CN102086277B - Polyisoprene composite rubber and preparation method thereof - Google Patents
Polyisoprene composite rubber and preparation method thereof Download PDFInfo
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- CN102086277B CN102086277B CN200910249950.7A CN200910249950A CN102086277B CN 102086277 B CN102086277 B CN 102086277B CN 200910249950 A CN200910249950 A CN 200910249950A CN 102086277 B CN102086277 B CN 102086277B
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- polyisoprene
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 86
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000005060 rubber Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract 6
- 239000010936 titanium Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- -1 aluminum halide Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004807 desolvation Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 229940100630 metacresol Drugs 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000012662 bulk polymerization Methods 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 2
- ILMNHXGPWWXWMD-UHFFFAOYSA-N 3,3-diacetylpentane-2,4-dione;iron Chemical compound [Fe].CC(=O)C(C(C)=O)(C(C)=O)C(C)=O ILMNHXGPWWXWMD-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- CTUKRAIAEPZKSG-UHFFFAOYSA-L [Br-].[Br-].O=[Mo+2]=O Chemical compound [Br-].[Br-].O=[Mo+2]=O CTUKRAIAEPZKSG-UHFFFAOYSA-L 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 235000011147 magnesium chloride Nutrition 0.000 claims 1
- 230000032696 parturition Effects 0.000 claims 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 2
- 239000000463 material Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A polyisoprene composite rubber and preparation method thereof. The composite rubber is composed of 30-80% parts by weight of trans-1,4-polyisoprene with a trans-1,4-unit content of more than 90% and 20-70% parts by weight of 3,4-polyisoprene with a 3,4-unit content of 40-65%. Two preparation methods are provided, wherein the first one adopts a composite catalytic system and the composite rubber of trans-1,4-polyisoprene and 3,4-polyisoprene is obtained by catalyzing the polymerization of isoprene through the composite catalytic system which is composed of a catalyst with trans-1,4-unit orientation characteristic (such as the TiX4 / MgCl2 supported catalyst) and a catalyst with 3,4-unit orientation characteristic (Ti(OR)4-xClx); the second one adopts a stepwise polymerization method and the method comprises the following steps: firstly adding a catalyst with trans-1,4-unit orientation characteristic (TiX4 / MgCl2 supported catalyst) into isoprene monomers for polymerization to obtain trans-1,4-polyisoprene, after a certain conversion rate is achieved adding one or more than one of the catalysts of the Ti(OR)4-xClx system, the Mo system, the Co system, or the Fe system with 3,4-unit orientation characteristic, continuatively catalyzing the polymerization of isoprene to obtain 3,4-polyisoprene and finally to obtain the composite rubber containing trans-1,4-polyisoprene and 3,4-polyisoprene.
Description
Technical field
The invention belongs to the polydiolefin field of rubber materials, more particularly relate to a kind of anti-form-1,4-and 3,4-polyisoprene composite rubber and in-situ polymerization synthetic method thereof.
Background technology
Fast development along with automotive industry and transportation, the continuous increase of the construction of high-grade highway and automobile speed per hour, people have proposed more and more higher requirement to the safety performance of automobile, and grabbing property of ground and wet-sliding resistant performance also become the important indicator of weighing tyre performance.But the dynamic viscous-elastic behaviour of rubber inherence is so that when improving the tire anti-slippery, often can't avoid the increasing of its rolling resistance and Sheng Re, and the decline of abrasion resistance.For this reason, people once attempted the synthetic rubber of different glass transition temperature and natural rubber blend are prepared tread rubber, because that blend glue is separated is larger, so effect is not extremely to be satisfied with.
Qingdao University of Science and Technology successfully adopts supported titanium catalyst catalysis isoprene bulk precipitation polymerization, synthesize high trans-1,4-polyisoprene (TPI) (Chinese invention patent: ZL95110352.0) powder granular products, present 500 ton/years of technical scale pilot scales have normally moved 2 years, and the ton industrialized unit is under preparation.The transconfiguration of polyisoprene chain link, make it have that dynamic heat build up is low, rolling resistance is little and have good dynamic fatigue property and wear resisting property (DE 3227757; Rubber industry, 2001,48 (12): 709-712; Rubber industry, 2002,49 (2): 69-72).The DMA test result shows that TPI has excellent dynamic properties, all tire with rubber in its rolling resistance be minimum.Tire trial-production and enforcement test show, only use 20～25 parts of TPI to substitute SBR in car and underloading half-steel meridian tyre tread rubber, can save fuel oil about 2.5%.
