CN102372823B - Terpolymer rubber with medium/high side group content and preparation method and applications thereof - Google Patents

Abstract

The invention discloses terpolymer rubber with medium/high side group content and a preparation method and applications thereof. The invention relates to a method which uses a bistetrahydrofuran compound as the structural modifier to synthesize monovinylarene/conjugated diene 1/conjugated diene 2 terpolymer rubber through solution polymerization, the monovinylarene/conjugated diene 1/conjugated diene 2 terpolymer rubber synthesized by the method and products based on the copolymer rubber, such as tires. The copolymer rubber synthesized by the method has good wet-skid resistance and low rolling resistance.

Description

The terpolymer rubber of high side group content, its preparation method and application thereof in a kind of

Invention field

The present invention relates to a kind of in the terpolymer rubber of high side group content, in particular to terpolymer of a kind of conjugated diene 1, conjugated diene 2 and monovinylarene and preparation method thereof.More particularly; The present invention relates to a kind ofly adopt the double tetrahydrofuran compound to prepare the novel tertiary copolymer rubber of the method for conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber and method preparation thus and, like tire etc. based on the goods of said terpolymer rubber as structure regulator.

Background of invention

The current elastomeric material of tread rubber of automobile tires that is applicable to not only will have good abrasion resistance, also will have high wet-sliding resistant property and low-rolling-resistance, could satisfy safety traffic and energy-conservation demand like this.And these two kinds of performance demands of high wet-sliding resistant property and low-rolling-resistance are conflicting, and the rubber of single variety is difficult to meet the demands simultaneously.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 property respectively, is difficult to obtain the ideal product.Along with going deep into of research, the scientific research personnel finds the design through molecular structure, can synthesize the multipolymer with high wet-sliding resistant property and low-rolling-resistance, thus the contradiction between balance elastomeric material anti-slippery and the rolling resistance preferably.See from present data; The anti-slippery of elastomeric material and rolling resistance can be come to characterize indirectly usually by the tan δ value when 0 ℃ and 60 ℃ in the dynamic viscoelasticity spectrum; Tan δ value in the time of 0 ℃ is high; The anti-slippery that shows rubber is good more, and the value of the tan δ in the time of 60 ℃ is low, shows that the low-rolling-resistance performance of rubber is good.The dynamic properties of elastomeric material and its composition and microtexture are closely related, thereby the microtexture of therefore in polymerization system, introducing the structure regulator controlling polymers is the technology that generally adopts.

The common structural regulator is gone up in industry at present has THF (THF), Tetramethyl Ethylene Diamine (TMEDA), diethylene glycol dimethyl ether (2G) etc.But all there are some problems in these structure regulators, mainly show: or addition is more and not easily separated in solvent, influences recycling of solvent system; Perhaps regulating power is relatively poor and have certain irritating smell under higher conditions of polymerization temperature vary, makes product have contaminative; Perhaps be prone to cause chain transfer, the carrying out and the coupling efficiency of influence reaction.Therefore develop the efficient configuration regulator and just become the hot issue of this area research at present.

US 5; 137; Mentioned a kind of method that adopts anionoid polymerization synthesis of ternary copolymer rubber in 998, adopted three piperidines phosphine oxides (TPPO) or alkali metal alcoholates (preferred potassium alcoholate) in this method as structure regulator, higher with the polymer pendant groups content that this method obtains; But polymerization temperature is-10 ℃ to 40 ℃, so the reaction times is longer.US 5; 448; Mentioned a kind of method that adopts anionoid polymerization synthesis of ternary copolymer rubber in 003, this method adopts alkyl tetrahydro furfuryl group ether as structure regulator, thereby obtains the multipolymer of high-vinyl-content; But this kind structure regulator has the strong impulse smell, aspect environmental protection and operation environment safety, exists not enough.

Summary of the invention

Based on above-mentioned prior art situation; Contriver of the present invention is through carrying out research extensively and profoundly to solution polymerization conjugated-diolefin/uni-vinyl-arene copolymer rubber field; The result finds through the double tetrahydrofuran compound is carried out the solution terpolymer as structure regulator to conjugated diene 1, conjugated diene 2 and monovinylarene; Can fully regulate the side group content in the gained multipolymer; Obtain conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer, the especially random copolymers of high side group content in having, the little block content of more oligomeric monovinylarene.

Thereby; One object of the present invention is to provide the preparation method of a kind of conjugated diene 1, conjugated diene 2 and monovinylarene terpolymer rubber; This method adopts the double tetrahydrofuran compound as structure regulator, makes the terpolymer rubber that obtains have high wet-sliding resistant property and low-rolling-resistance, is particularly suitable for making tire tread; It can use separately, also can use with other rubber mix.

Another object of the present invention provides a kind of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer that is obtained by aforesaid method.

