CN1269371A - Preparation of conjugated diene and/or monovinyl arene polymer - Google Patents
Preparation of conjugated diene and/or monovinyl arene polymer Download PDFInfo
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Abstract
A preparation method of conjugated diolefine and/or monovinyl aromatic polymer adopts a structure regulating agent expressed by the general formula, uses base lithium as initiating agent to initiate and polymerize conjugated diolefine and/or monovinyl arene at 0-150 deg.C in inert solvent to obtain the polymer.
Description
The present invention relates to the preparation method of a kind of conjugated diolefine and/or monovinyl arene polymer, particularly relate to and a kind ofly having in the presence of the novel texture conditioning agent, with the lithium alkylide is initiator, prepares the method for conjugated diolefine and/or monovinyl arene polymer in inert solvent.
In the living anion polymerization of conjugated diolefine and/or monovinylarene, anionoid polymerization structure regulator tetrahydrofuran (THF) commonly used (being called for short THF) regulating power a little less than, under usual conditions, be difficult to synthetic the have polydiolefin of high-vinyl structure or the multipolymer of conjugated diolefine and monovinylarene.As industrial when with THF being synthetic divinyl of conditioning agent and cinnamic random copolymers, mol ratio at THF and organic single-lithium is 40, in the 50-100 ℃ of polymerization resulting polymers, 1, the butadiene unit content of 2-structure (claiming vinyl structure again) is less than 40% of total butadiene unit amount.Therefore THF is very restricted on using.Once there were a lot of people to recommend to use diethylene glycol dimethyl ether (being called for short 2G), though its regulating power is stronger than THF, under the less situation of consumption, can synthesize the polydiolefin with high-vinyl structure or the multipolymer of conjugated diolefine and monovinylarene, but it not only influences the growth activity of anion active kind and monomer conversion is descended significantly, and makes the coupling of spike and coupling agent be difficult to maybe can not carry out.All there are this critical defect in general symmetry ether such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dibutyl ethylene glycol ether etc.As with 2G being conditioning agent three-stage process synthesizing styrene-divinyl (1, the 2-structural content is 50%)-during styrene triblock copolymer, mol ratio at 2G and organic single-lithium is 1, in the 50-100 ℃ of scope, elder generation's polymerizing styrene, the repolymerization divinyl, but when adding vinylbenzene at last since 2G have spike initiated polymerization vinylbenzene well, thereby can not get required triblock polymer; Be conditioning agent for another example with 2G, when synthetic divinyl with high-vinyl structure and styrene random branching type multipolymer, mol ratio at 2G and organic single-lithium is 1, behind 50-100 ℃ of polymerization divinyl and the vinylbenzene, when adding coupling agent commonly used such as silicon tetrachloride or tin tetrachloride carry out linked reaction, since 2G exist spike can not with coupling agent generation linked reaction, thereby can not get having the atactic butadiene styrene copolymer of long chain branching.
United States Patent (USP) U.S.P 5,231,153,5,359,016 and 5,470,929 disclose a kind of anionoid polymerization by divinyl or vinylbenzene and isoprene prepares divinyl or the elastomeric method of styrene isoprene, and wherein the structure regulator of Cai Yonging is shown in following molecular structure:
But contain cyclic ethers or cyclammonium structure preparation process complexity in this structure regulator.
In order to overcome above-mentioned problems of the prior art, the contriver is through exploratory development for many years and long-term industrialization production practice, in the performance history of anionoid polymerization field, find the structure regulator that a class is new, this structure regulator is in living anion polymerization, regulating power is strong, can synthesize the polymkeric substance with high-vinyl structure; Particularly do not influence the growth activity of anion active kind and the linked reaction of living polymer chain spike and coupling agent, and can significantly improve monomer polymerization reactions initiation and rate of growth.
The purpose of this invention is to provide a kind ofly in the presence of the novel texture conditioning agent, is initiator so that basic lithium to be arranged, and polymerized conjugated diene and/or monovinylarene prepare the method for polymkeric substance in inert solvent.
Another purpose of the present invention provides a kind of new effective anionoid polymerization structure regulator, is used to prepare conjugated diolefine and/or monovinyl arene polymer.
The preparation method of conjugated diolefine provided by the invention and/or monovinyl arene polymer adopts known active anion solution polymerization process.According to the preparation method of conjugated diolefine of the present invention and/or monovinyl arene polymer in high-purity nitrogen atmosphere, in the presence of new structure regulator, with the organolithium is initiator, in inert solvent, by living anion polymerization conjugated diolefine and/or vinyl-arene, obtain polymkeric substance at a certain temperature.
