CN1425699A - Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax - Google Patents
Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax Download PDFInfo
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Abstract
The low mass trans-1,4-polyisoprene wax and low mass trans-1,4-polybutadiene wax are waxy matter with molecular weight of 1000-3000 and have trans-1,4-structure component content greater than 90%. The low mass trans-1,4-polyisoprene wax has smelting point 40-55 deg.c, and the low mass trans-1,4-polybutadiene wax 80-130 deg.c. They are prepared through solution slurry polymerization or bulk deposition polymerization with hydrogen as chain transferring agent and loaded titanium as catalyst. Hydrogen pressure is maintained in a relatively high level and is regulated to prepare low mass trans-1,4-polyisoprene wax or low mass trans-1,4-polybutadiene wax of different molecular weight levels.
Description
(1) technical field
The invention belongs to the synthetic and Application Areas of organic polymer material, relate to two kinds of polymkeric substance novel materials, promptly, relative molecular-1,4-polyisoprene wax (Middle and Low Relative Molecular MassTrans-1,4-Polyisoprene Wax, be called for short LMTPIW) and in, relative molecular-1,4-butadiene wax (Middle and Low Relative Molecular Mass Trans-1,4-Polybutadiene Wax is called for short LMTPBW).The invention still further relates to the synthetic method of these two kinds of novel materials simultaneously.In the conjugated diene, the low relative molecular mass polymkeric substance should belong to same base polymer material, be commonly referred to fluid rubber, but consider from the angle in industrial significance and monomer source, polyhutadiene and polyisoprene are the conjugated diene polymers that relates at most in industry and the practical application, therefore in the isoprene and divinyl that is specifically related among the present invention, low relative molecular mass polymkeric substance, feature is to have a high regular anti-form-1,4-structure and be easy to crystalline solid wax.
(2) background technology
In, the polyhutadiene and the polyisoprene of low relative molecular mass, early commodity production and widespread use are arranged, normally adopt free radical to regulate polymerization process or anionic polymerisation process is synthetic, the former generally is with hydrogen peroxide (H
2O
2) for radical initiator makes divinyl or isoprene polymerization as chain-transfer agent again simultaneously, obtaining the telechelic polymer that the molecular chain two ends are hydroxyl, relative molecular mass is then by H
2O
2Consumption regulate; The latter then is to be that initiator causes divinyl or isoprene polymerization with lithium alkylide (RLi), molecular weight of polymer by lithium alkylide consumption or add toluene etc. and regulate as chain-transfer agent.These two kinds of methods all can in order in the preparation, the polyhutadiene or the polyisoprene of low relative molecular mass, but be difficult to the microtexture of polymkeric substance is carried out effectively control, generally all be to form cis-1,4-chain link, anti-form-1,4-chain link and 1,2-chain link (to divinyl) or 3, the hybrid structure molecular chain of 4-chain link (to isoprene), therefore, polymkeric substance normally is difficult to the crystalline amorphous state, be liquid or semi-solid dope under the room temperature, be commonly called as fluid rubber.Fluid rubber has the two keys or the end group that can react again because flow processability is good, is widely used in rubber or processing of plastic auxiliary agent, coating, tackiness agent, jointing material, injection rubber item and various chemical raw material.But, also brought many inconvenience, and, also be difficult to obtain the premium properties of many regular polymers because of its structure irregularity to its storing, use because they all are high heavy-gravity liquid.
Polycoordination catalyst system with transition metal, rare earth compound and organometallic compound composition, the microtexture of controlling polymers effectively, synthetic high trans-1,4-structure, high-cis-1,4-structure, high by 1,2-structure or 3, the polyhutadiene of 4-structure or polyisoprene, but general difficulty is effectively controlled the molecular weight of polymkeric substance, particularly is difficult to regulate in synthesizing, the polymkeric substance of low relative molecular mass.Therefore, also rarely adopt so far coordination polymerization process synthetic in, the bibliographical information or the Industrial products of low relative molecular mass polyhutadiene and polyisoprene.
U.S. Patent No. 4,931,376 have reported the organic acid salt of employing lanthanum or cerium and the composite catalyst that organic-magnesium is formed, make polymerizing butadiene or divinyl and other conjugate diene polymerizations, obtain the anti-form-1 of polyhutadiene section, 4-structural content 80～95%, but molecular weight is higher, and average weight-molecular mass is between 30000～300000.
