CN103159868B - The conjugated diene rubber of polar silicone modification, its method for making and the composition containing it - Google Patents
The conjugated diene rubber of polar silicone modification, its method for making and the composition containing it Download PDFInfo
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- CN103159868B CN103159868B CN201210228540.6A CN201210228540A CN103159868B CN 103159868 B CN103159868 B CN 103159868B CN 201210228540 A CN201210228540 A CN 201210228540A CN 103159868 B CN103159868 B CN 103159868B
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Abstract
The present invention discloses a kind of modified conjugated diene rubber, and its method for making comprises the conjugated diene rubber providing alkali metal containing ion; And by the conjugated diene rubber of this alkali metal containing ion and siloxane reactions, to generate this modified conjugated diene rubber, the structural formula of this siloxanes is as follows, wherein, R
1, R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms; And R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
Description
Technical field
The present invention relates to a kind of conjugated diene rubber, particularly with silicone-modified conjugated diene rubber.
Background technology
Solution styrene butadiene rubber (solutionstyrenebutadienerubber, SSBR) is made up of divinyl and styrene units.First propose batch preparation method and Firestone company proposition continuous preparation method by Phillips company of the U.S., and take the lead in realizing suitability for industrialized production.Because solution styrene butadiene rubber has the mechanical property more excellent than emulsion styren-butadiene rubber (emulsionstyrenebutadienerubber, ESBR) and rolling resistance, thus automotive industry and other rubber item more can be widely used in.
Along with recent automobile reduces the requirement of oil consumption, the property requirements of the elastomeric material for tire is also increased thereupon.Conjugated diene rubber has low rolling impedance, excellent abrasion impedance, and produces more excellent control stability because of anti-slippery, and its demand property is increased.On the other hand, industry (this area) is also set forth in the rubber combination of tire and adds silicon-dioxide (silicacompound) or silicon-dioxide and carbon black (carbonblack) using as strengthening agent.The tire tread of the mixture containing silicon-dioxide or silicon-dioxide and carbon black has low rolling impedance and by anti-slippery and more excellent control stability that is that produce.
In order to make conjugated diene rubber better can be combined with strengthening agent, industry has produced many technology of conjugated diene rubber being carried out to modification.US Patent No. 4,185,042 discloses a kind of coupler for SBS block copolymer, will containing the polymkeric substance of lithium with react containing silicon coupling agent, the coupling rate >90% of the polymkeric substance obtained and being present in polymkeric substance without Si-OR base.US Patent No. 5,219,938 steps disclosing a kind of two benches modification, by using two kinds of properties-correcting agent, first will containing the diene polymer chain end of lighium polymer and coupler R
nsiCl
4-nor R
nsnCl
4-nreaction, then again with coupler (R
5r
6r
7-Si-(CH
2)
n-N-R
8r
9) reaction modifying.US Patent No. 7,288,594 disclose and carry out two benches modification with two kinds of different silane compounds to the styrene-butadiene rubber(SBR) containing lithium.In addition, US Patent No. 7,807,747 disclose and carry out two benches modification with identical silane compound to containing the styrene-butadiene rubber(SBR) of lithium.
But the most difficulty of preparation method of the modified conjugated diene rubber synthesized by above-mentioned prior art is complicated and not easily implement, so the problem that industry still needs novel conjugated diene rubber modification technology to produce to solve prior art.
Summary of the invention
The present invention discloses a kind of with the manufacture method of silicone-modified conjugated diene rubber, the modified conjugated diene rubber made by it and the composition containing this modified conjugated diene rubber.
According to an embodiment, the invention provides a kind of manufacture method of modified conjugated diene rubber, comprise step (a): the conjugated diene rubber that alkali metal containing ion is provided; And step (b): by the conjugated diene rubber of this alkali metal containing ion and siloxane reactions, to generate this modified conjugated diene rubber, the structural formula of this siloxanes is as follows:
R
1, R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group.This C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and be preferably the ethers group of following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12.This C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms, and be preferably the imine group (iminegroup) of following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11.R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
According to an embodiment, the invention provides a kind of modified conjugated diene rubber, its structural formula is as follows:
Wherein, D is the polymkeric substance be made up of conjugate diene monomer or conjugate diene monomer and vinyl aromatic monomers; R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group.This C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and be preferably the ethers group of following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12.This C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms, and be preferably the imine group (iminegroup) of following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11.R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
The present invention also comprises other each side and various embodiment, is disclosed in detail in following embodiment to solve other problem and to merge above-mentioned each side.
Embodiment
For making the present invention and the claim that will advocate thereof be more fully understood, the preferred embodiments of the present invention of below demonstrating.For avoiding fuzzy content of the present invention, below illustrating and may omit known assembly, associated materials and correlation processing technique thereof.The following stated is only the preferred embodiments of the present invention, and is not used to limit the scope of the invention; All equivalent changes that other completes when not departing from disclosed spirit or modification, all should comprise within the scope of the appended claims.
