CN102050968B - Trans-1,4-polydialkene composite rubber and preparation methods thereof - Google Patents
Trans-1,4-polydialkene composite rubber and preparation methods thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 78
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 111
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract 4
- 229920001519 homopolymer Polymers 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000012662 bulk polymerization Methods 0.000 claims description 4
- 238000001125 extrusion 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
- 239000003960 organic solvent Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000086 alane Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- -1 aluminum compound Chemical class 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 abstract 3
- 238000006653 Ziegler-Natta catalysis Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000004513 sizing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 229920002449 FKM Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 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
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a polydialkene composite rubber of trans-1,4- structure and preparation methods thereof. The composite rubber consists of 10 to 80 mass percent of trans-1,4-polyisoprene and 20 to 90 mass percent of trans-1,4-butadiene-isoprene copolymer, wherein over 90 percent of structural units of all dialkenes in the composite rubber have trans-1,4-structures. The first preparation method comprises the following steps of: homopolymerizing isoprene to obtain trans-1,4-polyisoprene by adopting a Ziegler-Natta catalysis system consisting of MgCl2 supported titanium and organic aluminum compound, and then adding butadiene to synthesize the trans-butadiene-isoprene copolymer. The second preparation method comprises the following steps of: adding mixed monomers of butadiene and isoprene into a polymerization device at the same time, performing copolymerization to obtain the butadiene-isoprene copolymer of the trans-1,4-structure, and continuously polymerizing the isoprene to obtain the trans-1,4-polyisoprene after the butadiene with high polymerization speed is completely consumed. The used polymerization device is a stirring reaction kettle or a screw extruder. The composite rubber has excellent performance such as low rolling resistance, low generated heat, abrasion resistance, particularly fatigue break increment resistance and the like, and is suitable for dynamically used rubber products such as tyres, vibration absorption materials and the like.
Description
Technical field
The invention belongs to the polydiolefin field of rubber materials; Be particularly related to anti-form-1; The preparation method of the compounded rubber that 4-TR 301 and anti-form-1,4-butadiene isoprene copolymer are formed and by this method prepare trans 1, the polydiolefin compounded rubber of 4-structure.
Background technology
Along with public security, environmental consciousness constantly strengthen, people are also more and more urgent with the demand of high-performance tire sizing material for automobile.As a kind of new type rubber material; Anti-form-1, it causes people's attention to the diene polymer of 4-structure gradually in the application of high-performance tire sizing material with its excellent dynamic properties (comprising excellent flexible resistance, low rolling resistance, low compression heat generation and abrasion).With suitable-1, the polymer phase ratio of 4-structure has anti-form-1, and the polymer materials of 4-configuration has excellent dynamic performance more.Anti-form-1, the diene homopolymers of 4-structure be like high trans-1, and 4-TR 301 (TPI) and high trans-1 (TPB) are because its very strong crystallization trend and at room temperature be the crystal form plastics.Research shows, the Sulfur (4-6 part) through using high umber or can obtain having the TPI elastomerics of excellent in resistance flexural property, low-rolling-resistance with other blend rubber co-cure with the crystallization of breaking TPI (ZL 95110352.0, ZL200610043556.4; China Synthetic Rubber Industry, 2001,24 (1) 25-28; China Synthetic Rubber Industry 2001,24 (2) 82-86, rubber industry; 2002,49 (3) 133-137).This elastomerics dynamic property is excellent, is suitable for high-performance tire, particularly the tyre rubber material of low-rolling-resistance and low-heat-generation.But TPB is difficult to become elastomerics in order to last method because crystallinity is too strong.
Adopting the method for copolymerization is to be used for breaking the crystalline effective way.(US 5,100,965WO.Pat.97,23521 for patent; US 4,020.115, and US 5; 844,044, UK Pat.Appl.2; 029,426) divinyl (Bd)-isoprene (Ip) multipolymer of the dience rubber of report high trans structure such as high trans structure has excellent physical and mechanical property, is the desirable sizing material of development high-performance tire.Anti-form-1; The synthetic main coordination polymerization catalysts such as the (Rom.Pat.63 of nickel system of adopting of 4-structure Bd-Ip multipolymer; 446), vanadium system (Prom-st.Sint.Kauch.1982, (8): 4-8), cadmium system (Dokl.Akad.NaukSSSR, 1973; 209:369-71), group of the lanthanides/lithium system (JP 0260,907) and Titanium series catalyst.Nickel system, vanadium system, cadmium system and lithium are that catalystsystem exists problems such as the low or trans content of catalytic efficiency (is low.Viton seminar of Qingdao University of Science and Technology is the domestic research group that carries out the diene polymerization of transconfiguration the earliest.