U.S. Patent No. 5,753,579 have reported a kind of synthetic high trans-1,4-structure polyhutadiene, polyisoprene and with the method for styrenic block polymers, system adopts (a) at least a organolithium or organic-magnesium initiator, (b) organo-aluminium compound, (c) alkoxyl group barium and (d) method that is added in the polymerisation medium that organic solvent and at least a conjugated diene form of organic zinc compound is synthetic also is the polymkeric substance of synthetic macromolecule amount.
U.S. Patent No. 6,018,007 is to adopt (a) organolithium compound, (b) organic acid salt of lanthanon is by (a) and the selection proportioning synthesis of trans-1 (b) and the segmented copolymer of other conjugated diene.
U.S. Patent No. 5,089,574 have reported and have adopted three component catalysts: organic cobalt, organoaluminum and side-draw substituting phenol, i.e. Ziegler-Natta type catalyzer, successive polymerization obtains high trans-1.The polymkeric substance that this patent obtains has higher transformation efficiency and low gel content, but can't effectively control the molecular weight of polymkeric substance.Thereafter the U.S. Patent No. of delivering 5,448,002, in above-mentioned cobalt-aluminium-phenol system, added at least a sulfoxide compound such as dialkyl sulphoxide, diaryl sulphoxide or di alkylaryl sulfoxide, can realize the anti-form-1 that molecular weight is controlled, the polymerization of 4-polyhutadiene.But still more than 1.64dl/g, average weight-molecular mass is more than 20,000 for the intrinsic viscosity of its dilute solution.
Day disclosure special permission communique spy opens flat 9-324001 and has announced a kind of relative molecular-1, synthesizing of 4-polyhutadiene, its anti-form-1, the 4-structural content is 80-92%, the dilute solution intrinsic viscosity between 0.4～0.6dl/g, average weight-molecular mass 20,000～40,000, crystalline melt point Tm
1Be 30～50 ℃, Tm
2It is 70～130 ℃.System adopts organic nickel compound, organo-aluminium compound and organo phosphorous compounds composite catalyst catalysis polymerizing butadiene synthetic.And reported that this low-molecular(weight)polymer can be used as the processibility modifying agent and uses.
Chinese invention patent ZL95110352.0 (publication number CN1117501A) has reported a kind of employing load-type Titanium series catalyst and the synthetic high trans-1 of bulk precipitation polymerization technology, the method of 4-polyisoprene, under suitable polymerizing condition, its catalytic efficiency can be greater than 50kg TPI/gTi, the product anti-form-1, the 4-structural content is more than 98%.Molecular weight of polymer is higher, is suitable for the rubber plastic purposes.According to another " China Synthetic Rubber Industry " (1999,22 (57), 276～280) report, adopt this system catalysis polyhutadiene polymerization, also can obtain anti-form-1, the 4-structural content reaches 99%, high-molecular weight anti-form-1,4-polyhutadiene.
Yet about both having high trans-1, the 4-structure is had the anti-form-1 of low relative molecular mass again, 4-polyisoprene wax and anti-form-1, the synthetic report that yet there are no of 4-butadiene wax.
(3) summary of the invention
The present invention synthesizes high trans-1 at aforementioned employing load titanium catalyst system, on the basis of 4-polyisoprene (TPI) and high trans-1 (TPB), and through deep discovering, hydrogen (H
2) can be used as the active chain transfer agent or the relative molecular mass conditioning agent of titanium system catalysis isoprene or divinyl equiconjugate diene polymerization, and along with the raising of hydrogen partial pressure (concentration), the polymkeric substance relative molecular mass continues to reduce.According to this discovery, we adopt and improve the hydrogen pressure polymerization, after reaching certain hydrogen pressure (the used hydrogen pressure of Polymer Synthesizing is much higher usually), in having obtained, the TPI and the TPB waxy polymer of low relative molecular mass, be denomination of invention described in, relative molecular-1,4-polyisoprene wax (LMTPIW) and in, relative molecular-1 wax (LMTPBW).
Hydrogen is inexpensive abundant, easy handling, and being easy to volatilize from polymerization system after polymerization finishes removes, and therefore contaminated polymers and environment are not that the comparatively ideal of regulating molecular weight is selected, and help industrial implementation.