Yet because the crystallinity of TPI molecule causes its wet-sliding resistant performance to descend to some extent than NR, SBR, this is not enough for high-performance tire.Document (Chinese invention patent ZL01104025.4,2001; Rubber industry, 2002,49 (1): 5-8; Rubber industry, 2002,49 (2): 69-72) report adopts TPI and high vinyl polybutadiene rubber (HVBR) also with solving this to contradiction, has obtained the effect that improves wet-sliding resistant performance when reducing rolling resistance.(3,4-PIp) rubber is the extremely domestic and international another virgin rubber kind paid close attention to of rubber industry and research institution in recent years to 3,4-polyisoprene.Research finds that (JP 8223613; Kautu Gummi Kunstst, 1982,35 (12): 1032-1038), 3,4-PIp has extraordinary wet-sliding resistant performance, even be better than SBR, and its living ratio of specific heat SBR is low, but its mechanical property is relatively poor, can not be used for separately tire, can only compound use .3,4-PIp there is not yet the commercial production report, the synthesis catalytic system of 3,4-PIp mainly is divided into two large classes: (US 5082906,1992 for the coordination polymerization catalysts take titanic acid ester one alkyl aluminum system or Fe-series catalyst as representative and the anionic polymerization catalyst take lithium alkylide as initiator; US 3536690,1970; US 4894425,1990; US 5336739,1994).Wherein the document of anionoid polymerization research is a lot of, and its maximum characteristics are the adjustable easy controls of 3,4 structures; Titanic acid ester one alkyl aluminum system of polycoordination, synthetic PIp generally all are high by 3, the 4-structural content, but 3,4-structural content can't regulate and control, and catalytic activity is very low; The most important thing is that this two large class catalyst system all can't both be contained 3,4-structure and contain again anti-form-1, the polyisoprene rubber of 4 structures, and be difficult to carry out in-situ polymerization.
Chinese invention patent " a kind of preparation method of fatty alcohol modified load-type Titanium series catalyst and the application in diene polymerization thereof " (200510102792.4) has been reported and has been adopted fatty alcohol modified supported titanium catalyst, can make and contain 3, the compound polyisoprene rubber of 4-PIp and TPI, but this method of modifying is difficult to the structure of catalyzer is control effectively, thereby is unfavorable for the microtexture of institute's synthetic polymer is effectively regulated.
Summary of the invention
One of purpose of the present invention, it is exactly synthetic a kind of anti-form-1,4-polyisoprene and 3, the 4-polyisoprene composite rubber, have simultaneously 3, good and the anti-form-1 of 4-polyisoprene anti-slippery, 4-polyisoprene low-heat-generation, the characteristics that rolling resistance is low and resistance to fatigue is excellent are desirable sizing materials of preparation high-performance tire.
Two of purpose of the present invention is exactly with the synthetic above-mentioned polyisoprene composite rubber of in-situ polymerization.
Anti-form-1 of the present invention, 4-and 3, the 4-polyisoprene composite rubber is by 3 of reaction situ generation, the 4-polyisoprene is dispersed in anti-form-1, the compounded rubber that forms in the 4-polyisoprene, anti-form-1 in the compounded rubber wherein, the massfraction of 4-polyisoprene is 30-80%, its anti-form-1, the 4-structural content is greater than 90%; The massfraction of 3,4-polyisoprene is 20-70%, and 3,4-structural content is that 40-65% is adjustable.By the add-on and 3 of controlling two kinds of catalyzer, the joining day of 4-structure direction catalyzer etc. is regulated anti-form-1 in the compounded rubber, the content of each structure in 4-polyisoprene and 3, the 4-polyisoprene composite rubber, thereby the adjustable compounded rubber of the structure of obtaining and performance.
The preparation of polyisoprene composite rubber of the present invention is to adopt two kinds of different catalyst systems, carries out polymerization and realize that original position prepares anti-form-1,4-and 3,4-polyisoprene composite rubber in a reactor.One of its preparation method is: add simultaneously in the polymerization reactor and have anti-form-1,4-structure direction feature catalyzer and the catalyzer with 3,4-structure direction feature, the trigger monomer isoprene carries out polymerization and obtains anti-form-1,4-and 3,4-polyisoprene composite rubber; Or adopt another kind of polymerization process, be to add first the fs to have anti-form-1, the catalyzer of 4-structure direction ability synthesizes high trans-1, the 4-polyisoprene, then add the catalyzer with 3,4-structure direction ability in subordinate phase, thereby original position has been synthesized anti-form-1,4-and 3,4-polyisoprene composite rubber.By in polymerization system, adding the relative molecular mass that hydrogen comes telomerized polymer.
