CN104231120B - A kind of long chain branching high cis-1,4-polyisoprene and preparation method thereof - Google Patents
A kind of long chain branching high cis-1,4-polyisoprene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of long chain branching high cis-1,4-polyisoprene and preparation method thereof, specifically, relate to a kind of by linear high cis-1,4-polyisoprene, in the presence of a free-radical initiator, with Bifunctionalized or multiple functionalized organic compound reaction, prepare high long chain branching high cis-1,4-polyisoprene of branching factor and preparation method thereof.Prepare the long chain branching high cis-1,4-polyisoprene that branching factor is 0.40 ~ 0.99, the molecular chain degradation situation of material is very significantly improved, strain crystallization ability and tensile strength significantly improve, and the performance index such as thermostability, elongation at break, tear strength, hardness and anti-slippery are even better than natural rubber.
Description
Technical field:
The present invention relates to a kind of long chain branching high cis-1,4-polyisoprene and preparation method thereof, be more than or equal to 90% in particular to the cis-Isosorbide-5-Nitrae structural content of one, weight-average molecular weight is 30 × 10
4~ 400 × 10
4, branching factor is the long chain branching high cis-1,4-polyisoprene of 0.40 ~ 0.99, and prepares the method for this long chain branching high cis-1,4-polyisoprene by linear high cis-1,4-polyisoprene and Bifunctionalized or multiple functionalized organic compound reaction.
Background technology:
Natural rubber forms primarily of polyisoprene, and cis-content accounts for more than 98%.Natural rubber molecular structure regularity is good, has good winter hardiness, under tension can crystallization, and have from strengthening action, thus natural rubber has higher intensity, is the desirable glue kind in tire tread compound.Along with the fast development of automotive industry, natural rubber can not can not meet the demand of tire industry far away, the high cis-1,4-polyisoprene (polyisoprene rubber) of synthesis because of its structure similar to natural rubber, be called " natural synthetic rubber ".Main employing titanium system and Nd-based catalyst synthesizing cis content are greater than the high cis-1,4-polyisoprene (polyisoprene rubber) of the linear structure of 94%.
Cis-1 of polyisoprene, the raising of 4 structural contents, be conducive to improving its physical and mechanical properties and dynamic properties, therefore developing different rare earth catalyst is the main method realizing improving further polyisoprene cis-content, see CN101927186A, CN101186663 and US6992157.But linear structure high cis-1,4-polyisoprene (polyisoprene rubber) or natural rubber occur the phenomenon that obvious mooney viscosity declines causing molecular weight and molecular weight in the course of processing, thus affect the physical and mechanical properties of rubber.Linear structure high cis-1,4-polyisoprene (polyisoprene rubber) strain crystallization speed in rubber use procedure is relatively slow, and generation crystallization is relatively weak from reinforcing effect, also can affect the physical mechanical strength of rubber.
Short-chain branch polyisoprene or star hyperbranched poly isoprene have been reported, and wherein cis-structure content is lower than 94%, and weight-average molecular weight is less than 47 × 10
4.Short-chain branch polyisoprene carries out anionic polymerisation process to prepare by macromonomer, see Macromolecules2009, and 42,9592 – 9608; Macromolecules2009,42,1392-1399.Star-branched polyisoprene prepares polyisoprene living chain by Anionic Polymerization of Isoprene to carry out linked reaction to prepare with hyperbranched polyfunctional group terminator again, but coupling efficiency is lower than 64%, cis-content even lower than 75%, see China Synthetic Rubber Industry .2010,33:183 ~ 186.These short-chain branch polyisoprene or star hyperbranched poly isoprene cannot solve current high-cis polyisoprene rubber Problems existing because of character such as cis-content are relatively low, side chain is relatively short, molecular weight is relatively low, and the existence as short-chain branch also may reduce the strain crystallization performance of macromolecular chain.
US2005/0261453A1 and US7319126B2 discloses the method that the method adopting rare earth catalyst polycoordination and coupling agent to stop combining prepares three arms or the star-branched high cis-1,4-polyisoprene of four arms, adopt the catalyst isoprene of rare earth metal phosphonate, aluminum alkyls or alkyl aluminium hydride, alkyl aluminum halide and conjugated diene composition to be polymerized at-55 DEG C ~ 55 DEG C and obtain linear polyisoprene chain, then add coupling agent halo metal-salt (conventional TiCl
4, SnCl
4or PCl
3) or halo organic metal salt (RnM ' X
4-n, R is aliphatics, alicyclic or aromatic group, and M ' is IV or V race metal, and X is halogen, and n is 1 ~ 3) and be obtained by reacting star three arm or four arm polyisoprene, wherein cis-Isosorbide-5-Nitrae structural content is greater than 97%, and weight-average molecular weight is 28 × 10
4~ 148 × 10
4, but coupling efficiency is lower than 60%, and coupling agent residue is more weak with linking of macromolecular chain, may at sulfidation Fracture, see elastomerics, and 1997,7:34 ~ 37; 2001,11:6 ~ 8.