A further object of the present invention provides the application of above-mentioned conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber in the preparation high-performance tire.

Need to prove that term " terpolymer " and " terpolymer rubber " can exchange use in the present invention.

Term " side group content " is meant the summation of contents of ethylene and propenyl content in conjugated diene 1, conjugated diene 2 and the monovinylarene terpolymer rubber in the present invention.

Particularly; One aspect of the present invention provides a kind of method for preparing conjugated diene 1, conjugated diene 2 and monovinylarene terpolymer rubber; This method is included in and adopts anionic polymerization initiator under the inert gas environment; Use the double tetrahydrofuran compound as structure regulator, in solvent, carry out the random copolymerization of conjugated diene 1, conjugated diene 2 and mono vinyl arenes monomer.

It is a kind of by aforesaid method synthetic conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber that the present invention provides on the other hand.

Further aspect of the present invention provides a kind of goods based on said conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer, like tire.

Characteristics of the present invention are; Business-like structure regulation system and polymerizing condition are convenient in employing; Side group content with conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer is controlled at middle and high level and the content that gathers the little block of monovinylarene in the terpolymer is controlled at a lower level effectively; Make the terpolymer rubber that obtains have high wet-sliding resistant property and low-rolling-resistance, be particularly suitable for making tire tread.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, used structure regulator is the double tetrahydrofuran compound with following general formula (I) in the polymerization process,

Wherein R1, R2 are C₁-C₁₀Alkyl is preferably C₁-C₅Alkyl, more preferably methyl or ethyl, especially methyl.

In preferred embodiments, the compound of general formula of the present invention (I) is preferably two tetrahydrochysene chaff propane (DTHFP).

The present invention is used to prepare the anionoid polymerization of method under the anionoid polymerization condition, carrying out of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer; It is preferably the anionic solution polymerization of organolithium compound as initiator for adopting anionic polymerization initiator, and said solution polymerization comprises the steps:

Under inert gas environment, adopting anionic polymerization initiator, especially organolithium compound is initiator; Add the double tetrahydrofuran compound shown in the general formula (I) as structure regulator, in solvent, carry out the random copolymerization reaction of conjugated diene 1, conjugated diene 2 and monovinylarene.

Above-mentioned rare gas element refers to any gas of the random copolymerization reaction of not participating in conjugated diene 1, conjugated diene 2 and monovinylarene, for example nitrogen, helium etc.

Structure regulator of the present invention can join in the reaction system by any way, and for example, structure regulator can be with organic lithium initiator or joined in the polymerization system respectively.The consumption of structure regulator depends on the side group content of desired conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber.Usually, require the side group content of terpolymer rubber high more, the consumption of structure regulator is just big more, the mol ratio of general control texture regulator and anionic polymerization initiator (especially organic lithium initiator).In embodiments of the invention, preferably the mol ratio with structure regulator and organic lithium initiator is controlled in the scope of 0.1-1, more preferably is controlled in the scope of 0.4-0.7.

In embodiments of the invention; Double tetrahydrofuran compound shown in the said general formula (I) has stronger regulating effect as structure regulator; Make and can be effectively the side group content of multipolymer to be controlled at middle and high level and to be controlled at a lower level with gathering the little block content of monovinylarene in the multipolymer; And the second-order transition temperature of polymkeric substance is controlled at suitable scope, thereby has reached good dynamic properties.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention; Can use the disclosed anionoid polymerization of prior art to use initiator; The preferred organolithium compound that uses comprises organic single-lithium, organic pair of lithium or organic multi-lithium initiator as initiator.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 0.25-2.5mmol.

The disclosed anionoid polymerization of prior art all can be used for the present invention with the organic single-lithium initiator, and the limiting examples of said organic single-lithium initiator comprises C₁-C₆Lithium alkylide, C₆-C₁₂Lithium aryl, C₇-C₁₄Aralkyl lithium and C₃-C₁₂The naphthenic base lithium; For example lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, NSC 62789 base lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium, cyclohexyl lithium or 4-butyl cyclohexyl lithium; Preferred n-Butyl Lithium or s-butyl lithium, especially n-Butyl Lithium.

The disclosed anionoid polymerization of prior art all can be used for the present invention with organic dilithium initiator, and they are preferably two lithium methane, 1,4-two lithium butane, 1,10-two lithium decane or 1,4-two lithium hexanaphthenes.