The present invention has synthesized the anti-form-1 that composition, structure and performance can be regulated, 4-and 3,4-polyisoprene composite rubber by two kinds of different catalyzer compound uses in a big way.By controlling two elementary reaction times or catalyzer feed ratio etc., in in a big way, regulate anti-form-1,4-polyisoprene and 3, anti-form-1 in the 4-polyisoprene composite rubber, 4-structure and 3, the relative content of 4-structure, thus 4-polyisoprene composite rubber material formed, structure and the adjustable anti-form-1 of performance.
Anti-form-1 of the present invention, 4-and 3,4-polyisoprene composite rubber can use with natural gum, cis-butadiene cement, butadiene-styrene rubber and other rubber compoundings.
Anti-form-1 of the present invention, the preparation method of 4-and 3,4-polyisoprene composite rubber carries out according to the following steps:
1) add quantitative isoprene, organoaluminum to poly-unit, then adding has anti-form-1 simultaneously, and 4-structure direction feature catalyzer is such as TiX
4/ MgCl
2Loaded catalyst, and the catalyzer with 3,4-structure direction feature are such as Ti (OR)
4-xCl
xCarry out in the presence of the hydrocarbon organic solvent solution polymerization or solvent-free under carry out mass polymerization, anti-form-1, Ti element and 3 in the 4-structure direction catalyzer, the mol ratio of Ti element is 1～0.02: 1 in the 4-structure direction catalyzer, polymeric reaction temperature is-15 ℃～80 ℃, hydrogen partial pressure is 0～1MPa, the mol ratio of Ti element is 10～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the catalyzer, and polymerization time is 1～72 hour, then adds acidifying ethanol termination reaction, desolvation and unreacted monomer, drying obtains by anti-form-1, the polyisoprene composite rubber that 4-polyisoprene and 3,4-polyisoprene form.This poly-unit can be that stirred-tank reactor also can be screw extrusion press.
2) add quantitative isoprene, organoaluminum and have anti-form-1 in poly-unit, 4-structure direction feature catalyzer is such as TiX
4/ MgCl
2Loaded catalyst, carry out in the presence of the hydrocarbon organic solvent solution polymerization or solvent-free under carry out mass polymerization, polymeric reaction temperature is-15 ℃～80 ℃, hydrogen partial pressure is 0～1MPa, the mol ratio of Ti element is 10～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the loaded catalyst, the homopolymerization time is 1～72 hour, obtains the isoprene homopolymer of high trans Isosorbide-5-Nitrae-structure; When the homopolymerization time of above-mentioned reaction system reach any time point in 1～72 hour or monomer conversion surpass a certain amount of after, add in the poly-unit and have 3, the second catalyzer of 4-structure direction feature, such as titanium system or Fe system, Mo system and Co series catalysts etc., anti-form-1, Ti element and 3 in the 4-structure direction catalyzer, the mol ratio of metallic element is 1～0.02: 1 in the 4-structure direction catalyzer, keeping hydrogen partial pressure is 0～1MPa, polymerization temperature is-15 ℃～80 ℃, and polymerization time is 0.1～30 hour; Then add acidifying ethanol termination reaction, desolvation and unreacted monomer, drying obtains by anti-form-1, the polyisoprene composite rubber that 4-polyisoprene and 3,4-polyisoprene form.This poly-unit can be that stirred-tank reactor also can be screw extrusion press.
Described organoaluminum is a kind of in triethyl aluminum or triisobutyl aluminium or diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium or the poly-imido grpup aluminium alkane etc., preferred triisobutyl aluminium.
Described TiX
4/ MgCl
2Loaded catalyst is with MgCl
2Be the spherical or aspheric catalyzer that contains titanium compound of carrier, wherein, the Ti element account for catalyzer total mass 1%～5%.When this catalyzer is used for the equal polymerization of isoprene, the polyisoprene anti-form-1, the 4-structural content can reach more than 90%.
Described titanium compound is selected from TiCl
4, TiBr
4Or TiI
4In a kind of.
Described 3,4-structure direction catalyzer can be one or more in Fe-series catalyst or molybdenum series catalyst or cobalt series catalyst or the Titanium series catalyst.