Polyreaction: the conjugated diene rubber forming alkali metal containing ion
The manufacture method of the conjugated diene rubber of formation alkali metal containing ion of the present invention is included in suitable solvent, utilize anionic polymerization, make using organic alkali metal compound as initiator conjugate diene monomer or conjugate diene monomer and vinyl aromatic monomers polymerization with the conjugated diene rubber forming alkali metal containing ion.
Polymkeric substance of the present invention can be conjugate diene monomer polymkeric substance, or is the multipolymer of conjugate diene monomer (such as divinyl (butadiene) or isoprene (isoprene)) and vinyl aromatic monomers (such as vinylbenzene (styrene) or vinyl toluene (methylstyrene)).The polymerization single polymerization monomer of conjugated diene rubber of the present invention is not limited in divinyl, isoprene and vinylbenzene, and any suitable derivative of above-mentioned substance all can be used for the present invention.For example, conjugate diene monomer is independently selected from following items: 1,3-divinyl (1,3-butadiene), 2,3-dimethyl-1,3-divinyl (2,3-dimethyl-1,3-butadiene), 3-butyl-1,3-octadiene (3-butyl-1,3-octadiene), isoprene (isoprene), 1-dimethyl butadiene (1-methylbutadiene), 2-phenyl-1,3-butadiene (2-phenyl-1,3-butadiene) and above-mentioned every any combination.Vinyl aromatic monomers can independently selected from following items: vinylbenzene (styrene), vinyl toluene (methylstyrene) and all isomers thereof, ethyl styrene (ethylstyrene) and all isomers thereof, cyclohexylstyrenes (cyclohexylstyrene), vinyl biphenyl (vinylbiphenyl), 1-vinyl-5-hexyl naphthalene (1-vinyl-5-hexylnaphthalene), vinyl naphthalene (vinylnaphthalene), vinyl anthracene (vinylanthracene), and above-mentioned every any combination.
When being polymerized, using organolithium compound to be preferably select as initiator, therefore can obtain it has carbon lithium ion alkalimetal ion conjugated diene rubber at molecule chain end.The object lesson of organic lithium initiator comprises n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium etc., is preferably n-Butyl Lithium.
Be suitable for the solvent such as inert organic solvents of polyreaction, it means the solvent that can not participate in the polymerization reacting, this kind solvent comprises picture normal butane, Trimethylmethane, Skellysolve A, iso-pentane, 2, the aliphatic hydrocarbon of 2,4-trimethylpentane, isohexane, normal hexane, isoheptane, normal heptane, octane-iso, octane; Or cycloparaffin series's compound of picture hexanaphthene, methylcyclohexane, ethylcyclohexane, pentamethylene, suberane, methylcyclopentane; Or the arene compounds such as benzene,toluene,xylene, ethylbenzene, diethylbenzene and propyl benzene, being applicable to preferred solvent of the present invention is hexanaphthene.The polymeric solution weight concentration of conjugated diene rubber is generally 5% to 35%, is preferably 10% to 30%.In the ordinary course of things, use inert organic solvents as solvent if simple, the rate of polymerization of vinyl aromatic monomers or conjugate diene monomer is comparatively slow and both polyreaction sex differernce is quite large, and the mode now by adding polar solvent overcomes.The object lesson being applicable to polar solvent of the present invention comprises ether compound, the Tetramethyl Ethylene Diamines such as tetrahydrofuran (THF), diethyl ether, ring amyl ether, dipropyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, glycol ether, dme, methyl ethyl ether, is preferably tetrahydrofuran (THF) and diethyl ether.
The starting temperature of polymerization can be 10 DEG C to 80 DEG C, and outlet temperature can be 30 DEG C to 150 DEG C, and method for temperature manipulation can use adiabatic reaction mode, also can adopt thermostatic control, or adopts the part type of cooling.
In polymkeric substance of the present invention, the weight ratio of conjugate diene monomer/vinyl aromatic monomers is 100/0 to 50/50, is preferably 95/5 to 55/45, is more preferably 85/15 to 60/40.
According to various embodiments of the present invention, after being polymerized but the initial number average molecular weight (Mi) of the polymkeric substance not yet reacted with properties-correcting agent is 80kg/mol ~ 2000kg/mol, be preferably 100kg/mol ~ 1500kg/mol, be more preferably 150kg/mol ~ 1000kg/mol.The mensuration of number-average molecular weight uses gel permeation chromatograph (gelpermeationchromatography; GPC) carry out, this is the practices well of those skilled in the art.