Adopt loading type TiCl
4/ MgCl
2/ X is to obtain high trans-1 as Primary Catalysts, the essential condition of 4-structure polyisoprene and polyhutadiene, and wherein X is to electronics reagent, comprise ester class or ether compound, also can use, general consumption X/Ti=0～10 mol ratios depends on the circumstances.Promotor is an organo-aluminium compound, generally uses AlR
3, R represents to have the alkyl of 1～8 carbon atom, and the most frequently used is triisobutyl aluminium or triethyl aluminum.
Polymerization technique both can adopt solution polymerization (is solvent with aliphatic hydrocarbon, naphthenic hydrocarbon or aromatic hydrocarbons), also can take mass polymerization (with the conjugated diene monomer from as thinner), under suitable polymerizing condition, may be controlled to slurry polymerization or precipitation polymerization, to reduce system viscosity, improve the mass-and heat-transfer effect.Best mode is a bulk precipitation polymerization.Polymerization methods can adopt the tank reactor periodical operation, also can continuous or semicontinuous carrying out, and more easy to control with batch operation.Polymerization temperature is generally 0～60 ℃, with 20～40 ℃ of the bests.
Accompanying drawing 1 and accompanying drawing 2 have shown in the polymerization hydrogen pressure to institute's synthesis of trans-1, the influence of the relative molecular mass of 4-polyisoprene (representing with dilute solution intrinsic viscosity [η] and 150 ℃ of melt viscosities).As seen from the figure, when hydrogen pressure when 1.0MPa is elevated to 2.4MPa, the intrinsic viscosity of polymkeric substance [η] is reduced to 0.23dl/g from 0.58dl/g, melt viscosity (150 ℃) is from 8.5 * 10
4Pa.s is reduced to 0.5 * 10
4Pa.s, corresponding viscosity-average molecular weight drops to below 7,000 from about 30,000, has shown that polymkeric substance relative molecular mass and hydrogen pressure have good linear corresponding relation.
Accompanying drawing 3 be in the polymerization hydrogen pressure to the influence of the relative molecular mass of institute's synthesis of trans-1 (with dilute solution intrinsic viscosity [η] expression).From scheming as seen, when hydrogen pressure when 1.2MPa is elevated to 4.2MPa, the intrinsic viscosity of polymkeric substance can drop to 0.45dl/g from 0.85dl/g, its viscosity-average molecular weight has also dropped to below 20,000.As seen hydrogen pressure also is apparent in view to the influence of polymkeric substance relative molecular mass, the anti-form-1 of low relative molecular mass in can synthesizing with hydrogen accent method fully, the 4-polyhutadiene, for no other reason than that polymerizing butadiene speed is very fast, the polymkeric substance of synthetic same molecular weight needs higher hydrogen pressure than isoprene.
Can also infer that from the test-results of above accompanying drawing 1～3 polymkeric substance of low relative molecular mass more can also improve hydrogen pressure more if desired.But hydrogen pressure is too high, and the requirement to equipment such as polymerization reaction kettles improves low excessively on the other hand relative molecular mass on the one hand, to cause that the polymer crystallization degree reduces and the crystallization imperfection, fusing point reduces, thereby wax intensity is reduced and is clamminess, and may also be unnecessary.In fact, be exactly will be according to the different service requirementss of product, selected suitable hydrogen pressure, the sharp LMTPBW of the LMTPIW of synthetic different molecular weight ranges, different size.For the use field of liquids in general rubber, select the synthetic LMTPIW of hydrogen pressure 1.0～3.0MPa, select the synthetic LMTPBW of hydrogen pressure 2.0～5.0MPa, can synthesize the product of relative molecular mass in 3000～20000 scopes.
Polymerization temperature is seen accompanying drawing 4 to the influence of polymkeric substance relative molecular mass, as seen along with the rising of polymerization temperature, the intrinsic viscosity of polymkeric substance [η] rises, (normally polymerization temperature rises this point with general polycoordination reaction rule, polymericular weight descends) difference may be that the temperature rising causes solubleness (concentration) decline of hydrogen in system to cause.