Initiator used in the present invention can also be for the disclosed any multifunctional organic lithium initiator of prior art, for example by general formula R Li_nOr T (RLi)_nThose of expression, wherein R is that carbonatoms is the alkyl of 4-20; T is the metallic element that is selected from Sn, Si, Pb, Ti and Ge; N is the initiator functionality, and n is 3-150, preferred 3-50, the integer of 3-10 most preferably.Multifunctional organic lithium initiator RLi_nCan also be multi-chelate organolithium initiator, like GB2,124; 228A, US 3,280,084, EP 0; 573,893A2, CN1,197; The Vinylstyrene of mentioning among the 806A etc. (DVB) reacts the various multi-chelate organolithium initiators that obtain with lithium alkylide, and these prior art documents are specially introduced here as a reference.Multifunctional organic lithium initiator also can be the multifunctional organic lithium initiator T (RLi) that contains above-mentioned metal_n, multifunctional organic lithium initiator T (RLi)_nThe multifunctional organolithium that generally is selected from stanniferous Sn causes Sn (RLi)_n, like CN1,148, the multifunctional organic lithium initiator Sn (RLi) of the stanniferous Sn that mentions among the 053A₄In addition; Multifunctional organic lithium initiator can also be that other can be used in and causes divinyl, isoprene equiconjugate diolefine and styrene monomer polymeric functionality and be not less than 3 organic lithium initiator, like US 5,262; 213, US 5; The various multifunctional organic lithium initiator of mentioning in 595,951, these prior art documents are specially introduced here as a reference.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber of the present invention; Operable conjugated diene 1 is different with conjugated diene 2; They are meant any monomer that in its molecule, has conjugated double bond, and the example includes but not limited to C₄-C₆Conjugated diene monomer is like divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene or 2,3-dimethylbutadiene.Said conjugated diene 1 is preferably divinyl and isoprene with conjugated diene 2.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber of the present invention; Operable mono vinyl arenes monomer is meant the aromatic monomer that on its aromatic ring, has a vinyl substituted base; The example includes but not limited to vinylbenzene or the substituted vinylbenzene of alkyl; Like vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3; 5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene or 4-dodecyl vinylbenzene; Optimization styrene, Vinyl toluene and alpha-methyl styrene; Vinylbenzene most preferably.

Therefore, in the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber of the present invention, preferably use divinyl, isoprene and vinylbenzene as comonomer.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber of the present invention, be benchmark in the weight of terpolymer, the content of said mono vinyl arenes monomer is 10-40wt%, is preferably 15-25wt%; Conjugated diene 1 monomeric content is 5-85wt%, is preferably 20-60wt%; Conjugated diene 2 monomeric content are 5-85wt%, are preferably 20-60wt%.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention; The disclosed anionoid polymerization of prior art all can be used for the present invention with solvent; Preferably use varsol, for example contain naphthenic hydrocarbon, aromatic hydrocarbons, isoparaffin or its mixture of 5-7 carbon atom.Specific examples is hexanaphthene, normal hexane, Skellysolve A, normal heptane, benzene, one or more the mixture in raffinating oil.These solvents can use separately or mix use with two or more, and (wherein the weight ratio of the two is 80: 20-90: 10) for example to use the mixture of hexanaphthene and normal hexane.In embodiments of the invention, the consumption of said solvent should make in the reaction system total monomer in the scope of 10-20wt%.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, after polyreaction is accomplished, can stop living polymer chains by anionoid polymerization field mode commonly used.Used terminator is commonly used those in anionoid polymerization field, and for example water or alcohol are like methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.

In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, after polyreaction was accomplished, before terminator added, the optional coupling agent that can add carried out coupling to the multipolymer that generates.The consumption of coupling agent will guarantee the segment of 20-100% by coupling, and preferred coupling efficiency is 40-80%.Operable coupling agent includes but not limited to many vinyl aromatic (co)s hydro carbons, polyfunctional epoxies, imines class, aldehydes, ketone, acid anhydride class, ester class, isocyanates and polyhalogenide etc.; Be preferably the coupling agent of 2-4 functionality; For example silicon tetrachloride, tin tetrachloride, hexadiene oxalic acid, dimethyl adipate, Vinylstyrene, dimethyldichlorosilane(DMCS) or METHYL TRICHLORO SILANE, more preferably tin tetrachloride.The mol ratio of anionic polymerization initiator, especially organic lithium initiator that coupling agent and the present invention use is generally 0.05-0.5, is preferably 0.1-0.3.

For the present invention, can directly add the terminator termination reaction after the coupling, perhaps after coupling, can add sn-containing compound part or all of end-blocking is partly carried out in coupling not, carry out the termination reaction operation behind the end-blocking again.Used end-capping reagent is the conventional end-capping reagent in the synthetic field of rubber, and like trialkyltin chlorine, wherein alkyl contains 1-8 carbon atom, like tin trimethyl chlorine, triethyltin chlorine, tributyl tin chlorine.The mol ratio of the same not coupling part of end-capping reagent is 0.2-1.0, is preferably 0.5-1.0.