Summary of the invention:
The object of this invention is to provide the long chain branching polyisoprene of a kind of high molecular, high cis-Isosorbide-5-Nitrae structural content, the highly-branched factor, its weight-average molecular weight (M
w) be 30 × 10
4~ 400 × 10
4, cis-Isosorbide-5-Nitrae structural content is greater than 90%, and branching factor is in 0.40 ~ 0.99 scope.Preferably, weight-average molecular weight (M
w) be 50 × 10
4~ 380 × 10
4, cis-Isosorbide-5-Nitrae structural content is greater than 94%, and branching factor is in 0.42 ~ 0.98 scope.
Another object of the present invention is to provide the preparation method of long chain branching polyisoprene of a kind of high molecular, high cis-Isosorbide-5-Nitrae structural content, the highly-branched factor.Under radical initiator effect, by height cis-1, the polyisoprene of 4 structures (cis-content >90%) or natural rubber solution or latex and Bifunctionalized or multiple functionalized organic compound (branching agent) carry out efficiently " click " and react, preparation high molecular, highly-branched factor long chain branching high cis-1,4-polyisoprene.Temperature of reaction is 30 DEG C ~ 150 DEG C, preferably 35 DEG C ~ 120 DEG C, is more preferably 40 DEG C ~ 100 DEG C.Reaction times is relevant with temperature, and temperature is higher, and the reaction times is shorter.Reaction times is 1 minute ~ 2 hours, preferably 2 minutes ~ 1.8 hours, is more preferably 3 minutes ~ 1.6 hours.
Described high cis-1,4-polyisoprene, can be the polyisoprene solution adopting isoprene to be polymerized or to carry out under not having the condition of solvent mass polymerization in organic solvent medium to obtain, or commercially available high cis-1,4-polyisoprene or natural rubber are dissolved in the polyisoprene or natural rubber solution that obtain in organic solvent.Isoprene is polymerized in alkane medium or the method for carrying out mass polymerization under not having the condition of solvent and the catalyzer that adopts all belong to prior art, can adopt rare earth catalyst system or Titanium series catalyst system.
Described radical initiator is selected from any one in following material or their mixture: Diisopropyl azodicarboxylate, azo isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, diethyl azodiformate, diisopropyl azodiformate, azoformic acid dibenzyl ester, 2, two (the 4-methoxy-2 of 2 '-azo, 4-methyl pentane nitrile), 4, 4 '-azo two (4-cyano group valeryl (p-dimethylamino) aniline), 2, two (N-the methylol)-2-methyl-malonamic of 2 '-azo, Cellmic C 121, the different heptamide of azo two, benzoyl peroxide, dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, benzoyl peroxide ethyl ketone, dilauroyl peroxide, azo diisobutyl amidine hydrochloride, azo two different (N-amine ethyl) fourth amidine, azo two isobutyl imidazoline hydrochloride, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Potassium Persulphate or Sodium Persulfate.Be preferably Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, diisopropyl azodiformate, Cellmic C 121, benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide ethyl ketone or dilauroyl peroxide; Be more preferably Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Cellmic C 121, benzoyl peroxide.