Anti-form-1,4-butadiene-isoprene copolymer glue (TBIR) have excellent dynamic performance, particularly antifatigue and breach increases excellent performance.If synthetic so a kind of compounded rubber, the TPI of existing some amount has the TBIR of some amount again, and its inevitable existing the former low-heat-generation has the latter's antifatigue breach growth property again, is the desirable sizing material on sidewall etc.This patent just relates to the preparation method of this compounded rubber.
Divinyl and isoprene all belong to diolefine, are elastomeric main raw materials, and the TPI/TBIR compounded rubber is just synthetic by the two, adopts bulk precipitation polymerization or solution slurry polymerization.The catalystsystem that adopts is MgCl
2The Titanium series catalyst of load, this catalystsystem have characteristics such as catalytic efficiency (is higher, transconfiguration content height.The employing supported titanium catalyst carries out the isoprene homopolymerization and copolymerization research is significant.Utilize high directionality and selectivity and the isoprene of heterogeneous Titanium series catalyst and the difference that divinyl gathers rate unexpectedly simultaneously, can adopt twice feeding method or one feeding method synthesis of trans-1, the polydiolefin compounded rubber of 4-structure.
Summary of the invention
One of the object of the invention is the needs that are difficult to satisfy the rubber item as the tire to present single material; Provide the heterogeneous Ziegler-Natta catalyst of a kind of employing to carry out polymerization stage by stage or one-step polymerization; The in-situ preparing anti-form-1, the method for 4-polydiolefin compounded rubber.
Two of the object of the invention provides anti-form-1, the compound method of 4-isoprene-butadiene multipolymer.
Three of the object of the invention provides a kind of novel anti-form-1,4-polydiolefin compounded rubber.This compounded rubber comprises the high trans-1 of in-situ polymerization preparation, 4-TR 301 and high trans-1,4-isoprene-butadiene multipolymer.
Four of the object of the invention provides a kind of have excellent flexible resistance, low rolling resistance, low compression heat generation and the low abrasive NEW TYPE OF COMPOSITE rubber that can be used for high-performance tire tyre surface and sidewall rubber.
Anti-form-1 of the present invention, the preparation method of 4-polydiolefin compounded rubber utilizes heterogeneous Ziegler-Natta catalyst, in a reaction unit, carries out polymerization and realizes the in-situ preparing anti-form-1,4-polydiolefin compounded rubber.Can adopt two kinds of methods: a kind of method adds isoprene and divinyl simultaneously in reaction unit, under the catalysis of heterogeneous Ziegler-Natta catalyst, utilizes divinyl and isoprene to gather the difference synthesis of trans-1 of rate unexpectedly, 4-polydiolefin compounded rubber; Or adopt another kind of method: promptly the fs adds isoprene monomer; Synthetic high trans-1 under the catalysis of heterogeneous Ziegler-Natta catalyst; 4-TR 301 (TPI), subordinate phase adds divinyl, is utilized in the heterogeneous Ziegler-Natta catalyst that does not have inactivation in the fs polymerization and continues to cause isoprene and the synthetic butadiene isoprene copolymer of butadiene copolymer; Thereby original position has been synthesized anti-form-1; 4-polydiolefin compounded rubber, and because heterogeneous Ziegler-Natta catalyst has many active site and good hydrogen-sensitivity, prepared anti-form-1; 4-polydiolefin compounded rubber has wider molecular weight distribution, simultaneously can also be through 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-polydiolefin compounded rubber through heterogeneous Ziegler-Natta catalyst in a big way.Compare etc. through controlling two elementary reaction times or monomeric charge; In in a big way, regulate anti-form-1; The relative content of divinyl and isoprene copolymer and isoprene homopolymer and the composition of multipolymer in the 4-polydiolefin compounded rubber; Thereby formed, structure and the adjustable anti-form-1 of performance 4-polydiolefin composite rubber material.