Modified-reaction: the conjugated diene rubber of alkali metal containing ion and siloxane reactions
The properties-correcting agent that modified-reaction of the present invention uses is siloxanes, and its structural formula is as follows:
R
1, R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, wherein this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes be close to its carbon atom, and this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes be close to its nitrogen-atoms; R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
In the various embodiments of the invention, R
1, R
2, R
3the C of indication
2~ C
12oxy radical be preferably C
2~ C
12ethers (ether) group, R
1, R
2, R
3can be identical or not identical oxy radical.The preferred embodiment of ethers group can following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12.C
2~ C
12the preferred embodiment such as diformazan ether (CH of oxy radical
3-O-CH
2-), the first and second ether (CH
3-O-CH
2-CH
2-), metopryl base (CH
3-O-CH
2-CH
2-CH
2-), first n-butyl ether base (CH
3-O-CH
2-CH
2-CH
2-CH
2-), the tertiary butyl ether base of first (CH
3-O-C (CH
3)
2cH
2-), first n-hexyl ether base (CH
3-O-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-), diethyl ether (CH
3-CH
2-O-CH
2-CH
2-), B ether base (CH
3-CH
2-O-CH
2-), ethylene-propylene ether base (CH
3-CH
2-O-CH
2-CH
2-CH
2-), second n-butyl ether base (CH
3-CH
2-O-CH
2-CH
2-CH
2-CH
2-), the tertiary butyl ether base of second (CH
3-CH
2-O-C (CH
3)
2cH
2-), second n-hexyl ether base (CH
3-CH
2-O-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-), first 2-ethylhexyl ether (CH
3-O-C
4h
8-CH (C
2h
5)-CH
2-), second 2-ethylhexyl ether (C
2h
5-O-C
4h
8-CH (C
2h
5)-CH
2-), wherein with-CH
2-CH
2-O-CH
3(the first and second ethers) is particularly preferred selection.
In the various embodiments of the invention, R
1, R
2, R
3the C of indication
1~ C
12nitrogen-containing group be preferably C
1~ C
12imido grpup (iminegroup), wherein R
1, R
2, R
3can be identical or not identical nitrogen-containing group.The preferred embodiment of imido grpup can use following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11.Preferred embodiment such as Ketene dimethyl the imido grpup ((CH of the imido grpup of nitrogen-containing group
3)
2c=N-), diethyl ketone imido grpup ((CH
3cH
2)
2c=N-), two acetone imine base ((CH
3cH
2cH
2)
2c=N-), two positive butanone imido grpup ((CH
3cH
2cH
2cH
2)
2c=N-), two tertiary butanone imido grpup ((CH
3)
3c)
2c=N-), methylethylketone imido grpup (CH
3(CH
3cH
2) C=N-), methyl propyl ketone imido grpup (CH
3(CH
3cH
2cH
2) C=N-), the positive butanone imido grpup of first (CH
3(CH
3cH
2cH
2cH
2) C=N-), the tertiary butanone imido grpup of first (CH
3((CH
3)
3c) C=N-), second acetone imine base ((CH
3cH
2) (CH
3cH
2cH
2) C=N-), the positive butanone imido grpup of second ((CH
3cH
2) (CH
3cH
2cH
2cH
2) C=N-), the tertiary butanone imido grpup of second ((CH
3cH
2) ((CH
3)
3c) C=N-), formaldehyde imido grpup ((CH
3) CH=N-), acetaldehyde imido grpup ((C
2h
5) CH=N-), propionic aldehyde imido grpup ((CH
3cH
2cH
2) CH=N-), two positive butanone imido grpup ((CH
3cH
2cH
2cH
2) (CH
3cH
2cH
2cH
2) C=N-), two tertiary butanone imido grpup (((CH
3)
3c) ((CH
3)
3c) C=N-), wherein with methylethylketone imido grpup (-N=C (CH
2cH
3) CH
3) be particularly preferred selection.
In the various embodiments of the invention, R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group, the example has methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, hexyl, 2-ethylhexyl, vinyl (vinyl), 1-propenyl, 1-butylene base, 1-hexenyl, phenyl, tolyl, ethylbenzene, xylyl, propyl phenyl, first alkoxyl group, second alkoxyl group, the third alkoxyl group, normal butane oxygen base, isobutyl alkoxyl group, wherein with-CH=CH
2(vinyl) is preferred selection.
When modified-reaction carries out, properties-correcting agent siloxanes is combined with the diene chain end of the conjugated diene rubber of alkali metal containing ion.The mol ratio of the conjugated diene rubber of properties-correcting agent siloxanes and alkali metal containing ion is >=0.5, is preferably >=0.6, be more preferably >=0.7, but must lower than 10.
Conjugated diene rubber through above-mentioned modified-reaction is directly removed solvent and does not contact with water, and the mooney viscosity (MooneyViscosity) of this modified conjugated diene rubber is 10 to 150, is preferably 15 to 130.
