CN103374102B - The production method of 1,3-conjugated-diolefin/uni-vinyl-arene copolymer and successive polymerization thereof - Google Patents
The production method of 1,3-conjugated-diolefin/uni-vinyl-arene copolymer and successive polymerization thereof Download PDFInfo
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Abstract
The invention discloses a kind of successive polymerization and produce 1, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the method comprises containing monomer a, organic solvent, described reactor sent into continuously by the reaction mass of alkyl tetrahydro furfuryl alcohol ether and organolithium, under anionic polymerization conditions, monomer a is contacted with organolithium and obtains multipolymer, wherein, described monomer a is monovinylarene and 1, 3-conjugated diene, wherein, described reaction mass is also containing gel inhibitor 1, 2-divinyl, wherein, with the weight of monomer a for benchmark, 1, the consumption of 2-divinyl or ethyl acetylene is 100-250ppm.The method, within the short polymerization residence time, can obtain high transformation efficiency, the copolymer ethylene base content obtained and mooney viscosity high.
Description
Technical field
The present invention relates to the production method of 1,3-conjugated-diolefin/uni-vinyl-arene copolymer and successive polymerization thereof.
Background technology
Solution polymerized butadiene styrene rubber (SSBR) is over-all properties a kind of conventional rubber between emulsion polymerized styrene butadiene rubber (ESBR) and cis-1,4-polybutadiene rubber (BR).In actual use, compared with ESBR, the advantage such as it has abrasion performance, resistance toly to subdue, low temperature resistant, heat-dissipating is low, rolling resistance is little; Compared with BR, it has rubber not cold flow, and cross-linked rubber tensile strength is high, anti tear, the advantage such as anti-slippery.In process industrial art performance, SSBR rubber unvulcanizate shrinks little, and extrudate smooth surface, mold pressing good fluidity, cross-linked rubber decorative pattern is clear and in bright gay color, can in a large number for tire tread glue, shoemaking industry and other technical rubber goods.Along with the development of motorway and high-performing car and high-performance tire, the reinforcement of environmental protection and power conservation requirement, SSBR will have vast potential for future development in future.Research shows, improves SSBR styrene content and can improve second-order transition temperature (Tg) and sliding resistance, but also by dissipation factor (Tan δ) value at raising 60 DEG C, this means that rolling resistance increases.Improve contents of ethylene, Tg and sliding resistance can be improved, and rolling resistance does not increase.Therefore one of competitive glue kind of the most that can balance anti-slippery and rolling resistance is become compared with the SSBR of high-vinyl-content.
SSBR production technique has interval and continuous dividing, and current domestic and international most of company all adopts batch polymerization processes, only has a handful of company to adopt continuous polymerization technique.With regard to domestic and international existing continuous polymerization unit, polymerization technique carries out under high monomer concentration conditions under normal circumstances, the advantage of this technique is that polymerization temperature is high, transformation efficiency is high and throughput is strong, production cost can be reduced simultaneously, but such shortcoming is also obvious, under the high temperature conditions, the contents of ethylene of product can reduce, and is unfavorable for high-vinyl product in preparation.
US Patent No. 20070219316A describes with 2-methoxy ethyl tetrahydrofuran (THF) (THFA-ethyl) as properties-correcting agent, continuous polymerization technique is adopted to prepare vinyl-arene/conjugated diene copolymer, reactive polymeric temperature is at 80-110 DEG C, obtained copolymer ethylene aromaticity content scope is 15-50%, reaction time 30-120 minute by weight.Due to this preparation method carry out at 80-110 DEG C time, add the gel inhibitor of convention amount, the transformation efficiency of reaction is not high.If do not add gel inhibitor, then produce a large amount of gel.
CN101386667A discloses a kind of method that high temperature continuous polymerization technique prepares high-vinyl solution polymerized butylbenzene, the method adopts alkyl tetrahydro furfuryl group ether to be polar modifier, adopt continuous polymerization technique, under the condition of polymerization temperature 80-150 DEG C, synthesis high-vinyl solution polymerized butylbenzene.The product medium vinyl content obtained can reach more than 30%.The content of the vinyl structure of polymkeric substance when although this invention can improve high temperature polymerization, but high temperature successive polymerization prepare medium vinyl structure, high Mooney viscosity butylbenzene copolymer time, due to adding of ethyl tetrahydrofurfuryl ether, the transformation efficiency of reaction within the rational residence time can be made on the low side, in addition alkyl tetrahydro furfuryl group ether can suppress the branching of polymer molecular chain, the mooney viscosity of the butylbenzene copolymer of gained is low, when the butylbenzene copolymer obtained is for the preparation of oil-extended styrene-butadiene rubber, the requirement of mooney viscosity can not be met.