Anti-form-1 of the present invention, 4-polydiolefin compounded rubber are to be dispersed in the anti-form-1 that forms in the isoprene homopolymer, 4-polydiolefin compounded rubber by the butadiene isoprene copolymer that generates in the reaction; Wherein, Compounded rubber is the anti-form-1 of 10-80% by massfraction, the anti-form-1 of 4-TR 301 and 20-90%, and the 4-butadiene isoprene copolymer is formed; The structural unit of all diolefine is anti-form-1 more than 90% in the compounded rubber, the 4-structure.Wherein the mass content of divinyl in butadiene isoprene copolymer is 5%～40%.Copolymerization time, the feed ratio of homopolymerization time and isoprene and divinyl through the control isoprene wait regulates anti-form-1; The content of isoprene copolymer in the 4-polydiolefin compounded rubber; Thereby the anti-form-1 that the structure of obtaining and performance are adjustable, 4-polydiolefin compounded rubber.
Anti-form-1 of the present invention, 4-polydiolefin compounded rubber can be used with natural gum, cis-butadiene cement, butadiene-styrene rubber and other rubber.
Anti-form-1 of the present invention, the preparation method of 4-polydiolefin compounded rubber carries out according to the following steps:
1) in poly-unit, adds quantitative isoprene, organoaluminum and MgCl
2Supported titanium 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 1～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst; The homopolymerization time is 1～72 hour, obtains high trans 1, the isoprene homopolymer of 4-structure; When the homopolymerization time of above-mentioned reaction system reach any time point or monomer conversion in 1～72 hour surpass a certain amount of after; In poly-unit, add divinyl (wherein butadiene content is the 5-30 quality percentage composition of isoprene); Keeping hydrogen partial pressure is 0～1MPa; And make original heterogeneous Ziegler-Natta catalyst continuation initiation isoprene and divinyl carry out copolymerization, obtain anti-form-1, the 4-butadiene isoprene copolymer; Co-polymerization temperature is-15 ℃～80 ℃, and the copolymerization time is 0.1～30 hour; Add acidifying ethanol termination reaction then, remove unreacted monomer, it is described by isoprene homopolymer and trans 1 that drying obtains claim 1, the high trans-1 that the 4-butadiene isoprene copolymer is formed, the polydiolefin compounded rubber of 4-structure.This poly-unit can be that stirred autoclave also can be a screw extrusion press.
2) in poly-unit, add quantitative isoprene, divinyl, organoaluminum and MgCl simultaneously
2Supported titanium catalyst; Have 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 ℃, and hydrogen partial pressure is 0～1MPa, and the mol ratio of Ti element is 1～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst; The mass ratio of divinyl and isoprene is 5-60: 40-95; Polymerization time is 1～72 hour, adds acidifying ethanol termination reaction then and removes unconverted monomer, obtains the polydiolefin compounded rubber after the drying.Polymerization process obtains anti-form-1 for carrying out copolymerization earlier, the 4-butadiene isoprene copolymer, treat that the fast divinyl of polymerization velocity runs out after, isoprene continues polymerization and obtains anti-form-1,4-TR 301 homopolymer.This poly-unit can be that stirred autoclave also can be a screw extrusion press.
The present invention can generate has high trans-1; The isoprene homopolymer of 4-structure and high trans-1; The multipolymer of the butadiene-isoprene of 4-structure; Wherein the mass content of divinyl in multipolymer is 5% to 40%, and the mass ratio of isoprene homopolymer and isoprene copolymer is 10-80: 20-90.
Described organoaluminum is triethyl aluminum or triisobutyl aluminium or dimethyl-monochlor(in)ate aluminium, monomethyl al dichloride, diethylammonium monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or gathers a kind of in the inferior amine alane etc., preferred triisobutyl aluminium.