Modified conjugated diene rubber
The modified conjugated diene rubber with following structure can be formed after above-mentioned modified-reaction:
Wherein, D is the polymkeric substance be made up of conjugate diene monomer or conjugate diene monomer and vinyl aromatic monomers; R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, wherein this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms; And R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.In the preferred embodiment, C
2~ C
12oxy radical be the ethers group of following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12, is especially wherein-CH with oxy radical
2cH
2oCH
3for particularly preferred.In the preferred case, C
1~ C
12nitrogen-containing group be the imine group of following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11 is especially wherein-N=C (CH with nitrogen-containing group
2cH
3) CH
3for particularly preferred.Relevant D, R
2, R
3and R
4specific examples can see be above set forth in polymerization and modified-reaction in explanation.
Water contact reacts
Another aspect of the invention is and modified conjugated diene rubber is contacted with a large amount of water, to improve the stability of its mooney viscosity further.The contact method of modified conjugated diene rubber and water comprises steam stripped (steamstripping) method or other suitable method.For steam stripped, the modified conjugated diene rubber solutions containing solvent can be made to contact with water, temperature controls below 150 DEG C, wherein in the water yield and modified conjugated diene rubber solutions, solvent-laden weight ratio is more than 0.1, be more preferably more than 0.5, most preferably be more than 1, and pH can be made to be 4 ~ 10.Temperature during both contacts can be 20 to 150 DEG C, is more preferably 30 to 140 DEG C, most preferably is 40 to 130 DEG C, and both times of contact are 5 minutes to 10 hours, more preferably 10 minutes to 8 hours, most preferably 30 minutes to 6 hours.While modified conjugated diene rubber solutions contacts with water or steam, electric heating, warm air or other thermal source desolvation can be utilized afterwards, drying mode such as mechanical dehydration, oven drying or the process of curtain drying (aprondryer) mode again through knowing, or such as rubber is carried out at 110 DEG C hot-rolling (hotroll) drying.The coupling rate that conjugated diene rubber is recording after above-mentioned water contact pairs through modification of the present invention is 10% ~ 95%, is preferably 20 ~ 80%, is more preferably 25 ~ 75%, most preferably is 30 ~ 70%.
Through above-mentioned water contact pairs and the mooney viscosity of desolvation and dried modified conjugated diene rubber is 15 to 150, be preferably 25 to 120, be more preferably 30 to 100.
Conjugated diene rubber composition
Modified conjugated diene rubber of the present invention forms conjugated diene rubber composition by mixing with other rubber constituent.The object lesson of other rubber constituent comprises conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene isoprene copolymer rubber and isoprene-isobutylene rubber.Object lesson also comprises natural rubber, ethylene-propylene copolymer rubber and ethylene-octene copolymer rubber.Above-mentioned composition can two or more forms mixing application.Composition containing the conjugated diene rubber composition of modified conjugated diene rubber can be, and when the total amount of whole rubber constituent is 100 weight part, the content of modified conjugated diene rubber is preferably at least 10 weight parts, and is more preferably at least 20 weight parts.
Moreover conjugated diene rubber composition of the present invention also can contain additive.The object lesson of additive comprises vulcanizing agent such as sulphur; Vulcanization accelerator is such as based on (thiazole-based) vulcanization accelerator of thiazole, (thiuram-based) vulcanization accelerator based on thiuram or (sulfenamide-based) vulcanization accelerator based on sulphenamide; Vulcanization activator, such as stearic acid or zinc oxide; Organo-peroxide; Strengthening agent such as silicon-dioxide or carbon black; Weighting agent such as calcium carbonate or talcum; Silane coupling agent; Extending oil; Processing aid; Antioxidant; And lubricant etc.
Being mixed in the example of conjugated diene rubber composition of the present invention using silicon-dioxide as strengthening agent, when the total amount of whole rubber constituent is 100 weight part, the content of silicon-dioxide is generally 10 weight part to 200 weight parts.From the viewpoint of fuel-efficient, mixed amount is preferably at least 20 weight parts, and is more preferably at least 30 weight parts.From the viewpoint of reinforcing effect, preferably no more than 180 weight parts, and more preferably less than 150 weight parts.Silicon-dioxide can be amorphousness synthetic silica, such as, obtained by acidifying (acidification) soluble silicate (such as water glass or silicate and the coprecipitated of aluminate are analysed (co-precipitation)).Generally speaking, this type of precipitating silicon-dioxide is well known to those skilled in the art.The BET specific surface area of synthetic silica (precipitating silicon-dioxide), with radon survey, can be such as about 50 to about 300 square centimeters/g (meters squared per gram), can select about 100 to about 250 square centimeters/g in addition.Silicon-dioxide also can have dibutyl phthalate (dibutylphthalate, DBP) absorption value, and such as scope is about 100cc/g (cm
3/ g) to about 500cc/g, preferable range is about 120cc/g to about 350cc/g.The commercially available synthetic silica of other various business can be considered to be used in the present invention, includes but not limited to the commercially available silicon-dioxide of business such as provided by PPGIndustries, such as trade mark Hi-Siltrademark model 210,243 etc.; The commercially available silicon-dioxide of the business provided by Rhodia company, such as marque Zeosil1165MP and Zeosil165GR; The commercially available silicon-dioxide of the business provided by EVONIK company, such as marque VN2, VN3,7000GR, 9000GR; And the commercially available silicon-dioxide of business to be provided by Huber, such as marque Zeopol8745.