Among the preparation method according to conjugated diolefine of the present invention and/or single ethene aromatic polymer, described polymkeric substance is meant homopolymer and multipolymer, the homopolymer and the multipolymer that particularly have the line style and the different degrees of branching, the homopolymer of conjugated diolefine are the homopolymer of for example polyhutadiene, polyisoprene etc.; Multipolymer such as divinyl and isoprene, conjugated diolefine and monovinylarene copolymer such as random copolymers, line-type block polymer and coupling branching type segmented copolymer etc.
Described novel texture conditioning agent has the compound shown in the following general formula (a),
Wherein: R
1, R
2, R
3Each other can be identical or different, and be alkyl independently of one another; N is the positive integer of 1-4, described alkyl is preferably the alkyl of 1-16 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, base, 3-first amyl group, 1,3-dimethylbutyl, n-octyl, 1, the 3-dimethyl is base, 1, the 4-dimethyl is base, 2, and the 5-dimethyl is base, n-nonyl, 1,3, the 5-trimethylammonium is base, 2,5-dimethyl heptyl, decyl, undecyl, tridecyl, pentadecyl etc.The alkyl of 1-6 carbon atom more preferably, for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, base etc.
The compound of being represented by above-mentioned general formula α is preferably 2-(N, the N-dimethyl) amino-ethyl ethyl ether, 2-(N, the N-dimethyl) amino-ethyl n-butyl ether, 2-(N, the N-dimethyl) amino-ethyl sec-butyl ether, 2-(N, the N-dimethyl) amino-ethyl isobutyl ether, 2-(N, the N-dimethyl) amino-ethyl n-octyl ether, 2-(N, the N-dimethyl) amino-ethyl n-heptyl ether, 2-(N, the N-diethyl) amino-ethyl n-butyl ether, 2-(N, the N-diethyl) amino-ethyl sec-butyl ether, 2-(N, the N-diethyl) amino-ethyl isobutyl ether, 2-(N, the N-diethyl) the basic ether of amino-ethyl, 2-(N, the N-diethyl) amino-ethyl iso-octyl ether, 2-(N, the N-diethyl) amino-ethyl n-octyl ether, 2-(N, the N-diethyl) amino-ethyl n-nonyl ether, 2-(N, the N-diethyl) amino-ethyl dodecyl ether, 2-(N, the N-diethyl) amino-ethyl n-tetradecane base ether, 2-(N, the N-dimethyl) amino-ethyl n-propyl glycol ether, 2-(N, the N-dimethyl) amino-ethyl normal-butyl glycol ether, 2-(N, the N-dimethyl) amino-ethyl isobutyl-glycol ether, 2-(N, the N-dimethyl) amino-ethyl ethyl glycol ether just, 2-(N, the N-dimethyl) amino-ethyl n-heptyl glycol ether, 2-(N, the N-dimethyl) amino-ethyl n-heptyl diethylene glycol ether, 2-(N, the N-diethyl) amino-ethyl normal-butyl diethylene glycol ether, 2-(N, the N-diethyl) amino-ethyl isobutyl-diethylene glycol ether, 2-(N, the N-diethyl) amino-ethyl normal-butyl diethylene glycol ether, 2-(N, the N-diethyl) amino-ethyl n-pentyl diethylene glycol ether, 2-(N, N-diethyl) amino-ethyl n-heptyl diethylene glycol ether etc.
2-(N more preferably, the N-dimethyl) amino-ethyl n-butyl ether, 2-(N, the N-dimethyl) amino-ethyl isobutyl ether, 2-(N, the N-diethyl) amino-ethyl isobutyl ether, 2-(N, the N-diethyl) amino-ethyl sec-butyl ether, 2-(N, the N-diethyl) amino-ethyl n-butyl ether, 2-(N, N-dimethyl) amino-ethyl normal-butyl glycol ether, 2-(N, N-dimethyl) amino-ethyl normal-butyl diethylene glycol ether.
Described structure regulator can use separately, also can with known other conditioning agent such as alkoxy base metallic compound, be used, its type and consumption depend on required micmstructure of polymer or stereoblock, mol ratio with structure regulator and organolithium is expressed as 0.01: 1-40: 1, be preferably 0.02: 1-10: 1, more preferably 0.05: 1-5: 1, its mol ratio is close to the high limit when synthetic high-vinyl-content polymkeric substance.