Described heterogeneous Ziegler-Natta catalyst is with MgCl
2Be the spherical or aspheric catalyzer that contains titanium compound of carrier, wherein, the Ti element account for Ziegler-Natta (Z-N) catalyzer total mass 1%～5%.It is fashionable that this catalyzer is used for the isoprene homopolymerization, and TR 301 anti-form-1,4-structural content can reach more than 98%, the anti-form-1 of divinyl and isoprene during copolymerization, and 4-structural unit content is all more than 90%.
Described titanium compound is selected from TiCl
4, TiBr
4Or TiI
4In a kind of.
Described anti-form-1,4-polydiolefin compounded rubber can be applicable to tire, cushioning material etc. and dynamically use rubber item.
Ziegler-Natta catalyst described in the present invention is used for stage by stage that polymerization prepares anti-form-1, and 4-polydiolefin compounded rubber has following characteristics:
1) utilize the Z-N catalyzer to synthesize and have high trans-1, the characteristics of 4-structure diene polymer synthesize anti-form-1, the polydiolefin compounded rubber of 4-structure, and the tree elastomer that is different from cis-structure and other viton have particular performances.
2) regulate anti-form-1, the content of multipolymer and the composition of multipolymer in the 4-polydiolefin compounded rubber, thereby the adjustable anti-form-1 of the structure of obtaining and performance, 4-polydiolefin compounded rubber through control feed ratio and copolymerization condition.
Embodiment
Embodiment 1
In the reaction unit of 5L, add the 1500mL isoprene monomer successively, (wherein, titanium compound is selected from TiCl to the heterogeneous Ziegler-Natta catalyst of 15mmol triisobutyl aluminium, 1000mL normal heptane and 0.43g
4The mass content of titanium is 2.0%), polymerization temperature is 30 ℃, the homopolymerization time is 24h, obtains isoprene homopolymer; Add the 500ml divinyl, co-polymerization temperature is 40 ℃, and the copolymerization time is 12 hours.With 1wt% acidifying ethanol 500ml termination reaction, remove unreacted monomer, drying obtains 880 gram polydiolefin composite rubber materials.Anti-form-1,4-polydiolefin compounded rubber characteristic is seen table 1.Anti-form-1,4-polydiolefin compounded rubber has good dynamic characteristics, can be applicable to tire tread or sidewall sizing material, or is applied to cushioning material etc.
Embodiment 2
Operation is with embodiment 1, and just the isoprene homopolymerization time is 50h.The result sees table 1.
Embodiment 3
In reaction unit, add the 1500mL isoprene monomer successively, (wherein, titanium compound is selected from TiCl to the heterogeneous Ziegler-Natta catalyst of 17mmol triisobutyl aluminium and 0.43g
4The mass content of titanium is 2.0%), polymerization temperature is 15 ℃, the homopolymerization time is 70h, obtains isoprene homopolymer; Add the 500ml divinyl, co-polymerization temperature is 40 ℃, and the copolymerization time is 20 hours.With 1wt% acidifying ethanol 400ml termination reaction, remove unreacted monomer, drying obtains the anti-form-1 be made up of different 800 gram pentadiene homopolymer and isoprene copolymers, 4-polydiolefin composite rubber material.
Embodiment 4
In reaction unit, add 2000mL isoprene monomer, hexane 1000mL, (wherein, titanium compound is selected from TiCl4 to the Ziegler-Natta catalyst of 36mmol triisobutyl aluminium, 0.56g; The mass content of titanium is 3%), hydrogen partial pressure is 0.05MPa, and polymerization temperature is 10 ℃, and the homopolymerization time is 70h, obtains isoprene homopolymer; Add the 500ml divinyl, 40 ℃ of co-polymerization temperature, the copolymerization time is 15h.With 5wt% acidifying ethanol 500ml termination reaction, remove unreacted monomer, drying obtains the anti-form-1 that 1530 grams are made up of isoprene homopolymer and isoprene copolymer, 4-polydiolefin composite rubber material.The compsn characteristic is seen table 1.Anti-form-1,4-polydiolefin compounded rubber can be applicable to tire tread or sidewall sizing material, or is applied to cushioning material etc.