Bifunctionalized or multiple functionalized organic compound (branching agent) is selected from any one in following compounds containing thiol groups or their mixture: 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, Isosorbide-5-Nitrae-dimercapto butane, 2,3-dimercapto butane, 1,5-dimercapto pentane, 1,6-dimercaptohexane, 3,4-dimercaptohexane, 1,7-dimercapto heptane, 1,8-dimercapto octane, 1,9-dimercapto nonane, 1,10-dimercapto decane, 1,11-dimercapto undecane, 1,12-dimercapto dodecane, 2,5-dihydroxyl-1,6-dimercaptohexane, 2,6-dihydroxyl-1,7-dimercapto heptane, 3,6-dioxy-1,8-dimercapto octane, 1,2-thioresorcin, dimercapto dihydroxy acetic acid, two Thiovanic acid, two mercapto ethyl thioether, two sulfydryl diethyl thioether, two (2-mercaptoethyl) ether, two Thiovanic acid glycol ester, two mercapto-polyglycol, (two Thiovanic acid isobutyl ester) dioctyltin, dimercapto dihydroxy ethyl hexahydroaniline, 2,4-dimercapto-6-dibutyl amido triazine, 2,5-dimercapto-1,3,4-sulfo-ribavirin, 2,5-dimercaptothiodiazole, DMSA, 4,4'-dimercapto diphenyl sulfide, 2,4,6-tri-thiol-1,3,5-triazines, 1,2,3-trimercaptopropane, 1,3,5-tri-thiol pentane, 3-hydroxyl-1,2,4-tri-thiol butane, 1,2,3,4-tetra-sulfydryl butane, be preferably 1,2-dimercaptoethane, 1,2-dimercaptopropane, Isosorbide-5-Nitrae-dimercapto butane, 1,5-dimercapto pentane, 1,6-dimercaptohexane, 1,10-dimercapto decane, 1,12-dimercapto dodecane, two mercapto ethyl thioether, two sulfydryl diethyl thioether, 2,5-dimercaptothiodiazole, 4,4'-dimercapto diphenyl sulfide or 3-hydroxyl-1,2,4-tri-thiol butane, more preferably 1,3-dimercaptopropane, 1,10-dimercapto decane, two mercapto ethyl thioether, two sulfydryl diethyl thioether, 4,4'-dimercapto diphenyl sulfides or 3-hydroxyl-1,2,4-tri-thiol butane.
Consumption and the linear high cis-1,4-polyisoprene mass values of described branching agent are 0.001% ~ 1.3%, are preferably 0.0015% ~ 1.2%, more preferably 0.002% ~ 1.1%.
The mol ratio of described radical initiator and Bifunctionalized or multiple functionalized organic compound (branching agent) is 1:180 ~ 5:1, is preferably 1:150 ~ 3:1, more preferably 1:135 ~ 2:1.
The concentration of polyisoprene or natural rubber solution arranges relevant with the factor such as polymericular weight, organic solvent, temperature, and usual concentration is 3g/L ~ 150g/L, preferably 10g/L ~ 130g/L, is more preferably 15g/L ~ 110g/L.Described organic solvent is selected from C
4~ C
10saturated alkane or aromatic hydrocarbon in a kind of or their mixture, preferably: butane, pentane, hexane, heptane, iso-pentane, octane-iso, benzene,toluene,xylene, ethylbenzene, o-Xylol, m-xylene, trimethylbenzene or vinylbenzene.
Weight-average molecular weight (M can be prepared by the inventive method
w) be 30 × 10
4~ 400 × 10
4, molecular weight distribution (M
w/ M
n) be 1.1 ~ 4.0, cis-1,4 structural contents are greater than 95%, branching factor is in the high molecular, high cis-1 of 0.40 ~ 0.99 scope, the long chain branching polyisoprene of 4 structural contents, the highly-branched factor, its molecular chain degradation situation is very significantly improved, rubber strain crystallization ability and tensile strength significantly improve, and the performance index such as thermostability, elongation at break, tear strength, hardness and anti-slippery are even better than natural rubber.
Embodiment:
The present invention is further described by following examples, but does not form the restriction to scope and embodiment.
Long chain branching polyisoprene rubber described in the following example is according to GPC/MALLS technology, by by multi-angle light diffusion detector (MALLS) and the coupling of conventional SEC/RI and Viscometer detector system, characterize the weight-average molecular weight (Mw) of linear long-chain branched polymer, number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) and the branching factor ratio of all square rotation radius of linear product (the g=branched product with); Fourier transform infrared spectroscopy (FTIR) is utilized to characterize the content of the cis-Isosorbide-5-Nitrae structure of long chain branching polyisoprene rubber; The rubber being in stretched state is placed in liquid nitrogen cool fast, the above-mentioned sample then taking 5mg carries out DSC test, and test condition is 100 DEG C-100 DEG C, and heat-up rate is 10 DEG C/min, fast cooling; Adopted by rubber the TA-Q50 of TA company to carry out the test of thermostability, test condition is: 0 DEG C-600 DEG C, and heat-up rate is 10 DEG C/min; In rubber plastic steelmaking process, sample under different thin-pass number of times, then adopt the gpc analysis instrument of Waters, US, the molecular weight of working sample; Carry out RPA test to cross-linked rubber, the Δ G ' (difference of shearing modulus) of test gained is less, illustrates that the effect of its glue sample and filler is better; With reference to GB/T528-1998, use the mechanical property of tensilon test cross-linked rubber; Adopt the dynamic properties of TAQ800DMA dynamic mechanical analyzer test cross-linked rubber, test condition is: strain is 0.1%, rate of temperature fall 10 DEG C/min, heat-up rate 10 DEG C/min, and temperature range is-100 DEG C ~ 100 DEG C.