Randomly, can add anti-aging agent conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer rubber of the present invention is handled, for example before drying, anti-aging agent added in the glue.Passable anti-aging agent is generally phenols or amine; Comprise Irganox 1520 (Switzerland vapour Bagong department), four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (promptly 1010)/tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester (promptly 168)) compound anti-aging agent (wherein 168 content is not higher than 50wt%), 3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (promptly 1076)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (promptly 168) compound anti-aging agent (wherein 168 content is not higher than 50wt%), 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 a 0.005-2% weight based on polymkeric substance generally.After adding anti-aging agent, the polymkeric substance glue can precipitate from solvent through similar fashion such as alcoholization deposition, spinning, filtration, decant, hot water cohesions separates out, and also can adopt the stripping mode that the volatile organic solvent in the multipolymer is separated.

The polymerization method that the present invention relates to can the batchwise polymerization mode or the successive polymerization mode carry out, the temperature when wherein adding initiator is controlled at 35-80 ℃, preferred 40-70 ℃; Polymeric reaction temperature is generally 50-130 ℃, preferred 60-105 ℃; Polymerization pressure is the 0.005-1MPa gauge pressure, is preferably the 0.1-0.3MPa gauge pressure; Polymerization reaction time is 0.2-2 hour.

The invention also discloses a kind of by the conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of method for preparing, this terpolymer has following constitutional features:

1) the unit content that is derived from mono vinyl arenes monomer is 10-40wt%, is preferably 15-25wt%;

2) being derived from conjugated diene 1 monomeric unit content is 5-85wt%, is preferably 20-60wt%;

3) being derived from conjugated diene 2 monomeric unit content is 5-85wt%, is preferably 20-60wt%;

4) be 100% calculating with conjugated diene 1+ conjugated diene 2 quality, vinyl structure content is 10-40wt% in the terpolymer, is preferably 15-30wt%; The propenyl structural content is 10-40wt%, is preferably 15-40wt%; Wherein vinyl structure content and propenyl structural content sum are 20-80wt% in the terpolymer, are preferably 30-70wt%.

6) exist the content of the monovinylarene of (the repeated structural unit number is greater than 5) to be lower than 1wt% with little block;

7) before coupling, the number-average molecular weight of polymkeric substance is 10-50 ten thousand, is preferably 12-25 ten thousand, and MWD is 1.5-2.5;

8) through after the optional coupling, the coupling efficiency of terpolymer is 20-100%, is preferably 40-80%.

In conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention; Preferred vinylbenzene (ST), isoprene (IP) and three kinds of monomers of divinyl (BD) of using are as comonomer; Wherein the weight in this terpolymer rubber is benchmark; The content of ST is 10-40wt%, is preferably 15-25wt%; The content of IP is 5-85wt%, is preferably 20-60wt%; The content of BD is 5-85wt%, is preferably 20-60wt%; ST, IP and three kinds of monomers of BD can exist with random mode in multipolymer, can also have long polybutadiene block or polyisoprene blocks.The microtexture of gained terpolymer is: with the IP+BD mass ratio is 100% calculating, 1, and 2-BD structural content (corresponding to vinyl structure content) is 10-40wt%, is preferably 15-30wt%; 3,4-IP structural content (corresponding to the propenyl structural content) is 10-40wt%, is preferably 15-40wt%; Side group content (1,2-BD and 3,4-IP structural content sum) is 20-80wt%, and preferable range is 30-70wt%.

Ter-polymer rubber by compound method preparation of the present invention can be used to prepare various rubber items, especially is fit to manufacture of tires and uses.

Terpolymer rubber of the present invention has splendid wet-sliding resistant performance and excellent low-rolling-resistance performance owing to be described below:

(1) adopt the double tetrahydrofuran compound as structure regulator; Can regulate the side group structure of two kinds of conjugated diolefines; Making the little block content of monovinylarene remain below the situation of 1wt%, obtained the multipolymer of middle and high side group content, improved the wet-sliding resistant performance of copolymer rubber;

(2) most of polymer segment is carried out coupling, reduced the quantity of polymer free terminal, can effectively improve the rolling resistance performance of copolymer rubber, improved the anti-cold flow properties of rubber simultaneously.

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.