Polymerization temperature is also influential to catalytic efficiency.When using the catalyst system polymerization of oneself development of this chamber, with the rising of polymerization temperature, catalyst efficiency raises earlier and afterwards reduces, and catalytic efficiency is the highest when 30～50 ℃ of polymerizations.When surpassing 50 ℃, catalytic efficiency descends on the contrary, may cause owing to instability under catalyst active center's high temperature.Consider the characteristic of polymkeric substance, select 10～30 ℃ during isoprene polymerization, select during polymerizing butadiene 30～50 ℃ the most suitable.
Purpose of the present invention, synthesize in the class exactly, low relative molecular mass, usually state is the anti-form-1 of solid wax down, 4-polyisoprene and anti-form-1, the 4-polyhutadiene is with middle low relative molecular mass liquid polyisoprene rubber and the inconvenience of liquid polybutadiene rubber in using and measuring of avoiding using in the market; On the other hand, kept anti-form-1 again, 4-polyisoprene and anti-form-1,4-polyhutadiene excellent dynamic performance.Be used for Rubber processing with LMTPIW and LMTPBW substituted arene wet goods process oil, not only can improve processing characteristics, and the covulcanization that can participate in rubber avoid its in use ooze out contaminate environment, also can improve the dynamic use properties of tire simultaneously, good prospects for application is arranged.Technical conceive is to adopt TiCl
4/ MgCl
2Loaded catalyst catalysis isoprene or polymerizing butadiene (can obtain high trans-1, the 4-structure) are chain-transfer agent or molecular weight regulator with hydrogen, by improving hydrogen pressure, regulate LMTPIW and LMTPBW that polymerization obtains different relative molecular mass fractions.According to this design, under certain polymerizing condition, realized the synthetic of object, its intrinsic viscosity is below 1.0dl/g, and relative molecular mass is 3 * 10
4Below, anti-form-1,4-structural content are the solid-state wax of crystallinity under the room temperature more than 90%.
(4) description of drawings
Accompanying drawing 3 is hydrogen pressure influences to synthetic LMTPBW intrinsic viscosity; Polymerizing condition: Ti/Bd=4.0 * 10
-5, Al/Ti=100, T=35 ℃; Test condition: dilute solution viscosity method, solvent are tetracol phenixin, and 36 ℃ of temperature adopt dark type viscometer;
Accompanying drawing 4 is polymerization temperature influences to synthetic LMTPIW intrinsic viscosity; Polymerizing condition: Ti/Ip=4.0 * 10
-5, Al/Ti=100, PH2=1.62Mpa; Test condition: dilute solution viscosity method, solvent are toluene, and 30 ℃ of temperature adopt dark type viscometer.
(5) embodiment
Starting material
Isoprene (Ip) Shanghai Petrochemical Co. Ltd. produces, and purity is removed high boiling point things such as stopper with preceding through molecular sieve drying and distillation greater than 99.5%.
Rubber plant of divinyl (Bd) Qilu Petrochemical company product, purity also distill through molecular sieve dehydration with preceding greater than 99.5%.
Rubber plant of solvent Qilu Petrochemical company polymerization-grade hydrogenated gasoline, major ingredient is a hexane, 60～90 ℃ of boiling ranges are also distilled through molecular sieve drying with preceding.
Catalyzer (Ti) MgCl
2Load TiCl
4Type is added with or does not add to electronics reagent (ethers, ester class), this laboratory self-control.
Rubber plant of promotor (A1) Beijing Yanshan Petrochemical Company produces triisobutyl aluminium, is made into 2.15mol/L concentration gasoline solution and uses.
High-purity hydrogen (H
2) Qingdao oxygen installation product, purity is greater than 99.995%.
Analysis test method:
Intrinsic viscosity is by determination of ubbelohde viscometer, and LMTPIW and LMTPBW adopt toluene and tetracol phenixin to make solvent respectively.Test condition is respectively 36 ℃ in 30 ℃ of toluene and tetracol phenixin; The calculation formula of LMTPIW: [η]=9.83 * 10
-4M
η 0.6132
Melt viscosity is by NDJ-1 rotor viscometer determining, and measuring temperature is 150 ℃.
Fusing point and degree of crystallinity are measured by Shimadzu DSC-50 type differential thermal analyzer.
Micmstructure of polymer and anti-form-1, the 4-structural content is measured by the Magna-IR spectrometer750 of U.S. Nitolet company, adopts the sample preparation of solution coating method.