Be mixed in the example of conjugated diene rubber composition of the present invention using non-silicon-dioxide as strengthening agent, from the viewpoint of reinforcing effect, when the total amount of whole rubber constituent is 100 weight part, the content of described non-silica reinforcing agent preferably no more than 120 weight parts, and more preferably less than 100 weight parts.From the viewpoint of fuel-efficient, be preferably at least 1 weight part, and be more preferably at least 3 weight parts.But not the preferred object lesson of silica reinforcing agent is carbon black.
Modified conjugated diene rubber of the present invention mixes with another rubber constituent, additive etc. the method manufacturing conjugated diene rubber composition, can use with example mixing tank as is known, the method of picture roller (roller) or ten thousand horsepowers of closed batch mixing machine (Banbury mixer, Banburymixer) or Banbury mixer (internalmixer) kneading (knead) each component.About the condition of mediating, except vulcanizing agent or vulcanization accelerator, when mixed additive, weighting agent, silicon-dioxide and/or other strengthening agent, the temperature of mediating is generally 50 DEG C to 200 DEG C, be preferably 80 DEG C to 150 DEG C, and the time of mediating is generally 30 seconds to 30 minutes, be preferably 1 minute to 30 minutes.When vulcanizing agent or vulcanization accelerator mixing, the temperature of described kneading is no more than 100 DEG C usually, is preferably 25 DEG C to 90 DEG C.The sulfidizing mode of such as press cure (pressvulcanization) can be used to be implemented being mixed into the composition after vulcanizing agent or vulcanization accelerator.The temperature of described sulfidizing is generally 120 DEG C to 200 DEG C, is preferably 140 DEG C to 180 DEG C.
Modified conjugated diene rubber of the present invention and conjugated diene rubber composition thereof can be used for tire, sole, flooring material and vibrations and block material etc., and be particularly suitable for tire, with promote tire tread low rolling impedance and promote by anti-slippery and produce control stability and reliability.
Described in detail the method for polyreaction of the present invention and modified-reaction by following examples.
Embodiment 1 (oxy radical)
There is provided autoclave reactor, initial capacity about 5 liters, with nitrogen filling.By the hexanaphthene of 2750 grams, the tetrahydrofuran (THF) of 82.5 grams, the 1,3-butadiene of the vinylbenzene of 100 grams and 390 grams loads in this autoclave reactor.When the temperature of reactor content reaches 30 DEG C, add the n-Butyl Lithium (n-butyllithium) of 325 milligrams (5.03mmol) with initiated polymerization.Polyreaction is carried out under adiabatic condition.When polyreaction almost completes, the 1,3-butadiene adding 10g carries out polyreaction about 5 minutes again.Then vinyl three (2-methoxy ethoxy) silane (vinyltris (2-methoxyethoxy) silane, hereinafter referred to as M1) of 2.82g (10.06mmol) is added.Carry out the modified-reaction of about 15 minutes.Then, add 2,6 ditertiary butyl p cresol (2,6-di-tert-butyl-p-cresol) and make reaction terminating in polymers soln.By this polymers soln rubber except after desolventizing, at 110 DEG C, carry out the conjugated diene rubber that hot-rolling (hotroll) drying can obtain modification, be defined as the rubber of embodiment 1.The properties-correcting agent (siloxanes) of embodiment 1 and the mol ratio of conjugated diene rubber-lithium, initial number average molecular weight (Mi) and the various character of product obtained are listed in accompanying table 1 in detail.
Embodiment 2 to 5 (oxy radical)
The step of embodiment 2 to embodiment 5 can the step of reference example 1, and it all uses same solvent and reactant, and the difference of reaction conditions is only the content of each reactant.The mol ratio of the reaction conditions of each embodiment such as properties-correcting agent (siloxanes) and conjugated diene rubber-lithium, initial number average molecular weight (Mi) and the various character of product obtained are listed in accompanying table 1 in detail.