In the present invention, the microtexture of synthetic terpolymer rubber adopts the Switzerland AVANCE DRX 400MHz of Bruker company nuclear magnetic resonance spectrometer to measure, and solvent is a deuterochloroform; Molecular weight and coupling efficiency adopt the U.S. ALLIANCE2690 of WATERS company type gel permeation chromatograph (GPC) to measure, and THF is a moving phase, and narrow distribution polystyrene is a standard specimen, and temperature is 25 ℃; Second-order transition temperature adopts the U.S. MDSC2910 of TA company type dsc (DSC) appearance to measure 60s modulation period, modulated amplitude ± 1.5 ℃, 10 ℃/min of temperature rise rate, nitrogen protection, flow velocity 50mL/min; Dynamic properties adopts the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure frequency 2Hz, 5 ℃/min of temperature rise rate ,-120 ℃ to 100 ℃, sample size 40mm * 5mm * 1mm.Rubber adopt mill the roller temperature be carry out under 50 ± 5 ℃ mixing; Cure conditions: 145 ℃ of temperature, more than the pressure 10MPa, sulfuration 35min; The sulfuration basic components, rubber: 100g; Aromatic hydrocarbon oil: 5g; Carbon black: 45g; Sulphur: 1g; Promotor: 1g; Triple Pressed Stearic Acid: 2g; Anti-aging agent: 1g; Zinc oxide: 5g.Vulcanizating glue physical performance adopts Japanese SHIMADZUAG-20KNG type puller system, presses GB/T528-1998 and measures; Mooney viscosity adopts Japanese SHIMADZU SMV-300 tester, presses GB/T1232-92 and measures.

Embodiment 1

Under the high pure nitrogen protection; By ratio of components mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), vinylbenzene (ST), isoprene (IP), divinyl (BD) and pair tetrahydrochysene chaff propane (DTHFP) are joined in the stainless steel polymerization reaction kettle of 5 liter bands stirring.Through with the hot water heating jacket reaction kettle being warming up to 40 ℃, polymerization pressure is controlled between the 0.1MPa-0.3MPa, adds the n-Butyl Lithium initiation reaction, and polymerization added tin tetrachloride coupling 30 minutes after 60 minutes.Be incorporated as the Virahol termination reaction of 1.2 times (mol ratio) amount of n-Butyl Lithium then, obtain random terpolymer rubber product behind the water devaporation.Product microtexture and each item performance are seen table 1.

Embodiment 2-4

Carry out according to embodiment 1 said program, its difference is that the polymerization kick off temperature is respectively 50 ℃, 60 ℃, 70 ℃, and product microtexture and each item performance are seen table 1.

Table 1 product microtexture and each item performance

Project	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Solvent/g	2288	2288	2288	2288
ST/g	62.4	62.4	62.4	62.4
					BD/g	124.8	124.8	187.2	187.2
IP/g	124.8	124.8	62.4	62.4
					DTHFP/Li (mol ratio)	0.5	0.5	0.5	0.5
The polymerization kick off temperature/℃	40	50	60	70
					Molecular weight, MPeak value(ten thousand)	18.2	21.9	16.8	15.8
MWD, MWD	1.533	1.596	1.572	1.651
					Coupling efficiency/%	63.7	62.0	61.5	42.0
The rubber Mooney	64	70	53	43
					Mooney Viscosity of Rubber Mix	89	102	94	94
Shao Er hardness	76	76	74	76
					Tear strength/MPa	36	33	33	40
Tension set/%	10	9	8	8
					300% tensile modulus/Mpa	13.1	13.2	14.3	12.9
Tensile strength at yield/Mpa	19.9	21.3	20.5	21.0
					Specific elongation rate/%	425	451	400	459
ST is random/wt%	22.4	23.0	21.9	20.8
					ST block/wt%	0.0	0.0	1.3	3.4
1，2-BD/wt％	23.1	21.8	17.2	14.2
					1，4-BD/wt％	28.9	30.7	37.2	39.3
1，4-IP/wt％	23.4	23.8	30.3	34.3
					3，4-IP/wt％	24.6	23.7	15.3	12.2
Side group content/wt%	47.7	45.5	32.5	26.4
					Tanδ(0℃)	0.6029	0.4640	0.2678	0.1932
Tanδ(60℃)	0.1061	0.1072	0.1056	0.1267
					Tg/℃	-25.13	-26.72	-40.50	-48.40

Embodiment 5-11

Carry out according to embodiment 2 said programs; Its difference is to regulate the structure regulator amount that adds in the polymerization system; Make it to become 0.1,0.2,0.4,0.6,0.7,1.0,2.0 successively with the proportioning of organolithium, product microtexture and each item performance see the following form 2.