CN101255203A describes a kind of method suppressing gel to produce when preparing styrene-butadiene rubber(SBR), uses alpha-olefin or its mixture as gel inhibitor in the method.The method can solve the process that styrene-butadiene rubber(SBR) polymerization process easily produces gel effectively.But the contents of ethylene how improved in butylbenzene copolymer is not related to.When more not relating to employing ethyl tetrahydrofurfuryl ether as irregular agent, how to improve the transformation efficiency of polymerization thus the molecular weight of raising butylbenzene copolymer, making the styrene-butadiene rubber(SBR) prepared when the degree of branching is certain, improving the mooney viscosity of butylbenzene copolymer by improving molecular weight.
Under normal circumstances, the transformation efficiency of monomer can be improved by the consumption strengthening initiator, but along with the increase of initiator amount, the molecular weight of multipolymer can reduce, thus causes the mooney viscosity of the butylbenzene copolymer prepared low.In addition, by extending the residence time of polymerization, the transformation efficiency of monomer can also be improved.But for successive polymerization, the residence time extending polymerization will cause the reduction of production efficiency, thus makes the advantage of successive polymerization lose.
Summary of the invention
The object of the invention is to produce 1 to overcome successive polymerization in prior art, during 3-conjugated-diolefin/uni-vinyl-arene copolymer, in order to obtain medium vinyl content, 1 of higher molecular weight, during 3-conjugated-diolefin/uni-vinyl-arene copolymer, monomer conversion when needing the residence time extending polymerization to improve polymerization thus cause the inefficient shortcoming of continuous seepage, there is provided a kind of within the rational residence time, during polymerization, monomer conversion is high, and the successive polymerization production medium vinyl 1 that the mooney viscosity obtaining butylbenzene copolymer is high, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer.
The invention provides a kind of successive polymerization produce in 1, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the method comprises containing monomer a, organic solvent, described reactor sent into continuously by the reaction mass of alkyl tetrahydro furfuryl alcohol ether and organolithium, under anionic polymerization conditions, monomer a is contacted with organolithium and obtains multipolymer, wherein, described monomer a is monovinylarene and 1, 3-conjugated diene, described reaction mass is also containing gel inhibitor 1, 2-divinyl, wherein, with the weight of monomer a for benchmark, 1, the consumption of 2-divinyl is 100-250ppm.
Present invention also offers 1,3-conjugated-diolefin/uni-vinyl-arene copolymer prepared by a kind of aforesaid method.
Method of the present invention, 1 can be produced in successive polymerization, during 3-conjugated-diolefin/uni-vinyl-arene copolymer, improve 1, while the transformation efficiency of 3-conjugated-diolefin/uni-vinyl-arene, make that the contents of ethylene of the butylbenzene copolymer obtained is medium, mooney viscosity is high, and the gel content produced during reaction is lower.Such as, in embodiment 1 with the weight of monomer a for benchmark, the consumption of described gel inhibitor is that 250ppm, the polyreaction residence time are when being 50 ± 1 minutes, the transformation efficiency of the phenylethylene/butadiene of the first and second stills is respectively 89.3/93.7%, 97.3/98.1%, the contents of ethylene of obtained butylbenzene copolymer and mooney viscosity, molecular weight distribution are respectively 34.6 % by weight, 131,2.322, and the gel content that polymerization produces is 73ppm; And in comparative example 2 with the weight of monomer a for benchmark, the consumption of 1，2-butadiene is 50ppm, the polyreaction residence time when being 50 ± 1 minutes, and the transformation efficiency of the phenylethylene/butadiene of the first and second stills is respectively 95.1/98.4,99.8/99.9; The contents of ethylene of obtained butylbenzene copolymer and mooney viscosity, molecular weight distribution are respectively 33.5 % by weight, 144,2.872, although transformation efficiency and molecular weight distribution high, but the gel content that polymerization produces is 889ppm, and gel content value is obviously higher, does not meet the requirement of product to gel content; And in comparative example 3,1, the consumption of 2-divinyl is that 350ppm, the polyreaction residence time are when being 50 ± 1 minutes, the transformation efficiency of the phenylethylene/butadiene of the first and second stills is respectively 85.1/87.6,90.6/93.5, the contents of ethylene of the butylbenzene copolymer obtained is 33.7 % by weight, mooney viscosity is 125, molecular weight distribution is 2.334, and conversion rate of products is on the low side.Illustrate thus and adopt method of the present invention, within the rational residence time, while the product gel content that guarantee obtains is lower, 1 can be improved, the transformation efficiency of 3-conjugated-diolefin/uni-vinyl-arene, such that the contents of ethylene of the butylbenzene copolymer obtained is medium, mooney viscosity is high.