Described Fe-series catalyst is wherein a kind of as part such as the composite and Diisopropyl azodicarboxylate of in the organoiron compounds such as triacetyl acetone iron, isocaprylic acid iron one or more, o-phenanthroline, diethyl phosphite, phosphorous acid di-isooctyl, and wherein the mol ratio of the ferro element in the organoiron compound and part is 1: 0.5～4; Described molybdenum series catalyst be the composite and meta-cresol of in molybdenum tetrachloride, molybdenum pentachloride, the dibromo molybdenum dioxide one or more as part, the mol ratio of meta-cresol and molybdenum element is 20～60: 1; Described cobalt series catalyst is wherein a kind of as part such as the composite and dithiocarbonic anhydride of in cobalt naphthenate, cobalt octoate, the acetylacetone cobalt one or more, diethyl fumarate, thiocarbanil, and the mol ratio of its part and cobalt element is 2～40: 1; Described Titanium series catalyst is one or more in butyl (tetra) titanate, metatitanic acid pentyl ester, the own ester of metatitanic acid etc.
Described anti-form-1,4-and 3,20 ℃ of rebound values that the 4-polyisoprene composite rubber represents wet-sliding resistant performance are lower than TPI, 70 ℃ of rebound values of contemporary hypergene heat are higher than 3, the 4-polyisoprene, have concurrently and give birth to the hot low and good characteristics of wet-sliding resistant performance, can be applicable to the high-speed and energy-saving tire, also use with NR, SBR, BR etc. as one of tread glue formula.
Embodiment
Embodiment 1
In reaction unit, add successively the 1500mL isoprene monomer, the TiX of 17mmol triisobutyl aluminium and 0.43g
4/ MgCl
2(wherein, titanium compound is selected from TiCl to loaded catalyst
4The mass content of titanium is 2.0%) and 18ml tetrabutyl titanate catalyzer, polymerization temperature is 40 ℃, polymerization time is 72h.With 1wt% acidifying ethanol 400ml termination reaction, desolvation and unreacted monomer, drying obtains 780 gram anti-form-1s, 4-and 3,4-polyisoprene composite rubber material.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 63%, and weight-average molecular weight is 1250000g/mol; 3,4-polyisoprene accounts for 37%, and weight-average molecular weight is 200000g/mol, and wherein 3, in the 4-polyisoprene 3,4-structural content 40%.
Embodiment 2
In reaction unit, add successively the 1500mL isoprene monomer, the TiX of 17mmol triisobutyl aluminium and 0.43g
4/ MgCl
2(wherein, titanium compound is selected from TiCl to loaded catalyst
4The mass content of titanium is 2.0%), polymerization temperature is 15 ℃, polymerization time is 70h, obtains trans Isosorbide-5-Nitrae-polyisoprene; Add 12ml tetrabutyl titanate catalyzer, keep 30 ℃ of polymerization temperatures, continue polymerization 20 hours.With 1wt% acidifying ethanol 400ml termination reaction, desolvation and unreacted monomer, drying obtains 840 gram polyisoprene composite rubber materials.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 75%, and weight-average molecular weight is 1500000g/mol; 3,4-polyisoprene accounts for 25%, and weight-average molecular weight is 500000g/mol, and wherein 3, in the 4-polyisoprene 3, the 4-structural content is 55%.The composite gum dynamic property sees Table 1.
Embodiment 3
Operation is with embodiment 2, and the organoaluminum of just selecting is not triisobutyl aluminium, but triethyl aluminum.Final drying obtains 850 gram anti-form-1s, 4-and 3,4-polyisoprene composite rubber material.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 80%, and weight-average molecular weight is 1120000g/mol; 3,4-polyisoprene accounts for 20%, and weight-average molecular weight is 480000g/mol, and wherein 3, in the 4-polyisoprene 3,4-structural content 60%.
Embodiment 4
Operation is with embodiment 2, and adding hydrogen partial pressure when being polymerization is 0.2MPa.Final drying obtains 680 gram anti-form-1s, 4-and 3,4-polyisoprene composite rubber material.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 78%, and weight-average molecular weight is 800000g/mol; 3,4-polyisoprene accounts for 22%, and weight-average molecular weight is 360000g/mol, and wherein 3, in the 4-polyisoprene 3,4-structural content 53%.