The sulfuration mixing formula (mass fraction) of rubber: rubber: 100, stearic acid: 2, zinc oxide: 5, the N-tertiary butyl-2 benzothiazole sulphenamide: 0.9, sulphur: 2, carbon black (N330): 50, after component mixes in two roller mill, park 24h, sulfuration 22min at 145 DEG C on vulcanizing press.
Embodiment 1
Catalyst preparing and isoprene are all polymerized and carry out all under nitrogen protection.At 0 DEG C, 1g isoprene monomer and the rare earth catalyst containing neodymium octoate, triisobutyl aluminium and trichloromethane is added in polymerization reactor, start polymerization, adiabatic reaction, and add hexane (containing components such as normal hexane, hexanaphthene, methylcyclopentanes) gradually to reaction system in the course of the polymerization process, polymerization reaction time is 5h, add anti-aging agent again to mix, obtain linear polyisoprene/hexane solution, wherein the cis-content of polyisoprene is 96%, weight-average molecular weight (M
w) be 115 × 10
4, molecular weight distribution (M
w/ M
n) be 2.3.
Under 50 DEG C and air atmosphere, add 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1,3-dimercaptopropane to above-mentioned containing in linear polyisoprene/hexane solution (concentration=17g/L), 1,3-dimercaptopropane and polyisoprene mass ratio is made to be 0.0054%, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1, the mol ratio of 3-dimercaptopropane is 1.0, reaction 30min, add ethanol termination reaction, washes clean is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, obtain long chain branching polyisoprene, its cis-Isosorbide-5-Nitrae structural content is 96%, M
wbe 280 × 10
4, M
w/ M
nbe 1.4, branching factor (g) is 0.62.
Embodiment 2
Linear polyisoprene/hexane solution, branching reaction and polymer finishing process are with embodiment 1, and at being 70 DEG C, branching reaction 8min, PDS/PIP mass ratio is 0.0036%.The cis-Isosorbide-5-Nitrae structural content of gained branching polyisoprene is 96%, M
wbe 208 × 10
4, M
w/ M
nbe 2.0, g be 0.97.
Embodiment 3
Linear polyisoprene/hexane solution, branching reaction and polymer finishing process are with embodiment 1, and just 1,10-dimercapto decane and polyisoprene mass ratio are 0.01%, and 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1,10-dimercapto decane mol ratio are 1.0.The cis-Isosorbide-5-Nitrae structural content of gained long chain branching polyisoprene is 96%, M
wbe 226 × 10
4, M
w/ M
nbe 1.8, g be 0.87.
Embodiment 4
Linear polyisoprene/hexane solution, branching reaction and polymer finishing process are with embodiment 2, react 5min at being 70 DEG C, the mass ratio of 4,4'-dimercapto diphenyl sulfide and polyisoprene is 0.013%, the mol ratio of 2,2'-Azobis(2,4-dimethylvaleronitrile) and 4,4'-dimercapto diphenyl sulfide is 1.0.The cis-Isosorbide-5-Nitrae structural content of gained long chain branching polyisoprene is 95.5%, M
wbe 244 × 10
4, M
w/ M
nbe 1.7, g be 0.88.
Embodiment 5
The preparation method of linear polyisoprene/hexane solution is with embodiment 1, and wherein cis-Isosorbide-5-Nitrae structural content is 96%, M
wbe 264 × 10
4, M
w/ M
nbe 1.7.
Branching reaction and polymer finishing process are with embodiment 1, and just the mass ratio of 1,3-dimercaptopropane and polyisoprene is 1.0%.The cis-Isosorbide-5-Nitrae structural content of gained long chain branching polyisoprene is 96%, M
wbe 140 × 10
4, M
w/ M
nbe 2.1, g be 0.91.