Embodiment
The invention provides a kind of successive polymerization and produce 1, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the method comprises containing monomer a, organic solvent, described reactor sent into continuously by the reaction mass of alkyl tetrahydro furfuryl alcohol ether and organolithium, under anionic polymerization conditions, monomer a is contacted with organolithium and obtains multipolymer, wherein, described monomer a is monovinylarene and 1, 3-conjugated diene, wherein, described reaction mass is also containing gel inhibitor 1, 2-divinyl, with the weight of monomer a for benchmark, 1, the consumption of 2-divinyl is 100-250ppm.
According to of the present invention 1, the preparation method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, as long as owing to ensureing in solution continuous polymerization process, when employing alkyl tetrahydro furfuryl alcohol ether is structure regulator, adding 1，2-butadiene is gel inhibitor, and by 1, the amount ranges of 2-divinyl controls just can realize object of the present invention at 100-250ppm, has no particular limits the concrete operations in preparation process.Such as, the mol ratio between the monomer that the kind of the kind of described polymerizing condition, organolithium and consumption, polymerization solvent for use and consumption, copolymerization are used and monomer all can refer to prior art and carries out.
In the present invention, term " basic glue " refers to the multipolymer of gained after solution polymerization, and therefore, in the present invention, " butylbenzene copolymer " and " basic glue " can be interchangeable." residence time " refers to residence time of the reaction mass in single reactor, in the present invention, polymerization time=mono-still the residence time × still number.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, although meet 1 of above-mentioned requirements, the consumption of 2-divinyl just can realize object of the present invention, but under preferable case, with the weight of monomer a for benchmark, the consumption of 1，2-butadiene can be 150-200ppm.Meet the 1，2-butadiene of preferable amount, can, while the gel content of basic glue controls within the specific limits, improve the transformation efficiency in the reasonable successive polymerization residence time further, and the contents of ethylene of the product obtained be medium, mooney viscosity is high.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, although of the prior art various 1,3-conjugated diene all can realize object of the present invention, preferably, described 1,3-conjugated diene is the one in 1,3-butadiene, isoprene, m-pentadiene.
In the present invention, described monovinylarene such as formula shown in I,
In formula I, R
1can be C
6-C
20substituted or unsubstituted aryl.The specific examples of described monovinylarene can be, but not limited to: vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethyl, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene or 4-dodecylstyrene.
One of the present invention preferred embodiment in, described 1,3-conjugated diene is 1,3-butadiene, and described monovinylarene is vinylbenzene, and the butylbenzene copolymer particularly suitable so formed prepares tire synthetic rubber.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the consumption of the present invention to organolithium does not have particular requirement, preferably, the consumption of described organolithium is 0.25-0.9 mmole/100 gram monomer a, further preferably, the consumption of described organolithium is 0.28-0.42 mmole/100 gram monomer a.
