10～60 ℃.
The lithium aryl initiator changes with the different of designed molecular weight with monomeric consumption, and promptly the difference according to described a, b value changes.
Halid mol ratio is 2: 1 shown in low-molecular-weight oligomer and the general formula shown in the general formula (3 ') (2).
5. m=1 in the general formula (1), a, b all are not 0 o'clock, the compound of general formula (1) is corresponding to the compound of following general formula (1e):
R
2Sn(Y
a-Z-Y
b-Li)
2???????(1e)
Wherein R, Z, Y, a and b are as defined above.
The compound of general formula (1e) can prepare with the method that comprises the steps:
I) prepare two-lithium compound shown in the general formula (3) as defined above,
Be the polymerization that initiator causes conjugated dienes monomer, mono vinyl arenes monomer or its mixture ii), form the low-molecular-weight oligomer that the molecular chain two ends are the active centre with compound shown in the general formula (3),
Iii) to step I i) add as defined above halogenide shown in the general formula (2) in the products therefrom and make it reaction.
Halid selection is ditto described shown in the two-lithium compound that relates in this method (3), conjugated dienes monomer, mono vinyl arenes monomer, solvent and the general formula (2).
Polymeric reaction temperature is 10～60 ℃.
Step I i) halid temperature of reaction is preferably 0～60 ℃ shown in gained oligopolymer and the general formula (2), more preferably 5～30 ℃.
Step I i) halid reinforced mol ratio is 2: 1 shown in gained oligopolymer and the general formula (2).
Compound changes with the different of designed molecular weight with monomeric usage ratio shown in the general formula (3), and promptly the difference according to described a, b value changes.
Can be about other details of organic stannic dilithium compound of the present invention and preparation thereof with reference to Chinese patent application 00135343.8 and 00138011.7, its disclosure is hereby incorporated by reference.
In conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic, operable rare gas element is commonly used those in this area, as nitrogen, argon gas, helium etc.
In conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic, with Lewis base as randomizer and structure regulator.Operable Lewis base comprises diglyme, triglyme, glycol dimethyl ether, HMPA, Tetramethyl Ethylene Diamine, tetrahydrofuran (THF), P-Dioxane, triethylamine etc.The consumption of Lewis base is counted 0.5～100 (mole) with Louis's alkali number/active lithium amount, is preferably 0.5～60 (mole).
The varsol that uses in the copolymer rubber synthetic method of the present invention can comprise hexanaphthene, pentane, hexane, heptane, raffinate oil and benzene etc.These solvents can use separately or use with two or more mixture.The consumption of solvent should make monomer concentration be controlled at 5～20% (weight), is preferably 8～15% (weight).
In the method for synthetic copolymer rubber of the present invention, the temperature of reaction and the pressure of the polyreaction in the first step there is not special restriction, can use the temperature and pressure of conventional conjugated diene-monovinylarene anionoid polymerization.For example, polymerization can be preferably 50～150 ℃ temperature and 0.05～0.5MPa at 0～200 ℃, carries out preferred 0.5～3 hour under the pressure of preferred 0.1～0.3MPa 0.2～5 hour.
In conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention synthetic, can use terminator directly to stop polyreaction after the polyreaction of the first step is finished or carry out end-blocking or coupling.The terminator that is used to stop polyreaction can be an anionoid polymerization field terminator commonly used, as lower alcohol, and for example methyl alcohol, ethanol, Virahol etc.Being used for end-blocking or link coupled reagent can be anionoid polymerization field sn-containing compound commonly used, as be used for end capped trialkyltin chlorine, wherein alkyl contains 1-8 carbon atom, concrete as tin trimethyl chlorine, triethyltin chlorine, tributyl tin chlorine etc., and be used for link coupled tin protochloride, tin tetrachloride and dialkyl group tin dihalide (wherein alkyl contain 1-8 carbon atom and halogen is preferably chlorine, bromine etc.) etc.When adopting sn-containing compound to carry out end-blocking as end-capping reagent, the consumption of end-capping reagent is counted 0.7～1.1 (mole) with end-blocking dosage/active lithium amount, is preferably 0.8～1 (mole); When adopting sn-containing compound to carry out coupling as coupling agent, the consumption of coupling agent is counted 0.08～0.2 (mole) with coupling dosage/active lithium amount, is preferably 0.1～0.15 (mol ratio).