Embodiment 6 (nitrogen-containing group)
There is provided autoclave reactor, initial capacity about 5 liters, with nitrogen filling.The 1,3-butadiene of the hexanaphthene of 2750 grams, the tetrahydrofuran (THF) of 82.5 grams, the vinylbenzene of 100 grams and 390 grams is loaded in autoclave reactor.When the temperature of reactor content reaches 30 DEG C, add the n-Butyl Lithium (n-butyllithium) of 325 milligrams (5.03mmol) with initiated polymerization.Polyreaction is carried out under adiabatic condition.When polyreaction almost completes, the 1,3-butadiene adding 10g carries out polyreaction about 5 minutes again.Then vinyl three (methyl ethyl ketone oximido) silane (Vinyltris (methylethylketoxime) silane, hereinafter referred to as M2) of 5.03mmol is added.Carry out the modified-reaction of about 15 minutes.Then, add 2,6 ditertiary butyl p cresol (2,6-di-tert-butyl-p-cresol) and make reaction terminating in polymers soln.By this polymers soln rubber except after desolventizing, at 110 DEG C, carry out the conjugated diene rubber that hot-rolling (hotroll) drying can obtain modification, be defined as the rubber of embodiment 6.The properties-correcting agent (siloxanes) of embodiment 6 and the mol ratio of conjugated diene rubber-lithium, initial number average molecular weight (Mi) and the various character of product obtained are listed in accompanying table 2 in detail.
Embodiment 7 to 9 (nitrogen-containing group)
The step of embodiment 7 to embodiment 9 can the step of reference example 6, and it all uses same solvent and reactant, and the difference of reaction conditions is only the content of each reactant.The mol ratio of the reaction conditions of each embodiment such as properties-correcting agent (siloxanes) and conjugated diene rubber-lithium, initial number average molecular weight (Mi) and obtain product various character list in detail in accompanying table 2.
Comparative example 1
Polymerization procedure is with embodiment 1.During modified-reaction, replace the siloxanes of embodiment 1 with the tetraethoxysilane (tetraethoxysilane, TEOS) of 1.05g (5.03mmol), carry out about 10 minutes.Then, add 2,6 ditertiary butyl p cresol (2,6-di-tert-butyl-p-cresol) and make reaction terminating in polymers soln.By this polymers soln rubber except after desolventizing, at 110 DEG C, carry out the conjugated diene rubber that hot-rolling (hotroll) drying can obtain modification, be defined as the rubber of comparative example 1.The properties-correcting agent (siloxanes) of comparative example 1 and the mol ratio of conjugated diene rubber-lithium, initial number average molecular weight (Mi) and obtain product various character list in detail in accompanying table 1.
Comparative example 2 and 3
The step of comparative example 2 to 3 can with reference to the step of comparative example 1, and essential difference is that reactant species is different.The properties-correcting agent that comparative example 1 uses is tetraethoxysilane (tetraethoxysilane, TEOS); The properties-correcting agent that comparative example 2 uses is tetramethoxy-silicane (tetramethoxysilane, TMOS); The properties-correcting agent that comparative example 3 uses is methyltrimethoxy silane (trimethoxy (methyl) silane, hereinafter referred to as TMOMS).The properties-correcting agent of each comparative example and the reaction conditions such as the mol ratio of conjugated diene rubber-lithium, initial number average molecular weight (Mi) and after reacting the characteristic of products therefrom list in detail in accompanying table 1.
Below illustrate that the rubber that the various embodiments described above of the present invention obtain is made into conjugated diene rubber composition also forms sulfuration sheet plate film further to test the method for loss tangent.
Get the rubber of each embodiment of 100 weight parts, silicon-dioxide (the trade name Ultrasil7000GR of 78.4 weight parts, manufactured by EVONIK company), silane coupling agent (the trade name Si69 of 6.9 weight parts, manufactured by EVONIK company), extending oil (the TDAE of 50.0 weight parts, manufactured by IRPC company), the antioxidant (trade name Antigene3C) of 1.5 weight parts, the stearic acid of 2 weight parts, the zinc oxide of 2 weight parts, the wax of 1.5 weight parts, the sulphur of 1.4 weight parts, and 2 weight part vulcanization accelerator (each 1 weight part of trade name CZ and D) mediate to form composition.Described plate film, by twin-roll machine die casting plate film in blocks, is heated to 160 DEG C by described composition, maintains 45 minutes, carries out sulfuration, obtains sulfuration sheet plate film thus.
The loss tangent of described sulfuration sheet plate film at 60 DEG C (losstangent, tan δ (60 DEG C)) is measured by using viscoelastic instrument (viscoelastometer), and measuring condition is the strain of 1% and the frequency of 10Hz.Such as, using comparative example 1 as standard, make comparative example 1 be 100%, then the higher person of embodiment value, energy-saving effect is better.The loss tangent of described sulfuration sheet plate film at 0 DEG C (tan δ (0 DEG C)) is measured by using viscoelastic instrument, and measuring condition is the strain of 0.5% and the frequency of 10Hz.Such as, using comparative example as standard, make comparative example 1 be 100%, then the higher person of embodiment value, safe effect of braking with grabbing is better.The loss tangent of the sulfuration sheet plate film gained of each embodiment is as shown in table 1 and table 2.