Embodiment 5
Operation is with embodiment 4, and just hexane is 0ml.The result sees table 1.
Embodiment 6
In reaction unit, add 2000mL isoprene monomer, 527ml divinyl, hexane 1000ml, (wherein, titanium compound is selected from TiCl4 to the Ziegler-Natta catalyst of 34mmol triisobutyl aluminium, 0.6g; The mass content of titanium is 3%), hydrogen partial pressure is 0.1MPa, and polymerization temperature is 30 ℃, and polymerization time is 70h.With 5wt% acidifying ethanol 300ml termination reaction, remove unreacted monomer, drying obtains the anti-form-1 that 1470g is made up of isoprene homopolymer and isoprene copolymer, 4-polydiolefin composite rubber material.The compsn characteristic is seen table 1.
Embodiment 7
In reaction unit, add the 60L isoprene monomer, the 0.5mol triethyl aluminum, (wherein, titanium compound is selected from TiCl4 to the Ziegler-Natta catalyst of 6.8g; The mass content of titanium is 5.0%), hydrogen partial pressure is 0.2MPa, and polymerization temperature is 30 ℃, and the homopolymerization time is 24h, obtains isoprene homopolymer; Add the 4.5L divinyl and carry out copolymerization; 30 ℃ of co-polymerization temperature, the copolymerization time is 20h.With 1wt% acidifying ethanol 2000ml termination reaction, remove unreacted monomer, drying obtains the anti-form-1 that 25kg is made up of isoprene homopolymer and isoprene copolymer, 4-polydiolefin composite rubber material.The compsn characteristic is seen table 1.Anti-form-1,4-polydiolefin compounded rubber can be applicable to tire tread or sidewall sizing material, or is applied to cushioning material etc.
Embodiment 8
In reaction unit, add the 60L isoprene monomer, 4.5L divinyl, 0.58mol triisobutyl aluminium, (wherein, titanium compound is selected from TiCl4 to the Ziegler-Natta catalyst of 6.5g; The mass content of titanium is 5.0%), hydrogen partial pressure is 0.03MPa, and polymerization temperature is 30 ℃, and polymerization time is 24h.With 1wt% acidifying ethanol 2000ml termination reaction, remove unreacted monomer, drying obtains the anti-form-1 that 31kg is made up of isoprene homopolymer and isoprene copolymer, 4-polydiolefin composite rubber material.The compsn characteristic is seen table 1.Anti-form-1,4-polydiolefin compounded rubber can be applicable to tire tread or sidewall sizing material, or is applied to cushioning material etc.
Table 1 embodiment 1～8
| Embodiment | The polydiolefin composite gum, gram | Isoprene copolymer accounts for the mass content/% of compounded rubber | Divinyl accounts for the mass content/% of butadiene isoprene copolymer | The weight-average molecular weight M of polydiolefin compounded rubber W×10 -4/(g/mol) | The MWD M of polydiolefin compounded rubber W/M n | Instead-1,4-structural content Mol% |
| 1 | 880 | 26 | 20 | 33 | 6.4 | 98 |
| 2 | 960 | 20 | 50 | 58 | 4.3 | 99 |
| 3 | 800 | 30 | 28 | 43 | 3.9 | 97 |
| 4 | 1530 | 50 | 27 | 25 | 4.2 | 96 |
| 5 | 1390 | 41 | 21 | 22 | 3.9 | 98 |
| 6 | 1470 | 72 | 20 | 19 | 3.5 | 95 |
| 7 | 25000 | 61 | 5 | 15 | 3.4 | 99 |
| 8 | 31000 | 85 | 10 | 26 | 2.9 | 99 |
The typical anti-form-1 of table 2, the cured properties of 4-polydiolefin compounded rubber
Cross-linked rubber prescription: polydiolefin compounded rubber 100, Triple Pressed Stearic Acid 2, zinc oxide 5, carbon black N330 50, accelerant CZ 1, sulphur 2, process oil 7, antioxidant 264 1 (SBR sulphur 1-75).150 ℃ of curing temperatures
Claims (6)
1. anti-form-1, the polydiolefin compounded rubber of 4-structure is characterized in that; This compounded rubber is the anti-form-1 of 10-80% by massfraction; The anti-form-1 of 4-TR 301 homopolymer and 20-90%, the 4-butadiene isoprene copolymer is formed, and the structural unit of all diolefine is trans 1 more than 90% in the compounded rubber; 4-structure, this compounded rubber are to adopt organoaluminum and MgCl
2Supported titanium catalyst preparation, wherein Al element and the MgCl in the organoaluminum
2The mol ratio of Ti element is 1～200: 1 in the supported titanium catalyst, and the Ti element accounts for MgCl
21%～5% of the total mass of supported titanium catalyst.