Table 2 product microtexture and each item performance

Project	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11
								Solvent/g	2288	2288	2288	2288	2288	2288	2288
ST/g	62.4	62.4	62.4	62.4	62.4	62.4	62.4
								BD/g	124.8	124.8	124.8	124.8	124.8	124.8	124.8
IP/g	124.8	124.8	124.8	124.8	124.8	124.8	124.8
								DTHFP/Li (mol ratio)	0.1	0.2	0.4	0.6	0.7	1.0	2.0
Polymerization kick off temperature ℃	50	50	50	50	50	50	50
								Molecular weight, MPeak value(ten thousand)	16.5	18.0	18.2	23.9	14.4	15.3	18.8
Coupling efficiency/%	66.5	64.7	64.4	55.9	69.1	44.5	47.2
								MWD, MWD	1.467	1.536	1.559	1.636	1.569	1.620	1.722
The rubber Mooney	76	70	58	109	57	35	42
								Mooney Viscosity of Rubber Mix	125	125	100	131	79	68	88
Shao Er hardness	78	74	74	72	74	76	78
								Tear strength/MPa	36	37	36	34	32	34	36
Tension set/%	8	8	6	8	13	17	16
								300% tensile modulus/MPa	15.1	14.1	13.3	14.2	13.4	12.7	12.8
Tensile strength at yield/MPa	20.0	20.7	19.4	21.6	19.3	20.7	20.1
								Specific elongation rate/%	393	423	402	435	414	427	448
ST is random/wt%	19.8	22.9	24.0	25.3	23.5	22.0	21.6
								ST block/wt%	3.5	1.3	0.9	0.1	0.1	0.0	0.1
1，2-BD/wt％	12.3	14.5	19.2	23.2	24.6	25.5	25.7
								1，4-BD/wt％	42.0	39.1	35.0	30.3	25.4	24.8	23.9
1，4-IP/wt％	36.2	34.2	28.5	22.4	20.0	19.5	19.5
								3，4-IP/wt％	9.5	12.2	17.3	24.1	30.0	30.2	30.9
Side group content/wt%	21.8	26.7	36.5	47.3	54.6	55.7	56.6
								Tanδ(0℃)	0.1472	0.1765	0.4130	0.8144	0.8745	-	-
Tanδ(60℃)	0.1137	0.1066	0.1022	0.09960	0.1110	-	-
								Tg/℃	-54.15	-48.24	-35.24	-23.65	-17.07	-16.81	-14.57

Comparative Examples 1

Carry out according to embodiment 2 said programs, its difference is that structure regulator becomes THF (THF), and product microtexture and each item performance see the following form 3.

Comparative Examples 2-3

Carry out according to embodiment 2 said programs, its difference is that structure regulator becomes tetrahydrofurfuryl alcohol ether (ETE), and product microtexture and each item performance see the following form 3.

Table 3 product microtexture and each item performance

Project	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3
				Solvent/g	2288	2288	2288
ST/g	62.4	62.4	62.4
				BD/g	124.8	124.8	124.8
IP/g	124.8	124.8	124.8
				Structure regulator/Li (mol ratio)	THF/Li＝35	ETE/Li＝0.6	ETE/L?i＝2
The polymerization kick off temperature/℃	50	50	50
				Molecular weight, MPeak value(ten thousand)	23.6	20.1	18.5
Coupling efficiency/%	62.1	60.7	62.4
				MWD, MWD	1.380	1.535	1.538
The rubber Mooney	35	49	85
				Mooney Viscosity of Rubber Mix	55	65	68
Shao Er hardness	58	62	68
				Tear strength/MPa	34	35	36
Tension set/%	18	10	11
				300% tensile modulus/MPa	8.2	10.8	9.3
Tensile strength at yield/MPa	16.4	17.6	19.3
				Specific elongation rate/%	532	443	518
ST is random/wt%	26.9	20.0	23.9
				ST block/wt%	0.5	5.6	0.15
1，2-BD/wt％	17.1	14.7	23.8
				1，4-BD/wt％	33.3	33.4	22.5
1，4-IP/wt％	30.1	37.8	23.8
				3，4-IP/wt％	19.5	14.1	29.9
Side group content/wt%	36.6	28.8	53.7
				Tanδ(0℃)	0.5521	-	0.9601
Tanδ(60℃)	0.1107	-	0.1214
				Tg/℃	-34.32	-47.30	-18.01

Sum up:

Embodiment 1-4 uses of the present invention pair of tetrahydrochysene chaff propane (DTHFP) as structure regulator, has investigated under the certain condition of structure regulator consumption, and different kick off temperatures are to terpolymer rubber 1,2-BD and 3, the influence of 4-IP structural content.Data from table 1 can be found out: along with the rising of kick off temperature, and terpolymer rubber 1,2-BD and 3, the 4-IP structural content is downward trend gradually, and the little block content of vinylbenzene is the trend that increases gradually.Embodiment 5-11 is then under the condition of identical kick off temperature (50 ℃), and the DTHFP structure regulator of having investigated different amounts is to terpolymer rubber 1,2-BD and 3, the influence of 4-IP structural content.Data from table 2 can be found out: along with the increase of structure regulator consumption, and terpolymer rubber 1,2-BD and 3; The 4-IP structural content is gradually the trend that rises, and the little block content of vinylbenzene is downward trend, when DTHFP/Li (mol ratio) greater than 0.4 the time; The little block of vinylbenzene is all less than 1wt%; But, therefore must consider its second-order transition temperature, if DTHFP/Li (mol ratio) is excessive because this patent product is mainly used in tire tread; Then the second-order transition temperature of terpolymer is too high, is not suitable for tire tread.Therefore, in order to obtain over-all properties, can make in the terpolymer rubber 1 through regulating DTHFP consumption and polymeric reaction temperature than more excellent product; 2-BD and 3, the 4-IP structure is effectively controlled, i.e. regulation and control flexibly between 30%-70%; The terpolymer rubber that synthesizes high side group content in having; Make the little block content of vinylbenzene in the multipolymer maintain lower level and have suitable second-order transition temperature simultaneously, in sum, in certain TR; Structure regulator DTHFP/Li (mol ratio) is 0.1-1, preferred 0.4-0.7.