The method of 1,3-conjugated-diolefin/uni-vinyl-arene copolymer is produced, in order to improve 1 according to successive polymerization of the present invention, the over-all properties of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the weight ratio of optimization styrene of the present invention and 1,3-butadiene is 1: 1-4, is preferably 1: 2.5-3.5; The weight ratio of 1,3-butadiene and solvent is 0.05-0.27: 1, is more preferably 0.14-0.22: 1, most preferably is 0.18-0.2: 1.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the consumption of the present invention to described alkyl tetrahydro furfuryl alcohol ether does not have particular requirement, preferably, the mol ratio of alkyl tetrahydro furfuryl alcohol ether and organolithium is 0.4-8: 1, be preferably 1-7: 1, more preferably 5-5.2: 1.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, although the condition of anionoid polymerization of the prior art all can realize object of the present invention, preferably, described anionic polymerization conditions comprises: polymeric reaction temperature is 110-150 DEG C, is preferably 120-128 DEG C; Polymerization pressure is 0.5-0.9MPa; Be preferably 0.55-0.8MPa; Polymerization reaction time is 30-270min, is preferably 60-160min.Meet the anionic polymerization conditions of aforementioned optimum condition, the over-all properties of the multipolymer of polymerization gained can be improved further.
According to the present invention, the various organic lithium initiators that can cause anionoid polymerization that described organic lithium initiator can be known to the skilled person, such as, described organic lithium initiator can be chemical formula is R
2the organic lithium initiator of Li, wherein, R
2for the alkyl of straight or branched, cycloalkyl or aryl; Preferably, described organic lithium initiator can be selected from lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium one or more, be more preferably n-Butyl Lithium and/or s-butyl lithium.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the kind of the present invention to described alkyl tetrahydro furfuryl alcohol ether does not have particular requirement, preferably, the carbonatoms of the alkyl in described alkyl tetrahydro furfuryl alcohol ether is 1-6, described alkyl tetrahydro furfuryl alcohol ether be preferably in the tetrahydrofurfuryl alcohol ether of ethyl, butyl and hexyl one or more.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, for enforcement monovinylarene and 1, the reactor of the polyreaction of 3-conjugated diene, it can be any reactor being suitable for the continuous solution polymerization of 1,3-conjugated-diolefin/uni-vinyl-arene copolymer.Such as, this reactor can be single reactor, also can be the multiple reactors be connected in series.This reactor can be common reactor, also can be adiabatic reactor.Be preferably adiabatic reaction still.When using adiabatic reaction still, described reactor is the adiabatic reaction still of multiple series connection, and described reaction mass is sent into from the entrance of first reactor.Preferably, the preferred 2-6 of reactor number, preferably 2-4 is individual further, is further preferably 2 or 3.This reactor can be still reaction still, also can be tower reactor.When reactor adopts the adiabatic reaction still of multiple series connection, single still residence time of described reaction mass is 30-90 minute.
1 is produced according to successive polymerization of the present invention, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, polymerization technique of the present invention is solution polymerization process, those skilled in the art are obviously to be understood that, the solvent wherein used should be in a liquid state under the polymerization conditions, does not react with organolithium, and can not participate in polyreaction, also can not react with the polymkeric substance be obtained by reacting, namely this solvent is inertia.This kind solvent is apparent for the those of ordinary skill in styrene-butadiene rubber(SBR) solution polymerization field, and can easily select.However, for the purpose of the present invention, can use non-polar hydrocarbon kind solvent, the limiting examples of this non-polar hydrocarbon kind solvent is aliphatic hydrocrbon, alicyclic hydrocarbon, aromatic hydrocarbon and composition thereof, is preferably aliphatic hydrocrbon and alicyclic mixture.The example of this solvent comprises benzene, toluene, hexanaphthene, methylcyclopentane, butane and isomer thereof, hexane and isomer, octane and isomer thereof, hexane and isomer thereof, and any mixture of these solvents.Preferably, using the solvent of mixture as polyreaction of hexanaphthene and normal hexane, is 4-9: 1 in the weight ratio of this mixed solvent cyclohexane and normal hexane.
In the present invention, after polyreaction terminates, to process polymkeric substance, to stop reactive polymer, avoid it to contact with the oxygen in air.Conventional terminator is the alcohols such as water or methyl alcohol, ethanol, Virahol, preferably selects Virahol.The consumption of terminator should make the mol ratio of terminator and organic lithium initiator be 0.1 ~ 1.0.In addition, usually need to add a small amount of anti-aging agent before polymkeric substance desolvation, anti-aging agent selects phenols or amine usually, be preferably 2,6-ditertbutylparacresol (abbreviation antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (abbreviation antioxidant 2246) etc.The add-on of anti-aging agent is generally 0.5 ~ 2.0% of polymer weight.