Embodiment 6
The preparation method of linear polyisoprene, with embodiment 1, then adds ethanol termination reaction, and washes clean is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and obtaining weight-average molecular weight is 180 × 10
4and molecular weight distribution is the linear high cis-1,4-polyisoprene (cis-content=98%) of 1.8.Dissolved by this linear high cis-1,4-polyisoprene and obtain polyisoprene/hexane solution in hexane, concentration is 19g/L.Carry out branching reaction under 80 DEG C and nitrogen atmosphere, the mass ratio of 4,4'-dimercapto diphenyl sulfide and polyisoprene is 0.013%, and the mol ratio of Diisopropyl azodicarboxylate and 4,4'-dimercapto diphenyl sulfide is 1.0, reaction 30min.The cis-Isosorbide-5-Nitrae structural content of gained branching polyisoprene is 97%, M
wbe 219 × 10
4, M
w/ M
nbe 2.0, g be 0.90.
Embodiment 7
The preparation method of linear polyisoprene and aftertreatment are with embodiment 6.Be 104 × 10 by the weight-average molecular weight obtained
4linear high cis-1,4-polyisoprene (97%) dissolve obtain polyisoprene/hexane solution in hexane, concentration is 24g/L.
Branching reaction is 0.0024% with the mass ratio of embodiment 1,1,3-dimercaptopropane and polyisoprene, and the mol ratio of 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1,3-dimercaptopropane is 1:64, reacts 60min at lower 50 DEG C of nitrogen atmosphere.Polymer finishing process is with embodiment 1.The cis-Isosorbide-5-Nitrae structural content of gained branching polyisoprene is 97%, M
wbe 93 × 10
4, M
w/ M
nbe 1.7, g be 0.45.
Linear rare-earth isoprene rubber is by after branching reaction, and strain crystallization is accelerated, and crystalline fusion enthalpy improves 5 times, and higher than the melting enthalpy 2.8 times of right rubber.And thermostability improves, decomposition temperature all improves 20 DEG C relative to linear rare-earth isoprene rubber or natural rubber.
Linear rare-earth isoprene rubber is by after branching reaction, situation of degrading in rubber plastic steelmaking process be improved significantly, under the same conditions, during thin-pass 32 times, it is 20% that long chain branching polyisoprene molecular weight reduces amplitude, and linear polyisoprene molecular weight reduction amplitude is 51%, it is 48% that natural rubber molecular weight reduces amplitude.
By the mixed effect of the mineral fillers such as the high-cis long chain branching polyisoprene that obtains after branching reaction and carbon black be improved significantly, Payne effect reduces, and △ G' reduces degree and decreases 32.1%.
Compared with linear polyisoprene, the tensile strength of high-cis long chain branching polyisoprene cross-linked rubber improves 40.2%, tear strength improves 59.5%(and improves 25.6% than natural rubber), shore hardness improves 9.7%(and improves 8.0% than natural rubber), wear resistance improves, wet-sliding resistant performance improves 7.2%(and improves 12.4% than natural rubber), rolling resistance reduces 3.9%.
Embodiment 8
Be 166 × 10 by weight-average molecular weight
4, molecular weight distribution be 3.1 and cis-content be 99% natural rubber be dissolved in hexane, compound concentration is the solution of 32g/L.At 50 DEG C, add Diisopropyl azodicarboxylate and 1,3-dimercaptopropane in this solution, make the mass ratio of 1,3-dimercaptopropane and polyisoprene be 0.006%, the mol ratio of 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1,3-dimercaptopropane is 0.008, reaction 60min.Polymer finishing process is with embodiment 1.The cis-Isosorbide-5-Nitrae structural content of gained long chain branching natural rubber is 99%, M
wbe 140 × 10
4, M
w/ M
nbe 2.9, branching factor is 0.65.
By the mixed effect of the mineral fillers such as the long chain branching natural rubber that obtains after branching reaction and carbon black be improved significantly, Payne effect reduces, and △ G' reduces degree and decreases 11.9%.
Compared with natural rubber, long chain branching natural rubber vulcanized rubber performance is further improved, and tensile strength improves 12.6%, tear strength improves 32.6%, and shore hardness improves 11.1%, and wear resistance improves, wet-sliding resistant performance improves 8.8%, and rolling resistance reduces 0.7%.
Claims (8)
1. a long chain branching high cis-1,4-polyisoprene, its cis-Isosorbide-5-Nitrae structural content is greater than 90%, and weight-average molecular weight is 30 × 10
4~ 400 × 10
4, branching factor is 0.40 ~ 0.99.