Table 1
Table 2
Above Akron abrasion rate table wear resistant, tan δ (0 ° of C) shows wetland earth-grasping force, and tan δ (60 ° of C) shows rolling resistance, and three's numerical value is separately more high better.
In table 1 and table 2, mooney viscosity (MV, MooneyViscosity) is preheating 1 minute and measures under the condition continuing 4 minutes at 100 DEG C.Mooney viscosity measures time point (time point) to be had: modified-reaction completes and (is labeled as after directly removing desolventizing) after remove desolventizing; Steam stripped also (is labeled as stripping also dry rear) after mechanical drying; And through 90 DEG C, after relative humidity 80% and storage test in 40 hours (being labeled as after storage test).In table 1, MV (stripping is also dry rear) is more equal with MV (after storage test) numeric ratio, represents the improvement of the stability of mooney viscosity.Coupling rate (CouplingRatio (C/R%)) is measured with gel permeation chromatograph (GPC) and refractometer, refer to that molecular weight accounts for the ratio of whole polymkeric substance higher than the polymkeric substance of molecular weight before non-coupling, when measuring using tetrahydrofuran (THF) (tetrahydrofuran) as mobile phase (mobilephase).Coupling rate measures time point to be had: the polymers soln state (being labeled as polymers soln) after modified-reaction completes; Steam stripped also (is labeled as stripping also dry rear) after mechanical drying.Other characteristic is then tested with technology well-known to those skilled in the art, such as styrene content, measure with fourier transform infrared spectroscopy (FTIR) containing the content of the structural unit of vinyl.Akron abrasion (Akronabrasion) is measured wear resistant and is used Akron abrasion machine, measure in loading be 6 pounds, wear loss under 3300 rotation numbers.Index is higher, and to represent wear loss fewer.
Akron abrasion rate (Idex), the tan δ (0 DEG C) and tan δ (60 DEG C) of the embodiment 1-5 shown in table 1 are all high than comparative example 1-3, indicate the performance boost of wear resistance, rolling resistance and wetland adherence properties.
Akron abrasion rate (Idex), the tan δ (0 DEG C) and tan δ (60 DEG C) of the embodiment 6-9 shown in table 2 are all high than comparative example 4, indicate the performance boost of wear resistance, rolling resistance and wetland adherence properties.
Although the present invention with preferred embodiment openly as above; but it is not intended to limiting the invention; without departing from the spirit and scope of the present invention, can carry out changing and retouch, therefore protection scope of the present invention is when being as the criterion of defining with claims for those skilled in the art.
Claims (29)
1. the manufacture method of modified conjugated diene rubber, comprising:
Step (a): the conjugated diene rubber that alkali metal containing ion is provided, wherein this conjugated diene rubber is the polymkeric substance be made up of conjugate diene monomer and vinyl aromatic monomers; And
Step (b): by the conjugated diene rubber of this alkali metal containing ion and siloxane reactions, to generate this modified conjugated diene rubber, the structural formula of this siloxanes is as follows:
Wherein, R
1, R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, wherein this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms; And
R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
2. the manufacture method of modified conjugated diene rubber as claimed in claim 1, wherein this C
2~ C
12oxy radical be the ethers group of following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12.
3. the manufacture method of modified conjugated diene rubber as claimed in claim 2, wherein this C
2~ C
12oxy radical be-CH
2cH
2oCH
3.
4. the manufacture method of modified conjugated diene rubber as claimed in claim 1, wherein this C
1~ C
12nitrogen-containing group be the imine group of following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11.
5. the manufacture method of modified conjugated diene rubber as claimed in claim 4, wherein this C
1~ C
12nitrogen-containing group be-N=C (CH
2cH
3) CH
3.
6. the manufacture method of modified conjugated diene rubber as claimed in claim 1, wherein R
4for-CH=CH
2.
7. the manufacture method of modified conjugated diene rubber as claimed in claim 1, wherein the mol ratio of the conjugated diene rubber of this siloxanes and this alkali metal containing ion is >=0.5.
8. the manufacture method of modified conjugated diene rubber as claimed in claim 1, also comprises step (c): the reaction product contacting this step (b) with water.
9. the manufacture method of modified conjugated diene rubber as claimed in claim 8, wherein the treatment process of this step (c) comprises steam stripped.