For Comparative Examples; From the data of Comparative Examples 1, can find: at the little block content of vinylbenzene all under the prerequisite less than 1wt%; When THF/Li (mol ratio)=35; The side group content of terpolymer rubber is 36.6wt%, and when reaching identical side group content, the mol ratio of DTHFP and Li is merely 0.4; From Comparative Examples 2 data, can find when ETE/Li (mol ratio) is 0.6; The side group content of sample is 28.8wt%; The little block content of vinylbenzene reaches 5.6wt%; And DTHFP/Li (mol ratio) is 0.6 o'clock, and the side group content of sample has reached 47.3wt%, and the little block content of vinylbenzene is merely 0.1wt%; From Comparative Examples 3 data, can find to obtain side group content is 53.7wt%; The terpolymer rubber that the little block content of vinylbenzene is 0.15wt%; ETE/Li (mol ratio)=2, and when reaching the little block contents level of identical side group content and vinylbenzene, the mol ratio of DTHFP and Li is merely 0.7.

On the other hand; Adopt DTHFP of the present invention to have outstanding dynamic properties as structure regulator synthetic sample; Show: outstanding especially (DTHFP/Li was greater than 0.4 o'clock for the value of the Tan δ under its 0 ℃ of the terpolymer of high side group content in having; Tan δ value under 0 ℃ is all more than 0.4), promptly the anti-slippery of sample is very excellent.For tire tread applications, simultaneously also require sample to have low-rolling-resistance, promptly the Tan δ value under 60 ℃ is low as far as possible.But like the independent structure regulator (Comparative Examples 3) that uses in the Comparative Examples, when the Tan δ value under 0 ℃ reaches 0.8 when above, the Tan δ value under 60 ℃ also can surpass 0.12, preferably the contradiction between balance anti-slippery and the rolling resistance.Solution route is or development of new structure regulator or adopt the composite use of structure regulator; DTHFP of the present invention then preferably the contradiction between balance anti-slippery and the rolling resistance (the Tan δ value under 0 ℃ was greater than 0.8 o'clock; Tan δ value under 60 ℃ is about 0.1; See embodiment 9), be a kind of structure regulator of excellence.

Above data prove absolutely; Use DTHFP of the present invention as structure regulator; Its regulating power is superior to common structural regulator in the tradition; And under less consumption, can obtain higher side group content, and make the little block content of vinylbenzene in the terpolymer lower, even under higher kick off temperature, still have fabulous regulating power and stability.Therefore double tetrahydrofuran compound of the present invention has overcome the shortcoming of traditional structure regulator, and the preparation that is used for the terpolymer of conjugated diene 1, conjugated diene 2 and monovinylarene is a kind of comparatively ideal structure regulator.

Claims (29)

1. the preparation method of a conjugated diene 1, conjugated diene 2 and monovinylarene ter-polymer rubber; Be included in and adopt organic lithium initiator under the inert gas environment; Use the double tetrahydrofuran compound as structure regulator, in solvent, carry out the random copolymerization of conjugated diene 1, conjugated diene 2 and mono vinyl arenes monomer; The mol ratio of said structure regulator and organic lithium initiator is 0.4-1;

Wherein said double tetrahydrofuran compound is the compound with following general formula (I),

Wherein R1, R2 are C₁-C₁₀Alkyl.

2. method as claimed in claim 1, the mol ratio of wherein said structure regulator and organic lithium initiator are 0.4-0.7.

3. method as claimed in claim 1, wherein R1, R2 are C₁-C₅Alkyl.

4. method as claimed in claim 1, wherein R1, R2 are methyl or ethyl.

5. method as claimed in claim 1, wherein said double tetrahydrofuran compound are two tetrahydrochysene chaff propane.

6. like each method among the claim 1-5, wherein said conjugated diene 1 is different with conjugated diene 2, is selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethylbutadiene.

7. method as claimed in claim 6, wherein said conjugated diene 1 is selected from divinyl and isoprene with conjugated diene 2.

8. like each method among the claim 1-5, wherein said mono vinyl arenes monomer is selected from vinylbenzene or the substituted vinylbenzene of alkyl.

9. method as claimed in claim 8; Wherein said mono vinyl arenes monomer is selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3; 5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene.