Do not carrying out under the link coupled situation, having following feature by above-mentioned processing step synthetic conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention:
(1) the unit content that is derived from mono vinyl arenes monomer is 5～30% (weight), is preferably 15～25% (weight);
(2) vinyl structure content is 20～60% (weight) in the polymkeric substance, is preferably 30～50% (weight);
(3) molecular weight is 20～400,000, is preferably 25～350,000; With
(4) the molecular weight distribution coefficient is 1.06-1.2.
Yet, when using coupling agent to carry out coupling, the base molecule amount of polymkeric substance must be controlled at 8～160,000, in preferred 10～140,000 the scope.Can make the gained copolymer rubber have following feature like this:
(1) the unit content that is derived from mono vinyl arenes monomer is 530% (weight), is preferably 15～25% (weight);
(2) vinyl structure content is 20～60% (weight) in the polymkeric substance, is preferably 30～50% (weight);
(3) molecular weight is 20～400,000, is preferably 25～350,000; With
(4) the molecular weight distribution coefficient is 2.0-2.8.
Mono vinyl arenes monomer unit content, vinyl structure content adopt determination of infrared spectroscopy in the polymkeric substance, and the mensuration of molecular weight and molecular weight distribution adopts gel permeation chromatograph (GPC).
Copolymer rubber by synthetic method preparation of the present invention can be used to prepare various rubber items, especially tire.
Compared with prior art, the present invention has following effect:
(1) because synthetic method of the present invention has adopted the stanniferous dilithium initiator, make the base molecule amount distribution of copolymer rubber can be controlled between 1.06～1.2, owing to contain tin atom in the initiator, make the hysteresis resistance of copolymer rubber reduce to some extent simultaneously;
(2) adopt sn-containing compound to carry out end-blocking as end-capping reagent to polymerisate, can further introduce tin atom in polymer molecular chain, tin content is higher than with single lithium or the initiation of two lithium and with the prepared superpolymer of sn-containing compound end-blocking in the molecular chain;
(3) adopt sn-containing compound to carry out coupling to polymerisate, both can increase the tin content of polymkeric substance, can obtain the product of molecular weight distribution broad simultaneously again as coupling agent; With
(4) compare with using prior art synthetic SSBR, the resulting SSBR of the present invention has the excellent wet-sliding resistant performance and the rolling resistance of reduction.
Embodiment
Following examples are used to illustrate the present invention, and never should regard limitation of the present invention as.
Reference example: the preparation of organic stannic dilithium compound
In the there-necked flask of 250ml, the pump drainage applying argon gas adds the two-lithium compound Li (CH for preparing
2)
4The diethyl ether solution 20ml of Li drips (CH
3(CH
2)
7)
2SnCl
2Tetrahydrofuran solution 15ml, two-lithium compound Li (CH wherein
2)
4Li and (CH
3(CH
2)
7)
2SnCl
2Mol ratio be 2: 1,10 ℃ of following reaction stopped reaction after 2 hours.Adopt two titration measuring active lithium concentration, the result is that 0.530M and functionality are 1.86.
The universal program of preparation copolymer rubber:
In the reactor of nitrogen replacement, the varsol that adds load weighted conjugated diene monomer-mono vinyl arenes monomer, its amount makes monomer concentration be controlled at 5～20% (weight), add the organic dilithium initiator of stanniferous according to the design basis molecular weight, temperature of reaction is 0～200 ℃, and reaction pressure is 0.05～0.5MPa; The amount of Lewis base is: Louis's alkali number/active lithium amount=0.5～100 (mol ratio); Reaction times is 0.2～5 hour.When adopting sn-containing compound to carry out end-blocking as end-capping reagent, the amount of end-capping reagent is: end-blocking dosage/active lithium amount=0.7～1.1 (mol ratio); When adopting sn-containing compound to carry out coupling as coupling agent, the amount of coupling agent is: coupling dosage/active lithium amount=0.08～0.2 (mol ratio).After reaction finishes, through devaporation, to copolymer rubber.Polymerisate is carried out mixing, sizing compound formula such as table 1 are measured the polymer properties parameter then.