Experimental technique:
(band stirs to use 3 liters of stainless steel pressure reactors, rated pressure 5MPa), clean clean, dry, vacuumize, behind the nitrogen replacement, the monomer or the monomer gasoline solution that add about 2 liters, add quantitative Al agent and Ti catalyzer more successively, keep certain stir speed (S.S.) and temperature, and import hydrogen and keep certain hydrogen partial pressure and carry out polymerization.After reaching certain polymerization time and monomer conversion, stop polymerization, remove unconverted monomer and solvent, just obtain powder shape or bulk polymer with the ethanolic soln that contains antioxidant 264.Powder is heated to it more than fusing point, just becomes thick liquid, through cooling, be block wax again.
Add monomer I p1594g in the reactor, with Ti/Ip=6 * 10
-5(mol ratio, down together), Al/Ti=150 (mol ratio, down together), be metered into triisobutyl aluminium (Al) and supported titanium catalyst (Ti) under stirring, and feed the hydrogen of 1.0MPa pressure, in 20 ℃ of following polymerization 29h, stop getting powder shaped polymer 685g, monomer conversion 43%, catalytic efficiency 9900g/gTi after the drying.Body viscosities il=8.5 * 10 of 150 ℃ of following polymer melts
4PaS, intrinsic viscosity [η]=0.51dl/g in 30 ℃ of toluene, the calculating viscosity-average molecular weight is Mn=26,000.Record its anti-form-1, the 4-structural content is greater than 96%.
Experimental procedure is got Ti/Ip=5.1 * 10 with embodiment 1
-5, polymerization time is extended to 72h.Get polymkeric substance 1001g, monomer conversion reaches 77%, catalytic efficiency 2.13 * 10
4G/gTi, polymer body viscosities il=1.2 * 10
4PaS (150 ℃), intrinsic viscosity [η]=0.24dl/g, the calculating viscosity-average molecular weight is M
η=7,800.As seen, prolong polymerization time, help improving polymerisation conversion and catalytic efficiency, and can also effectively reduce the relative molecular mass of resulting polymers.This can be interpreted as, and under this polymerizing condition, the catalytic active center life-span is very long, therefore, prolongs with polymerization time, and catalytic efficiency improves; Simultaneously, along with the polymer beads that generates is constantly grown up, monomer I p (volume is bigger) is more difficult to the less hydrogen molecule of the volume of the diffusion ratio in granule interior active centre, so molecular weight of polymer descends.
Embodiment 3
With embodiment 1, hydrogen pressure is brought up to 1.6MPa, polymerization 21h, monomer conversion are 47%, catalytic efficiency is 1.02 * 10
4G/gTi.Polymer body viscosities il=6.8 * 10
4PaS, intrinsic viscosity [η]=0.47dl/g.
Embodiment 4
With embodiment 1, hydrogen pressure is brought up to 2.0MPa, polymerization 24h, monomer conversion 42.1%, catalytic efficiency are 7.02 * 10
3G/gTi.Polymer body viscosities il=3.2 * 10
4PaS, intrinsic viscosity [η]=0.38dl/g.
Embodiment 5
With embodiment 1, hydrogen pressure further is increased to 2.42MPa, polymerization 24h, monomer conversion 38%, catalytic efficiency are 6.61 * 10
3G/gTi.Polymer body viscosity 9 * 10
3PaS, intrinsic viscosity [η]=0.25dl/g.As seen, improving hydrogen pressure is effectively to reducing the polymkeric substance relative molecular mass, but polymerization velocity and catalytic efficiency are decreased.
Embodiment 6
With embodiment 3, promptly keep hydrogen pressure 1.6MPa, improve polymerization temperature to 30 ℃, polymerization 24h, the final transformation efficiency of monomer is 44%, catalytic efficiency 7.7 * 10
3G/gTi.Polymer body viscosity 8.5 * 10
4PaS, intrinsic viscosity [η]=0.46dl/g.As seen, the rising polymerization temperature, though rate of polymerization and catalytic efficiency increase, the polymkeric substance relative molecular mass also has raising, is disadvantageous to synthetic low-molecular(weight)polymer.