According to 1,3-conjugated-diolefin/uni-vinyl-arene copolymer of the present invention, be prepared by aforesaid method.
Describe the present invention in detail by embodiment and comparative example below, but scope of the present invention is not limited to these embodiments.
In the following examples and comparative example, various performance is evaluated by the following method:
(1) the molecular weight and molecualr weight distribution gel permeation chromatograph (Japanese Shimadzu Corporation LC-10Atvp series) of polymkeric substance, normal temperature measures, and mobile phase solvent is THF test.
(2) microtexture in the copolymer sample of synthesizing adopts Switzerland Bruker company AVANCE DRX 400MHz nmr determination, and measure and adopt normal temperature, method is hydrogen nuclear magnetic resonance spectroscopy, and solvent is deuterochloroform.
(3) gel content mensuration adopt dissolving weigh filtration method measure, this testing method is:
10 grams, the dried sample glue of precise, is mixed with 5 % by weight toluene solutions, after sample glue dissolves completely, weighs, record the gel content in sample through 360 order stainless (steel) wire suction filtration post-dryings.
(4) mooney viscosity (ML) adopts Japanese SHIMADZU SMV-300 tester, measures by GB/T1232-92.
In the present invention, transformation efficiency calculation formula is as follows:
Embodiment 1
Experiment adopts continuous polymerization technique, reacts and carries out in 2 the 5 liters of polymerization reaction kettles be connected in series.Under high pure nitrogen protective atmosphere, polymeric kettle internal pressure controls in 0.7Mpa (gauge pressure), add 700g hexanaphthene and normal hexane (hexanaphthene and normal hexane, weight ratio is 88: 12) to first still, after being warming up to 100 DEG C by chuck, in first still, add continuously the hexanaphthene of the aforesaid weight ratio of 25 DEG C and normal hexane mixed solvent and monomer, the input speed of various reaction mass is: mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 3538g/h, 1, 3-divinyl 669g/h, vinylbenzene 329g/h, ethyl tetrahydrofurfuryl ether 1.810g/h, n-Butyl Lithium 0.2201g/h and 1, 2-divinyl 0.2495g/h.Each polymeric kettle reaction pressure is 0.6-0.8Mpa, and temperature of reaction is 125 DEG C, and the residence time of single still is 50 ± 1 minutes.End still outlet is that 0.36g/h adds terminator Virahol and is that 5.86g/h adds anti-aging agent 2,6 ditertiary butyl p cresol with input speed with input speed, carries out termination reaction.The performance data of sample as shown in Table 1 and Table 2.
Embodiment 2
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of n-Butyl Lithium is 0.2661g/h, records the data of sample as shown in Table 1 and Table 2.
Embodiment 3
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.1996g/h.Record the data of sample as shown in Table 1 and Table 2.
Embodiment 4
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.1497g/h.Record the data of sample as shown in Table 1 and Table 2.
Embodiment 5
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.0998g/h.Record the data of sample as shown in Table 1 and Table 2
Embodiment 6
Experiment adopts continuous polymerization technique, reacts and carries out in 2 the 5 liters of polymerization reaction kettles be connected in series.Under high pure nitrogen protective atmosphere, polymeric kettle internal pressure controls in 0.6Mpa (gauge pressure), add 700g mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) to first still, after being warming up to 100 DEG C by chuck, hexanaphthene and normal hexane mixed solvent (hexanaphthene and the normal hexane of 25 DEG C is added continuously in first still, weight ratio is 88: 12) and monomer, the input speed of various reaction raw materials is: mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 5897g/h, 1, 3-divinyl 1115g/h, vinylbenzene 548g/h, ethyl tetrahydrofurfuryl ether 3.017g/h, n-Butyl Lithium 0.3668g/h and 1, 2-divinyl 0.2495g/h.Each polymeric kettle reaction pressure is 0.55-0.80Mpa, and temperature of reaction is 125 DEG C, and the residence time of single still is 30 ± 1 minutes.End still outlet adds terminator Virahol 0.60g/h and anti-aging agent 2,6 ditertiary butyl p cresol 9.77g/h, carries out termination reaction.The performance data of sample as shown in Table 1 and Table 2.