10. the manufacture method of modified conjugated diene rubber as claimed in claim 8, wherein this modified conjugated diene rubber records the first mooney viscosity through this step (c) after drying, again through 90 DEG C, record the second mooney viscosity after relative humidity 80% and storage test in 40 hours, the difference between this first mooney viscosity and second mooney viscosity is zero or 1 or 3.
The manufacture method of 11. modified conjugated diene rubber as claimed in claim 1, wherein this alkali metal containing ion conjugated diene rubber with this siloxane reactions before initial number average molecular weight be 80kg/mol ~ 2000kg/mol.
The manufacture method of 12. modified conjugated diene rubber as claimed in claim 9, wherein this coupling rate through this modified conjugated diene rubber of step (c) is 10% ~ 95%, this coupling rate measures with gel permeation chromatograph and refractometer, refer to that molecular weight accounts for the ratio of whole polymkeric substance higher than the polymkeric substance of molecular weight before non-coupling, when measuring using tetrahydrofuran (THF) as mobile phase.
13. modified conjugated diene rubber, it is made with the manufacture method such as according to any one of claim 1 to 12.
14. conjugated diene rubber compositions, comprise:
Modified conjugated diene rubber as claimed in claim 13; And
Silicon-dioxide.
15. conjugated diene rubber compositions as claimed in claim 14, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this modified conjugated diene rubber is more than 10 weight parts.
16. conjugated diene rubber compositions as claimed in claim 14, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this silicon-dioxide is 10-200 weight part.
17. modified conjugated diene rubber, the structural formula of this modified conjugated diene rubber is as follows:
Wherein, D is conjugated diene rubber, and wherein this conjugated diene rubber D is the polymkeric substance be made up of conjugate diene monomer and vinyl aromatic monomers; R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, wherein this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms; And
R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group.
18. modified conjugated diene rubber as claimed in claim 17, wherein this C
2~ C
12oxy radical be the ethers group of following general formula :-C
mh
2m-O-C
nh
2n+1, wherein m and n is positive integer, and m+n=2 ~ 12.
19. modified conjugated diene rubber as claimed in claim 18, wherein this C
2~ C
12oxy radical be-CH
2cH
2oCH
3.
20. modified conjugated diene rubber as claimed in claim 17, wherein this C
1~ C
12nitrogen-containing group be the imine group of following general formula: (C
nh
2n+1) (C
mh
2m+1) C=N-, the wherein integer of m=0 to 10, the integer of n=1 to 11.
21. modified conjugated diene rubber as claimed in claim 20, wherein this C
1~ C
12nitrogen-containing group be-N=C (CH
2cH
3) CH
3.
22. modified conjugated diene rubber, wherein R as claimed in claim 17
4for-CH=CH
2.
23. modified conjugated diene rubber as claimed in claim 17, wherein the coupling rate of this modified conjugated diene rubber is 10% ~ 95%, this coupling rate measures with gel permeation chromatograph and refractometer, refer to that molecular weight accounts for the ratio of whole polymkeric substance higher than the polymkeric substance of molecular weight before non-coupling, when measuring using tetrahydrofuran (THF) as mobile phase.
24. modified conjugated diene rubber as claimed in claim 17, wherein this modified conjugated diene rubber have passed through water contact pairs.
25. modified conjugated diene rubber as claimed in claim 24, wherein this modified conjugated diene rubber records the first mooney viscosity through this water contact pairs after drying, again through 90 DEG C, record the second mooney viscosity after relative humidity 80% and storage test in 40 hours, the difference between this first mooney viscosity and second mooney viscosity is zero or 1 or 3.
26. conjugated diene rubber compositions, comprise:
Modified conjugated diene rubber as described in any one of claim 17 to 25; And silicon-dioxide.
27. conjugated diene rubber compositions as claimed in claim 26, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this modified conjugated diene rubber is more than 10 weight parts.
28. conjugated diene rubber compositions as claimed in claim 26, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this silicon-dioxide is 10-200 weight part.
The manufacture method of 29. modified conjugated diene rubber, comprising:
Step (a): the conjugated diene rubber that alkali metal containing ion is provided;
Step (b): by the conjugated diene rubber of this alkali metal containing ion and siloxane reactions, to generate this modified conjugated diene rubber, the structural formula of this siloxanes is as follows:
Wherein, R
1, R
2, R
3be selected from C independently of one another
2~ C
12oxy radical and C
1~ C
12nitrogen-containing group, wherein this C
2~ C
12oxy radical be directly combined with the Sauerstoffatom of this siloxanes with its carbon atom, and this C
1~ C
12nitrogen-containing group be directly combined with the Sauerstoffatom of this siloxanes with its nitrogen-atoms; And
R
4be selected from C
1~ C
12alkyl, C
2~ C
12thiazolinyl, C
6~ C
12aromatic base and C
1~ C
12alkoxyl group; And
Step (c): the reaction product contacting this step (b) with water.
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