Embodiment 7
With embodiment 6, further improve polymerization temperature to 40,50,60 ℃, equal polymerization 24h, monomer conversion is respectively 48%, 32% and 41%, and catalytic efficiency is respectively 5.63,7.31 and 4.83 * 10
3G/gTi.During 40 ℃ of polymerizations of polymer body viscosity is 7.4 * 10
4PaS, intrinsic viscosity 0.45dl/g, 50 ℃, 60 ℃ polymeric body viscosity surpass 8.5 * 10
4PaS (surpass viscometer rotor range), intrinsic viscosity are respectively 0.52 and 0.50dl/g.As seen, too high polymerization temperature is not favourable to improving catalytic efficiency and reducing the polymkeric substance relative molecular mass.
Embodiment 8
Add industrial naptha 630g and Ip monomer 636g at reactor, press Ti/Ip=6 * 10
-5, Al/Ti=150 adds Al and Ti, feeds the hydrogen of 1.0MPa pressure, 20 ℃ are stirred polymerization 42h down, stop and separate out polymkeric substance with ethanol, after the drying polymkeric substance 269g, monomer conversion 42%, catalytic efficiency 1.03 * 10
4G/gTi, polymer body viscosity 6.6 * 10
4PaS (150 ℃), intrinsic viscosity 0.444dl/g (in 30 ℃ of toluene).As seen, adopt solution polymerization process, result and mass polymerization are approaching, and just catalytic efficiency decreases, and the polymkeric substance relative molecular mass is lower.Occasion needing polymers soln directly to use can adopt solution polymerization to synthesize LMTPIW.
Embodiment 9
In, relative molecular-1, the synthetic method of 4-butadiene wax (LMTPBW) is similar to the method for above synthetic LMTPIW, just the rate of polymerization of divinyl is faster, needs higher hydrogen partial pressure, could obtain the polymkeric substance than low relative molecular mass.For example: in reactor, add the gasoline solution (containing the about 600g of divinyl) of 2L divinyl, press Ti/Bd=4 * 10
-5(mol ratio), Al/Ti=150 (mol ratio) add Al and Ti, and feeding and keep hydrogen pressure is 4.2MPa, and 30 ℃ are stirred polymerization 14h down, stop polymerization and evaporation and remove poly-monomer and solvent, exsiccant finely powdered polymkeric substance 480g.Monomer conversion 80%, catalytic efficiency 2.29 * 10
4G/gTi, polymkeric substance 36 ℃ of intrinsic viscosities that record in tetracol phenixin are 0.44dl/g, 100-120 ℃ of molten limit, and state is the hard wax shape down usually.Record its anti-form-1, the 4-structural content is greater than 94%.
Embodiment 10
With embodiment 9, in reactor, add the divinylic monomer of 2L (about 1250g), carry out bulk precipitation polymerization without solvent, press Ti/Bd=1 * 10
-5, Al/Ti=150 adds Al and Ti, under hydrogen pressure 4.2MPa, and 30 ℃ of polymerization 20h, the termination polymerization is also steamed and is removed poly-monomer, gets dry polymer powder 840g.Monomer conversion 67.2%, catalytic efficiency 7.58 * 10
4G/gTi.Recording intrinsic viscosity under the polymkeric substance equal conditions is 0.58dl/g, and molten limit and rerum natura are with embodiment 9.
Claims (10)
1. in one kind, the anti-form-1 of low relative molecular mass, the 4-polyisoprene, the relative molecular mass that it is characterized in that described polyisoprene is 1000～30000, its anti-form-1, the 4-structural content is greater than 90%.
Claim 1 described in, the anti-form-1 of low relative molecular mass, the 4-polyisoprene is characterized in that described polyisoprene is the crystallinity wax, fusing point is 40～55 ℃.
Claim 1 described in, the anti-form-1 of low relative molecular mass, the 4-polyisoprene, the relative molecular mass that it is characterized in that described polyisoprene is 2000～15000, its anti-form-1, the 4-structural content is greater than 95%.
Claim 3 described in, the anti-form-1 of low relative molecular mass, the 4-polyisoprene is characterized in that described polyisoprene is the crystallinity wax, fusing point is 45～55 ℃.
5. in one kind, the anti-form-1 of low relative molecular mass, the 4-polyhutadiene, the relative molecular mass that it is characterized in that described polyhutadiene is 2000～40000, its anti-form-1, the 4-structural content is greater than 90%.