Embodiment 7
Adopt the experiment condition identical with embodiment 6, unique difference is that the speed that adds of 1，2-butadiene is 0.1663g/h.The data of properties of sample as shown in Table 1 and Table 2.
Embodiment 8
Experiment adopts continuous polymerization technique, carry out in 25 liters of polymerization reaction kettles, before experiment starts, under high pure nitrogen protective atmosphere, polymeric kettle internal pressure controls in 0.6Mpa (gauge pressure), add 700g solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) to first still, after being warming up to 100 DEG C by chuck, mixed solvent (hexanaphthene and the normal hexane of 25 DEG C is added continuously in first still, weight ratio is 88: 12) and monomer, the feed rate of various reaction raw materials is: mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 2211g/h, 1, 3-divinyl 418g/h, vinylbenzene 206g/h, ethyl tetrahydrofurfuryl ether 1.276g/h, n-Butyl Lithium 0.133g/h and 1, 2-divinyl 0.094g/h.Each polymeric kettle reaction pressure is 0.55-0.8Mpa, temperature of reaction is 125 DEG C, the residence time of single still is 80 ± 1 minutes, end still outlet adds terminator Virahol 0.188g/h and anti-aging agent 2,6-ditertbutylparacresol 3.05g/h, carry out termination reaction, the performance data of sample as shown in Table 1 and Table 2.
Comparative example 1
Adopt the experiment condition identical with embodiment 1, its difference is not add ethyl tetrahydrofurfuryl ether, and the add-on of 1，2-butadiene is 0.3493g/h.The performance data of sample as shown in Table 1 and Table 2.
Comparative example 2
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.0499g/h.The performance data of sample as shown in Table 1 and Table 2.
Comparative example 3
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.3493g/h.The performance data of sample is as shown in 1 and table 2.
Comparative example 4
Adopt the experiment condition identical with embodiment 1, unique difference is not add 1，2-butadiene.The performance data of sample as shown in Table 1 and Table 2.
Comparative example 5
Experiment adopts continuous polymerization technique, carry out in 2 the 5 liters of polymerization reaction kettles be connected in series, before experiment starts, under high pure nitrogen protective atmosphere, polymeric kettle internal pressure controls in 0.3Mpa (gauge pressure), add 700g hexanaphthene and normal hexane (hexanaphthene and normal hexane, weight ratio is 88: 12) to first still, after being warming up to 100 DEG C by chuck, hexanaphthene and normal hexane (hexanaphthene and the normal hexane of 25 DEG C is added continuously in first still, weight ratio is 88: 12) mixed solvent and monomer, mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 2527g/h, 1, 3-divinyl 478g/h, vinylbenzene 235g/h, ethyl tetrahydrofurfuryl ether 1.293g/h, n-Butyl Lithium 0.1572g/h and 1, 2-divinyl 0.250g/h.Each polymeric kettle reaction pressure is 0.55-0.80Mpa, temperature of reaction is 125 DEG C, the residence time of single still is 70 ± 1 minutes, end still outlet adds terminator Virahol 0.26g/h and anti-aging agent 2,6-ditertbutylparacresol 4.19g/h, carry out termination reaction, the performance data of sample as shown in Table 1 and Table 2.
Table 1
In table 1, St % by weight refers to the styrene content in butylbenzene copolymer; Bv % by weight refers to the contents of ethylene that the 1,3-butadiene in butylbenzene copolymer produces with 1,2-polymerization.