2. the preparation method of a long chain branching high cis-1,4-polyisoprene, under radical initiator effect, cis-1,4 structural contents be greater than 90% high cis-1,4-polyisoprene or natural rubber and Bifunctionalized or multiple functionalized organic compound react, temperature of reaction is 30 DEG C ~ 150 DEG C, reaction times is 1min ~ 2h, and obtained branching factor is the long chain branching high cis-1,4-polyisoprene of 0.40 ~ 0.99;
Described Bifunctionalized or multiple functionalized organic compound is two sulfydryls or many sulfhydryl compounds, is selected from any one in following material or their mixture: 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, Isosorbide-5-Nitrae-dimercapto butane, 2,3-dimercapto butane, 1,5-dimercapto pentane, 1,6-dimercaptohexane, 3,4-dimercaptohexane, 1,7-dimercapto heptane, 1,8-dimercapto octane, 1,9-dimercapto nonane, 1,10-dimercapto decane, 1,11-dimercapto undecane, 1,12-dimercapto dodecane, 2,5-dihydroxyl-1,6-dimercaptohexane, 2,6-dihydroxyl-1,7-dimercapto heptane, 3,6-dioxy-1,8-dimercapto octane, 1,2-thioresorcin, two Thiovanic acid, two mercapto ethyl thioether, two sulfydryl diethyl thioether, two (2-mercaptoethyl) ether, two Thiovanic acid glycol ester, two mercapto-polyglycol, (two Thiovanic acid isobutyl ester) dioctyltin, dimercapto dihydroxy ethyl hexahydroaniline, 2,4-dimercapto-6-dibutyl amido triazine, 2,5-dimercapto-1,3,4-sulfo-ribavirin, 2,5-dimercaptothiodiazole, DMSA, 4,4'-dimercapto diphenyl sulfide, 2,4,6-tri-thiol-1,3,5-triazines, 1,2,3-trimercaptopropane, 1,3,5-tri-thiol pentane, 3-hydroxyl-1,2,4-tri-thiol butane, 1,2,3,4-tetra-sulfydryl butane.
3. preparation method according to claim 2, it is characterized in that: described radical initiator is selected from any one in following material or their mixture: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, diethyl azodiformate, diisopropyl azodiformate, azoformic acid dibenzyl ester, 2, two (the 4-methoxy-2 of 2 '-azo, 4-methyl pentane nitrile), 4, 4 '-azo two (4-cyano group valeryl (p-dimethylamino) aniline), 2, two (N-the methylol)-2-methyl-malonamic of 2 '-azo, Cellmic C 121, the different heptamide of azo two, benzoyl peroxide, dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, benzoyl peroxide ethyl ketone, dilauroyl peroxide, azo diisobutyl amidine hydrochloride, azo two different (N-amine ethyl) fourth amidine, azo two isobutyl imidazoline hydrochloride, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Potassium Persulphate, Sodium Persulfate.
4. preparation method according to claim 2, is characterized in that: branching reaction temperature is 35 ~ 120 DEG C, and the reaction times is 2min ~ 1.8h.
5. preparation method according to claim 3, is characterized in that: radical initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, diisopropyl azodiformate, Cellmic C 121, benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide ethyl ketone or dilauroyl peroxide.
6. preparation method according to claim 2, is characterized in that: Bifunctionalized or multiple functionalized organic compound is selected from 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,4-dimercapto butane, 1,5-dimercapto pentane, 1,6-dimercaptohexane, 1,10-dimercapto decane, 1,12-dimercapto dodecane, two mercapto ethyl thioether, two sulfydryl diethyl thioether, 2,5-dimercaptothiodiazoles, 4,4'-dimercapto diphenyl sulfides or 3-hydroxyl-1,2,4-tri-thiol butane.
7. according to the preparation method of claim 2 or 4, it is characterized in that: the mass ratio of Bifunctionalized or multiple functionalized organic compound consumption and high cis-1,4-polyisoprene or natural rubber is 0.001% ~ 1.3%; The mol ratio of radical initiator and Bifunctionalized or multiple functionalized organic compound is 1:180 ~ 5:1.
8. preparation method according to claim 7, it is characterized in that: the mass ratio of Bifunctionalized or multiple functionalized organic compound consumption and high cis-1,4-polyisoprene or natural rubber is 0.0015% ~ 1.2%, the mol ratio of radical initiator and Bifunctionalized or multiple functionalized organic compound is 1:150 ~ 3:1.
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