2. the preparation method one of the described compounded rubber of claim 1 is synthetic according to the following steps, it is characterized in that: in poly-unit, add quantitative isoprene, organoaluminum and MgCl
2Supported titanium 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 MgCl in the organoaluminum
2The mol ratio of Ti element is 1～200: 1 in the supported titanium catalyst, and the homopolymerization time is 1～72 hour, obtains high trans 1, the isoprene homopolymer of 4-structure; Reach any time point in 1～72 hour when the homopolymerization time of above-mentioned reaction system, in poly-unit, add divinyl, the mass ratio of divinyl and isoprene is 5-30: 100, and keeping hydrogen partial pressure is 0～1MPa, and makes original MgCl
2Supported titanium catalyst continues to cause isoprene and divinyl carries out copolymerization, obtains anti-form-1, the 4-butadiene isoprene copolymer; Co-polymerization temperature is-15 ℃～80 ℃, and the copolymerization time is 0.1～30 hour; Add acidifying ethanol termination reaction then; Remove unreacted monomer; It is described by anti-form-1 that drying obtains claim 1,4-isoprene homopolymer and anti-form-1, the high trans-1 that the 4-butadiene isoprene copolymer is formed; The polydiolefin compounded rubber of 4-structure, this poly-unit can be that stirred autoclave also can be a screw extrusion press.
3. the preparation method two of the described compounded rubber of claim 1 is synthetic according to the following steps, it is characterized in that: in poly-unit, add quantitative isoprene, divinyl, organoaluminum and MgCl simultaneously
2Supported titanium catalyst, have 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 MgCl in the organoaluminum
2The mol ratio of Ti element is 1～200: 1 in the supported titanium catalyst, and the mass ratio of divinyl and isoprene is 5-40: 60-95, and polymerization time is 1～72 hour; Add acidifying ethanol termination reaction then and remove unconverted monomer, obtain anti-form-1 after the drying, 4-polydiolefin compounded rubber; Polymerization process obtains anti-form-1 for carrying out copolymerization earlier, the 4-butadiene isoprene copolymer; After treating that the fast divinyl of polymerization velocity runs out; Isoprene continues polymerization and obtains anti-form-1, and 4-TR 301 homopolymer, this poly-unit can be that stirred autoclave also can be a screw extrusion press.
4. according to claim 2 or 3 described preparing methods, it is characterized in that: described organoaluminum is triethyl aluminum, triisobutyl aluminium, dimethyl-monochlor(in)ate aluminium, monomethyl al dichloride, diethylammonium monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or gathers a kind of in the inferior amine alane.
5. according to claim 2 or 3 described preparing methods, it is characterized in that: described MgCl
2Supported titanium catalyst is to be the spherical or non-spherical catalyst that contains titanium compound of carrier with the magnesium dichloride, and wherein, the Ti element accounts for MgCl
21%～5% of the total mass of supported titanium catalyst.
6. one kind by any described anti-form-1 of claim 1～3; 4-polydiolefin compounded rubber is characterized in that: described anti-form-1, and 4-polydiolefin compounded rubber is by anti-form-1; The isoprene homopolymer of 4-structure and anti-form-1; The 4-butadiene isoprene copolymer is formed, and all isoprene copolymers are that isoprene and butadiene copolymer obtain, and wherein the mass content of divinyl in isoprene copolymer is 5%～60%.
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| CN103059368A (en) * | 2011-10-21 | 2013-04-24 | 黄宝琛 | Application of low molecule trans-1, 4-polyisoprene wax |
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