Table 2
As can be seen from table 1,2 data, when single still residence time of the present invention is 30-80 minute, the transformation efficiency preparing butylbenzene copolymer all can reach more than 97%, and the mooney viscosity of obtained butylbenzene copolymer, contents of ethylene all meet the requirements.Embodiment 1 can be found out compared with comparative example 1, when not add ethyl tetrahydrofurfuryl alcohol ether be structure regulator, when the consumption of 1，2-butadiene is 350ppm, the contents of ethylene be polymerized in the butylbenzene copolymer obtained is only 12.6%, and the contents of ethylene of the product obtained is on the low side.Embodiment 1 can be found out compared with comparative example 2, when adding ethyl tetrahydrofurfuryl alcohol ether and be structure regulator and the consumption of 1，2-butadiene being 50ppm, the gel content that polymerization produces is higher, does not meet the requirement of gel content during polymerization; Embodiment 1 can be found out compared with comparative example 3, add ethyl tetrahydrofurfuryl alcohol ether be structure regulator and the consumption of 1，2-butadiene is 350ppm time, the vinylbenzene of the second still, the transformation efficiency of 1,3-butadiene are only respectively 90.6% and 93.5%; As can be seen from data with comparative example 4 of embodiment 1, do not add gel when suppressing, the gel content that reaction produces is too high; As can be seen from data with comparative example 5 of embodiment 1, when monomer is identical with the ratio of initiator, namely molecular weight is designed identical, although be 70 ± 1 minutes by the extended residence time of single still, due to 1, the consumption of 2-divinyl is 350ppm, and the second still 1,3-butadiene and cinnamic transformation efficiency still can not reach 97%; Can find out that the consumption when 1，2-butadiene is 150ppm from embodiment 8, the residence time becomes 80 minutes, and the first still transformation efficiency reaches more than 97%, illustrates and adopts method of the present invention, namely uses single still to be polymerized and just can synthesize satisfactory polymkeric substance.Above data can be found out, adopt method of the present invention, can in raising 1, while the transformation efficiency of 3-conjugated-diolefin/uni-vinyl-arene, make the contents of ethylene of the butylbenzene copolymer obtained meet medium requirement, and the mooney viscosity of obtained product is high, gel content during polymerization is low.
Claims (12)
1. a successive polymerization produces 1, the method of 3-conjugated-diolefin/uni-vinyl-arene copolymer, the method comprises sends into reactor continuously by the reaction mass containing monomer a, organic solvent, alkyl tetrahydro furfuryl alcohol ether and organolithium, under anionic polymerization conditions, monomer a is polymerized and obtains multipolymer, wherein, described monomer a is monovinylarene and 1,3-conjugated diene, it is characterized in that, described reaction mass is also containing gel inhibitor 1,2-divinyl, wherein, with the weight of monomer a for benchmark, the consumption of 1，2-butadiene is 200-250ppm; The consumption of described organolithium is 0.25-0.9 mmole/100 gram monomer a; Described anionic polymerization conditions comprises: temperature of reaction is 120-128 DEG C, and reaction pressure is 0.55-0.8MPa, and the reaction times is 60-160 minute.
2. method according to claim 1, wherein, described 1,3-conjugated diene is the one in 1,3-butadiene, isoprene, m-pentadiene;
Described monovinylarene such as formula shown in I,
In formula I, R
1for C
6-C
20substituted or unsubstituted aryl.
3. method according to claim 2, wherein, described 1,3-conjugated diene is 1,3-butadiene, and described monovinylarene is vinylbenzene.
4. method according to claim 3, wherein, the weight ratio of vinylbenzene and 1,3-butadiene is 1:1-4; The weight ratio of 1,3-butadiene and solvent is 0.05-0.27:1; The mol ratio of described alkyl tetrahydro furfuryl alcohol ether and organolithium is 0.4-8:1.
5. the method according to claim 1 or 3 or 4, wherein, the chemical formula of described organolithium is R
2li, wherein, R
2for the alkyl of straight or branched, cycloalkyl or aryl; The carbonatoms of the alkyl in described alkyl tetrahydro furfuryl alcohol ether is 1-6.
6. method according to claim 5, wherein, described organolithium be selected from lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium one or more.
7. method according to claim 6, wherein, described organolithium is n-Butyl Lithium and/or s-butyl lithium.
8. method according to claim 5, wherein, described alkyl tetrahydro furfuryl alcohol ether be selected from the tetrahydrofurfuryl alcohol ether of ethyl, butyl and hexyl one or more.
9. method according to claim 1, wherein, described reactor is multiple adiabatic reaction stills of series connection, and described reaction mass is sent into from the entrance of first reactor.
10. method according to claim 9, wherein, the number of described reactor is 2 or 3.
11. methods according to claim 9 or 10, wherein, single still residence time of described reaction mass is 30-90 minute.
1,3-conjugated-diolefin/uni-vinyl-arene copolymer prepared by the method in 12. claim 1-11 described in any one.
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