Table 1 sizing compound formula
| Project | Weight fraction |
| ????SSBR | ????100 |
| ????ZnO | ????5 |
| ????S | ????1.7 |
| Stearic acid | ????2 |
| High wear-resistant carbon black | ????45 |
| Accelerant CZ | ????1 |
| Process oil | ????5 |
Embodiment 1
Vacuumize, 5 liters of stainless steel cauldrons of inflated with nitrogen pump drainage add the tetrahydrofuran (THF) of hexanaphthene 2700g, the vinylbenzene 100g refine, divinyl 300g, amount as shown in table 2 then therein, add (the CH that measures according to the design molecular weight then
3(CH
2)
7)
2Sn ((CH
2)
4Li)
2(prepared) 1.72mmol as reference example.Under 50 ℃ and 0.1MPa, cause and carried out polyreaction 2 hours, take to add 2ml methyl alcohol after reaction finishes and stop (directly cohesion) and adding 3.2mmol tributyl tin chlorine and carry out two kinds of methods of end-blocking and obtain polymerisate.The performance perameter of polymerisate sees Table 2.
Table 2
| Numbering | ????1 | ????2 | ????3 | ????4 |
| Tetrahydrofuran (THF) add-on/active lithium add-on (mol ratio) | ????30 | ????38 | ||
| The termination mode | Directly cohesion | Tributyl tin chlorine end-blocking | Directly cohesion | Tributyl tin chlorine end-blocking |
| Design molecular weight (ten thousand) | ????25 | ????25 | ????25 | ????25 |
| Molecular weight distributing index | ????1.15 | ????1.11 | ????1.1 | ????1.09 |
| Contents of ethylene % | ????33.2 | ????33.7 | ????37.5 | ????37.1 |
| Tanδ?0℃ | ????0.182 | ????0.199 | ????0.196 | ????0.228 |
| Tanδ?50℃ | ????0.116 | ????0.106 | ????0.121 | ????0.107 |
Embodiment 2
Vacuumize, 5 liters of stainless steel cauldrons of inflated with nitrogen pump drainage add hexanaphthene 2700g, vinylbenzene 100g, the divinyl 300g that refines then therein, add (the CH that measures according to the design molecular weight then
3(CH
2)
7)
2Sn ((CH
2)
4Li)
2(as preparation as described in the reference example) and THF cause under 50 ℃ and 0.1MPa and carried out polyreaction 2 hours.Take to add 2ml methyl alcohol after reaction finishes and stop (directly cohesion) and adding tributyl tin chlorine and carry out two kinds of methods of end-blocking and obtain polymerisate, the performance perameter of polymerisate sees Table 3.
Table 3
| Numbering | ??5 | ??6 | ??7 | ??8 | ??9 | ????10 |
| The termination mode | Directly cohesion | Tributyl tin chlorine end-blocking | Directly cohesion | Tributyl tin chlorine end-blocking | Directly cohesion | Tributyl tin chlorine end-blocking |
| Design molecular weight (ten thousand) | ??25 | ????25 | ??30 | ????30 | ??35 | ????35 |
| Initiator amount (mmol) | ??1.72 | ????1.72 | ??1.43 | ????1.43 | ??1.23 | ????1.23 |
| ??THF(mmol) | ??102 | ????102 | ??85.8 | ????85.8 | ??73.8 | ????73.8 |
| Tributyl tin chlorine consumption (mmol) | ??- | ????3.2 | ??- | ????2.66 | ??- | ????2.28 |
| Molecular weight distributing index | ??1.12 | ????1.09 | ??1.13 | ????1.11 | ??1.11 | ????1.1 |
| Contents of ethylene % | ??33.2 | ????33.7 | ??33.2 | ????33.7 | ??32.7 | ????33.4 |
| ??Tanδ?0℃ | ??0.184 | ????0.186 | ??0.192 | ????0.187 | ??0.194 | ????0.201 |
| ??Tanδ?50℃ | ??0.114 | ????0.087 | ??0.120 | ????0.089 | ??0.119 | ????0.093 |
Embodiment 3
In purifying 5 liters of good stainless steel cauldrons, add the hexanaphthene 2700g that refines, add vinylbenzene then, divinyl, add-on is as shown in table 4, adds (the CH that measures according to the design molecular weight
3(CH
2)
7)
2Sn ((CH
2)
4Li)
2(as preparation as described in the reference example) 1.43mmol and tetrahydrofuran (THF) 85.8mmol causes under 50 ℃ and 0.1MPa and carried out polyreaction 2 hours.Take to add 2ml methyl alcohol after reaction finishes and stop (directly cohesion) and adding 2.66mmol tributyl tin chlorine and carry out two kinds of methods of end-blocking and obtain polymerisate, the performance perameter of polymerisate sees Table 4.