Embodiment 5
In reaction unit, add successively the 1500mL isoprene monomer, the TiX of 15mmol triisobutyl aluminium, 1000mL normal heptane and 0.43g
4/ MgCl
2(wherein, titanium compound is selected from TiCl4 to loaded catalyst; The mass content of titanium is 2.0%), polymerization temperature is 50 ℃, polymerization time is 24h, obtains anti-form-1, the 4-polyisoprene; Add 8mmol molybdenum series catalyst (mol ratio of molybdenum element and meta-cresol is 1: 2), keep 50 ℃ of polymerization temperatures, continue polymerization 12 hours.With 1wt% acidifying ethanol 500ml termination reaction, desolvation and unreacted monomer, drying obtains 880 gram polyisoprene composite rubbers.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 30%, 3,4-polyisoprene and accounts for 70%, and wherein 3, in the 4-polyisoprene 3,4-structure (with 1,2-structure) content 65%.The composite gum dynamic property sees Table 1.
Embodiment 6
In reaction unit, add successively the 1500mL isoprene monomer, the TiX of 15mmol triisobutyl aluminium, 1000mL normal heptane and 0.43g
4/ MgCl
2(wherein, titanium compound is selected from TiCl to loaded catalyst
4The mass content of titanium is 2.0%), polymerization temperature is 50 ℃, polymerization time is 24h, obtains anti-form-1, the 4-polyisoprene; The cobalt series catalyst (mol ratio of cobalt element and diethyl fumarate is 1: 10) that adds 5mmol molybdenum series catalyst (mol ratio of molybdenum element and meta-cresol is 1: 2) and 4mmol keeps 50 ℃ of polymerization temperatures, continues polymerization 12 hours.With 1wt% acidifying ethanol 500ml termination reaction, desolvation and unreacted monomer, drying obtains 820 gram polyisoprene composite rubbers.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 36%, 3,4-polyisoprene and accounts for 64%, and wherein 3, in the 4-polyisoprene 3,4-structure (with 1,2-structure) content 58%.
Embodiment 7
Operation is with embodiment 6.The catalyzer with 3,4-structure direction feature that just adds is not molybdenum series catalyst and cobalt series catalyst, but the metatitanic acid n-pentyl ester of 8mmol.Obtain at last the 560g polyisoprene composite rubber.Anti-form-1 in the composite gum, the 4-polyisoprene accounts for 53%, 3,4-polyisoprene and accounts for 47%, and wherein 3, in the 4-polyisoprene 3,4-structure (with 1,2-structure) content 41%.
The typical anti-form-1 of table 1,4-and 3,4-polyisoprene composite rubber cross-linked rubber rebound resilience
| TPI | Embodiment 2 | Embodiment 5 | 3,4-polyisoprene | |
| Rebound value/% (20 ℃) | 51 | 25 | 23 | 16 |
| Rebound value/% (70 ℃) | 62 | 32 | 26 | 24 |
Cross-linked rubber prescription: rubber 100, stearic acid 2.5, zinc oxide 5, carbon black N33050, accelerant CZ 0.6, altax 0.5, Vulcanization accelerator TMTD 0.3. sulphur 2, antioxidant 4010NA 1.5.150 ℃ of curing temperatures.
Claims (8)
1. a polyisoprene composite rubber is characterized in that, this compounded rubber is the anti-form-1 of 30-80% by massfraction, the 4-structural content is greater than 90% anti-form-1,4-polyisoprene and massfraction are 3 of 20-70%, and the 4-structural content is 3 of 40-65%, and the 4-polyisoprene forms.
2. the preparation method of compounded rubber claimed in claim 1 is synthetic according to following steps, it is characterized in that: add quantitative isoprene, organoaluminum to poly-unit, then adding has anti-form-1, the TiX of 4-structure direction feature simultaneously
4/ MgCl
2Loaded catalyst, and the Ti (OR) with 3,4-structure direction feature
4-xCl
xCatalyzer, carry out in the presence of the hydrocarbon organic solvent solution polymerization or solvent-free under carry out mass polymerization, anti-form-1, Ti element and 3 in the 4-structure direction catalyzer, the mol ratio of Ti element is 1～0.02: 1 in the 4-structure direction catalyzer, polymeric reaction temperature is-15 ℃～80 ℃, hydrogen partial pressure is 0～1MPa, the mol ratio of Ti element is 10～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the catalyzer, polymerization time is 1～72 hour, then add acidifying ethanol termination reaction, desolvation and unreacted monomer, drying obtains claimed in claim 1 by anti-form-1, the polyisoprene composite rubber that 4-polyisoprene and 3,4-polyisoprene form.