Claim 5 described in, the anti-form-1 of low relative molecular mass, the 4-polyhutadiene is characterized in that described polyhutadiene is the crystallinity wax, fusing point is 80～130 ℃.
Claim 5 described in, the anti-form-1 of low relative molecular mass, the 4-polyhutadiene, the relative molecular mass that it is characterized in that described polyhutadiene is 3000～20000, its anti-form-1, the 4-structural content is greater than 95%.
Claim 7 described in, the anti-form-1 of low relative molecular mass, the 4-polyhutadiene is characterized in that described polyhutadiene is the crystallinity wax, fusing point is 100～120 ℃.
Aforesaid right require 1～4 each described in, the anti-form-1 of low relative molecular mass, the preparation method of 4-polyisoprene is characterized in that described polyisoprene is with loading type TiCl
4/ MgCl
2/ X-AlR
3Be Preparation of Catalyst, wherein X represents to electronics reagent, comprise ethers or ester compound, the X consumption is X/Ti=0～10 mol ratios, R represents to have the alkyl of 1～8 carbon atom, polymerization process is solution slurry polymerization method or bulk precipitation polymerization method, 0～60 ℃ of polymerization temperature, with hydrogen is the chain-transfer agent of telomerized polymer relative molecular mass, the hydrogen partial pressure of keeping polymerization system is 0.5～5MPa, and molecular weight size adjustment hydrogen partial pressure as required, directly produce the anti-form-1 of different relative molecular mass fractions, 4-polyisoprene.
Aforesaid right require 5～8 each described in, the anti-form-1 of low relative molecular mass, the preparation method of 4-polyhutadiene is characterized in that described polyhutadiene is with loading type TiCl
4/ MgCl
2/ X-AlR
3Be Preparation of Catalyst, wherein X represents to electronics reagent, comprise ethers or ester compound, the X consumption is X/Ti=0～10 mol ratios, R represents to have the alkyl of 1～8 carbon atom, polymerization process is solution slurry polymerization method or bulk precipitation polymerization method, 0～60 ℃ of polymerization temperature, with hydrogen is the chain-transfer agent of telomerized polymer relative molecular mass, the hydrogen partial pressure of keeping polymerization system is 1.0～10MPa, and molecular weight size adjustment hydrogen partial pressure as required, directly produce the anti-form-1 of different relative molecular mass fractions, 4-polyhutadiene.
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| CN102199232A (en) * | 2011-03-24 | 2011-09-28 | 北京化工大学 | Anion trigger system and polymerization method for synthesizing trans polybutadiene and copolymer thereof |
| CN103059368A (en) * | 2011-10-21 | 2013-04-24 | 黄宝琛 | Application of low molecule trans-1, 4-polyisoprene wax |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN105646755A (en) * | 2016-01-25 | 2016-06-08 | 山东玉皇化工有限公司 | Method for increasing polymerization rate of trans-1,4-polyisoprene |
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| CN105601814B (en) * | 2016-03-24 | 2020-11-27 | 青岛科技大学 | Industrial production method of trans-butadiene-isoprene copolymer rubber and device for implementing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007115486A1 (en) * | 2006-04-11 | 2007-10-18 | Qingdao Qust Fangtai Material Engineering Co., Ltd. | Industrial synthesis process of high trans-1, 4-polyisoprene |
| US7718742B2 (en) | 2006-04-11 | 2010-05-18 | Qingdao Qust Fangtai Material Engineering Co., Ltd. | Industrial syntheses process of high tran-1, 4-polyisoprene |
| CN102199232A (en) * | 2011-03-24 | 2011-09-28 | 北京化工大学 | Anion trigger system and polymerization method for synthesizing trans polybutadiene and copolymer thereof |
| CN103059368A (en) * | 2011-10-21 | 2013-04-24 | 黄宝琛 | Application of low molecule trans-1, 4-polyisoprene wax |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN105646755A (en) * | 2016-01-25 | 2016-06-08 | 山东玉皇化工有限公司 | Method for increasing polymerization rate of trans-1,4-polyisoprene |
| CN105646755B (en) * | 2016-01-25 | 2018-03-27 | 山东玉皇盛世化工股份有限公司 | A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization |
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