Table 4
| Numbering | ??11 | ????12 | ????13 | ????14 |
| Vinylbenzene add-on (g) | ??60 | ????80 | ||
| Divinyl add-on (g) | ??340 | ????320 | ||
| The termination mode | Directly cohesion | Tributyl tin chlorine end-blocking | Directly cohesion | Tributyl tin chlorine end-blocking |
| Design molecular weight (ten thousand) | ??30 | ????30 | ????30 | ????30 |
| Molecular weight distributing index | ??1.14 | ????1.12 | ????1.15 | ????1.1 |
| Contents of ethylene % | ??32.7 | ????33.1 | ????33.5 | ????33.3 |
| ????Tanδ?0℃ | ??0.177 | ????0.198 | ????0.191 | ????0.212 |
| ????Tanδ?50℃ | ??0.103 | ????0.091 | ????0.106 | ????0.098 |
Embodiment 4
In purifying 5 liters of good stainless steel cauldrons, add hexanaphthene 2700g, vinylbenzene 100g, the divinyl 300g that refines, add (the CH that measures according to the design molecular weight then
3(CH
2)
7)
2Sn ((CH
2)
4Li)
23.91mmol (as preparation as described in the reference example) and tetrahydrofuran (THF) 274mmol cause under 50 ℃ and 0.1MPa and carried out polyreaction 2 hours.Reaction finishes the back and uses the tin protochloride coupling, obtains polymerisate.The add-on of tin protochloride is as shown in table 5, and the performance perameter of polymerisate sees Table 5.
Table 5
| Numbering | ????15 | ????16 | ????17 |
| Tin protochloride add-on (mmol) | ????0.727 | ????0.80 | ????0.872 |
| Design molecular weight (ten thousand) | ????11 | ????11 | ????11 |
| Molecular weight distributing index | ????2.3 | ????2.4 | ????2.6 |
| Contents of ethylene % | ????35.3 | ????34.8 | ????34.1 |
| ??Tanδ?0℃ | ????0.226 | ????0.232 | ????0.241 |
| ??Tanδ?50℃ | ????0.083 | ????0.081 | ????0.091 |
Claims (12)
1. the method by solution polymerization synthesis of conjugate diolefine/uni-vinyl-arene copolymer rubber is characterized in that this method comprises the steps:
1) adopting organic stannic dilithium compound under inert gas environment is initiator, is randomizer and structure regulator with the Lewis base, carries out the random copolymerization of conjugated diene monomer and mono vinyl arenes monomer in one or more varsols; With
2) directly stop polyreaction or use sn-containing compound that step 1) gained living polymer chains is carried out end-blocking or coupling.
2. according to the process of claim 1 wherein that organic stannic dilithium compound is shown in following general formula (1):
R
2Sn (Y
a-Z
m-Y
b-Li)
2(1) wherein R is C
1～C
20Alkyl, C
3～C
20Cycloalkyl or C
6～C
20The aryl of aryl or replacement; Z is C
1～C
20Straight chain or branched bivalent hydrocarbon radical, C
6～C
20Arylidene or replacement arylidene; Y is the group that is derived from the multipolymer of conjugated dienes homopolymer, monovinylarene homopolymer or conjugated dienes and monovinylarene; M is 0 or 1; A is 0～6, and b is 0～6, and a+b is 0～6.