3. the preparation method of compounded rubber claimed in claim 1 is synthetic according to following steps, it is characterized in that: add quantitative isoprene, organoaluminum and TiX in poly-unit
4/ MgCl
2Loaded catalyst, carry out in the presence of the hydrocarbon organic solvent solution polymerization or solvent-free under carry out mass polymerization, polymeric reaction temperature is-15 ℃～80 ℃, hydrogen partial pressure is 0～1MPa, Al element and TiX in aluminum alkyls or the aikyl aluminum halide
4/ MgCl
2The mol ratio of Ti element is 10～200: 1 in the loaded catalyst, and the homopolymerization time is 1～72 hour, obtains the isoprene homopolymer of high trans Isosorbide-5-Nitrae-structure; When the homopolymerization time of above-mentioned reaction system reach any time point in 1～72 hour or monomer conversion surpass a certain amount of after, add in the poly-unit and have 3, in the Fe-series catalyst of 4-structure direction feature or molybdenum series catalyst or cobalt series catalyst or the Titanium series catalyst one or more, anti-form-1, Ti element and 3 in the 4-structure direction catalyzer, the mol ratio of metallic element is 1～0.02: 1 in the 4-structure direction catalyzer, keeping hydrogen partial pressure is 0～1MPa, polymerization temperature is-15 ℃～80 ℃, and polymerization time is 0.1～30 hour; Then add acidifying ethanol termination reaction, desolvation and unreacted monomer, drying obtains claimed in claim 1 by anti-form-1, the polyisoprene composite rubber that 4-polyisoprene and 3,4-polyisoprene form.
4. it is characterized in that according to claim 2 or 3 described methods: described organoaluminum is a kind of in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium or the poly-imido grpup aluminium alkane.
5. it is characterized in that: described TiX according to claim 2 or 3 described methods,
4/ MgCl
2Loaded catalyst is the spherical or non-spherical catalyst of the titanium compound of containing take magnesium dichloride as carrier, and wherein X can be Cl, Br or I, and the Ti element accounts for 1%～5% of catalyzer total mass.
6. method claimed in claim 2 is characterized in that: 3,4-structure direction catalyzer Ti (OR)
4-xCl
xIn R be alkyl, the number of its carbon atom be 4,5 or 6, x be 0-3.
7. method claimed in claim 3, it is characterized in that: described Fe-series catalyst be in the composite and Diisopropyl azodicarboxylate of in triacetyl acetone iron, the isocaprylic acid iron organoiron compound one or more, o-phenanthroline, diethyl phosphite, the phosphorous acid di-isooctyl any as part, wherein the mol ratio of the ferro element in the organoiron compound and part is 1: 0.5～4; Described molybdenum series catalyst be the composite and meta-cresol of in molybdenum tetrachloride, molybdenum pentachloride, the dibromo molybdenum dioxide one or more as part, the mol ratio of meta-cresol and molybdenum element is 20～60: 1; Described cobalt series catalyst be in the composite and dithiocarbonic anhydride of in cobalt naphthenate, cobalt octoate, the acetylacetone cobalt one or more, diethyl fumarate, the thiocarbanil any as part, the mol ratio of its part and cobalt element is 2～40: 1; Described Titanium series catalyst is that in butyl (tetra) titanate, metatitanic acid pentyl ester, the own ester of metatitanic acid one or more are composite.
8. one kind by the synthetic polyisoprene composite rubber of the described method of claim 2～3, has both had an anti-slippery good, has again the low characteristics of the heat of giving birth to, and is specially adapted to the tread mix of high-speed tire.
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| CN103387641B (en) * | 2012-05-08 | 2016-04-06 | 青岛科技大学 | A kind of anti-form-1, butadiene-isoprene copolymer glue of 4-structure and preparation method thereof |
| CN103289000B (en) * | 2013-07-01 | 2015-09-02 | 青岛科技大学 | A kind of High molecular weight polyisoprene rubber and preparation method thereof |
| CN103819761A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Novel isoprene rubber |
| FR3044315B1 (en) * | 2015-11-27 | 2017-12-08 | Michelin & Cie | RUBBER COMPOSITION |
| CN112625159B (en) * | 2020-12-23 | 2022-05-10 | 青岛竣翔科技有限公司 | Preparation method and application of catalyst for synthesizing hydroxyl-terminated trans-1, 4-polyisoprene polymer |
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