10. method as claimed in claim 9, wherein said mono vinyl arenes monomer is selected from vinylbenzene, Vinyl toluene and alpha-methyl styrene.

11. like the method for claim 10, wherein said mono vinyl arenes monomer is a vinylbenzene.

12. like each method among the claim 1-5, wherein said conjugated diene 1 is selected from divinyl and isoprene with conjugated diene 2, said mono vinyl arenes monomer is a vinylbenzene.

13. like each method among the claim 1-5, wherein the weight in terpolymer is benchmark, the content of said mono vinyl arenes monomer is 10-40wt%; Conjugated diene 1 monomeric content is 5-85wt%; Conjugated diene 2 monomeric content are 5-85wt%.

14. like the method for claim 13, wherein the weight in terpolymer is benchmark, the content of said mono vinyl arenes monomer is 15-25wt%; Conjugated diene 1 monomeric content is 20-60wt%; Conjugated diene 2 monomeric content are 20-60wt%.

15. like each method among the claim 1-5, wherein said solvent is a varsol, this varsol is selected from naphthenic hydrocarbon, aromatic hydrocarbons, isoparaffin or its mixture that contains 5-7 carbon atom.

16. like the method for claim 15, wherein said varsol is selected from hexanaphthene, normal hexane, Skellysolve A, normal heptane, benzene, one or more the mixture in raffinating oil.

17. like the method for claim 16, wherein said varsol is that weight ratio is 80: 20-90: 10 the hexanaphthene and the mixture of normal hexane.

18. like the method for claim 15, wherein control said varsol consumption so that monomer concentration in the scope of 10-20wt%.

19. like each method among the claim 1-5, the temperature when wherein adding initiator is controlled at 35-80 ℃; Polymeric reaction temperature is 50-130 ℃; Polymerization pressure is the 0.005-1MPa gauge pressure.

20. like the method for claim 19, the temperature when wherein adding initiator is controlled at 40-70 ℃; Polymeric reaction temperature is 60-105 ℃; Polymerization pressure is the 0.1-0.3MPa gauge pressure.

21. like each method among the claim 1-5, it further is included in after polyreaction accomplishes, and adds before the terminator, in reaction system, adds optional coupling agent, wherein the mol ratio of coupling agent and organic lithium initiator is 0.05-0.5.

22. like the method for claim 21, wherein the mol ratio of coupling agent and organic lithium initiator is 0.1-0.3.

23. like the method for claim 21, wherein said coupling agent is selected from silicon tetrachloride, tin tetrachloride, hexadiene oxalic acid, dimethyl adipate, Vinylstyrene, dimethyldichlorosilane(DMCS) and METHYL TRICHLORO SILANE.

24. like the method for claim 21, wherein said coupling agent is a tin tetrachloride.

25. like each method among the claim 1-5, it further comprises after the coupling, adds trialkyltin chlorine and as end-capping reagent link coupled segment is not carried out termination process, wherein end-capping reagent is 0.2-1.0 with the mol ratio of coupling part not.

26. like the method for claim 25, wherein the mol ratio of the same not coupling part of end-capping reagent is 0.5-1.0.

27. conjugated diene 1, conjugated diene 2 and a monovinylarene ter-polymer rubber that is obtained by each method among the claim 1-26 has following characteristic:

1) the unit content that is derived from mono vinyl arenes monomer is 10-40wt%;

2) being derived from conjugated diene 1 monomeric unit content is 5-85wt%;

3) being derived from conjugated diene 2 monomeric unit content is 5-85wt%;

4) vinyl structure content is 10-40wt% in the terpolymer; The propenyl structural content is 10-40wt%; Wherein vinyl structure content and propenyl structural content sum are 20-80wt% in the terpolymer;

5) the repeated structural unit number that exists with little block is lower than 1wt% greater than the content of 5 monovinylarene;

6) before coupling, the number-average molecular weight of polymkeric substance is 10-50 ten thousand, and MWD is 1.5-2.5;

7) through after the optional coupling, the coupling efficiency of terpolymer is 20-100%;

28. like the ter-polymer rubber of claim 27, the unit content that wherein is derived from mono vinyl arenes monomer is 15-25wt%; Being derived from conjugated diene 1 monomeric unit content is 20-60wt%; Being derived from conjugated diene 2 monomeric unit content is 20-60wt%; Vinyl structure content is 15-30wt% in the terpolymer, and the propenyl structural content is 15-40wt%, and wherein vinyl structure content and propenyl structural content sum are 30-70wt% in the terpolymer; Before coupling, the number-average molecular weight of polymkeric substance is 12-25 ten thousand; After optional coupling, the coupling efficiency of terpolymer is 30-80%.

29. one kind based on the tire according to the ter-polymer rubber of conjugated diene 1/ conjugated diene 2/ monovinylarene of claim 27 or 28.