3. according to the method for claim 1, it is characterized in that described Lewis base comprises diglyme, triglyme, glycol dimethyl ether, HMPA, Tetramethyl Ethylene Diamine, tetrahydrofuran (THF), P-Dioxane, triethylamine, and its consumption is counted 0.5～100 (mole) with Louis's alkali number/active lithium amount, is preferably 0.5～60 (mole).
4. according to the method for claim 1, it is characterized in that described varsol comprises hexanaphthene, pentane, hexane, heptane, raffinates oil and benzene, and the consumption of described solvent makes monomer concentration be controlled at 5～20% (weight), be preferably 8～15% (weight).
5. according to the method for claim 1, it is characterized in that after the polyreaction of the first step is finished, using the terminator that is selected from methyl alcohol, ethanol and Virahol directly to stop.
6. according to the method for claim 1, it is characterized in that after the polyreaction of the first step is finished, using sn-containing compound to carry out end-blocking as end-capping reagent.
7. according to the method for claim 1, it is characterized in that using sn-containing compound after the polyreaction of the first step is finished is 8～160,000 as the base molecule amount that coupling agent carries out coupling and coupling prepolymer, preferred 10～140,000.
8. according to the method for claim 6, it is characterized in that end-capping reagent is that the consumption of tributyl tin chlorine and tributyl tin chlorine is counted 0.7～1.1 (mole) with the amount/active lithium amount of tributyl tin chlorine, is preferably 0.8～1 (mole).
9. according to the method for claim 7, it is characterized in that coupling agent is that the consumption of tin protochloride and tin protochloride is counted 0.08～0.2 (mole) with the amount/active lithium amount of tin protochloride, is preferably 0.1～0.15 (mol ratio).
10. conjugated-diolefin/uni-vinyl-arene copolymer rubber that can be obtained by the method for claim 5 or 6 has following feature:
(1) the unit content that is derived from mono vinyl arenes monomer is 5～30% (weight), is preferably 15～25% (weight);
(2) vinyl structure content is 20～60% (weight) in the polymkeric substance, is preferably 30～50% (weight);
(3) molecular weight is 20～400,000, is preferably 25～350,000; With
(4) the molecular weight distribution coefficient is 1.06～1.2.
11. the conjugated-diolefin/uni-vinyl-arene copolymer rubber that can be obtained by the method for claim 7 has following feature:
(1) the unit content that is derived from mono vinyl arenes monomer is 5～30% (weight), is preferably 15～25% (weight);
(2) vinyl structure content is 20～60% (weight) in the polymkeric substance, is preferably 30～50% (weight);
(3) molecular weight is 20～400,000, is preferably 25～350,000; With
(4) the molecular weight distribution coefficient is 2.0-2.8.
12. one kind based on the tire according to the conjugated-diolefin/uni-vinyl-arene copolymer rubber of claim 11 or 12.
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| CN 03142830 CN1216086C (en) | 2002-06-13 | 2003-06-13 | Method for preparing conjugated diolefine/monovinyl aromatic hydrocarbon copolymer rubber by means of solution polymeriaztion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255223B (en) * | 2007-02-28 | 2010-12-01 | 中国石油化工股份有限公司 | Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof |
| CN110325560A (en) * | 2017-02-17 | 2019-10-11 | 株式会社普利司通 | Conjugated diene polymer, rubber composition, crosslinking rubber, rubber product and tire |
-
2003
- 2003-06-13 CN CN 03142830 patent/CN1216086C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255223B (en) * | 2007-02-28 | 2010-12-01 | 中国石油化工股份有限公司 | Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof |
| CN110325560A (en) * | 2017-02-17 | 2019-10-11 | 株式会社普利司通 | Conjugated diene polymer, rubber composition, crosslinking rubber, rubber product and tire |
| US11286375B2 (en) | 2017-02-17 | 2022-03-29 | Bridgestone Cornoration | Conjugated diene polymer, rubber composition, crosslinked rubber, rubber product, and tire |
| CN110325560B (en) * | 2017-02-17 | 2022-11-01 | 株式会社普利司通 | Conjugated diene polymer, rubber composition, crosslinked rubber, rubber product, and tire |
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| CN1216086C (en) | 2005-08-24 |
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