The preparation method of described structure regulator is: with N, the N-dialkylamino ethanol splashes in the excessive sulfur oxychloride and reacts, after reaction finishes with crystallisate (N, the hydrochloride of N-dialkyl amido monochloroethane) leaches, this crystallisate is dissolved in the toluene, and the sodium carbonate solution with 15% is neutralized to about pH=9.5, tells toluene layer through the Calcium Chloride Powder Anhydrous drying, obtain N, the toluene solution of N-dialkyl amido monochloroethane.With R
3(OCH
2CH
2)
N-1After OH and sodium Metal 99.5 reaction generate sodium alkoxide, splash into dried N, the toluene solution of N-dialkyl amido monochloroethane, reaction finishes after air distillation obtains required structure regulator product of the present invention.
In method for producing polymer of the present invention, described conjugate diene monomer is a 4-20 carbon atom, be preferably 4-12 carbon atom, the conjugated diolefine of 4-8 carbon atom more preferably, divinyl or replace divinyl such as 1,3-butadiene, 2,3-dimethyl-1 for example, 3-divinyl, 1-phenyl-1,3-butadiene etc.; Isoprene, pentadiene or replace pentadiene as 1,3 pentadiene etc.Wherein most preferred conjugated diolefine is 1,3-butadiene and isoprene.Conjugated diolefine can be used separately, also can mix use.The conjugate diene monomer consumption is counted 20-100% (weight) with total monomer weight, is determined by polymer property and kind.The polymer solution concentration scope is 10-60% (weight).According to mono vinyl arenes monomer described in the method for producing polymer of the present invention is 8-20 carbon atom, be preferably the monovinylarene of 8-12 carbon atom, for example vinylbenzene or cinnamic derivative as-vinyl toluene, p-methylstyrene, right-t-butyl styrene, alpha-methyl styrene etc.Mono vinyl arenes monomer can use separately, also can mix use, and is actual from obtaining complexity and industrialization, is preferably vinylbenzene and p-methylstyrene, more preferably vinylbenzene.Monovinylarene content in multipolymer does not have strict the qualification, general 0-100% (weight) (is benchmark with the total monomer weight).
In method for producing polymer of the present invention, described organic lithium initiator can be organic single-lithium and organic many lithiums etc.Described organic single-lithium is lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, amyl group lithium, phenyl lithium, cyclohexyl lithium, tolyl lithium, 4-tert-butyl-phenyl lithium, vinyl lithium, propenyl lithium, 2-phenyl lithium etc.; Described organic many lithiums are organic pair of lithium such as ethyl two lithiums, four methynes, two lithiums, five methynes, two lithiums, six methynes, two lithiums, 1, two (the 1-lithium base-3-aminomethyl phenyl) benzene, 1 of 3-, two (1-lithium base-1, the 3-3,5-dimethylphenyl) benzene, 1 of 3-, 4-two lithiums-1,4 phenyl butanes, 1,4-two lithiums-1,1,4,4 '-tetraphenyl butane, 1,4-two lithium butane; And the organic many lithiums of many chelating types, for example in varsol, react for example organic many lithiums of many chelating types that form of n-Butyl Lithium and DVB of the organic many lithiums of the many chelating types that obtain by organic single-lithium and Vinylstyrene (DVB).Organolithium is preferably n-Butyl Lithium or s-butyl lithium, the organic many lithiums of many chelating types that n-Butyl Lithium and DDB form.The consumption of organic lithium initiator depends on design molecular weight size, and general consumption is that per 100 gram monomers need add 0.2-5.0 mmole organolithium.
In method for producing polymer of the present invention, if preparation random copolymers, adopt the alkoxy base metallic compound, described alkoxy base metallic compound is alkoxyl group potassium or sodium alkylate, methoxyl group potassium, sodium methoxide, oxyethyl group potassium, Sodium Ethoxide, positive propoxy potassium, positive propoxy sodium, isopropoxy potassium, isopropoxy sodium, tert.-butoxy potassium, tert.-butoxy sodium, uncle's pentyloxy potassium, uncle's pentyloxy sodium, positive hexyloxy potassium, positive hexyloxy sodium, cyclohexyloxy potassium, cyclohexyloxy sodium, octadecane oxygen base potassium, octadecane oxygen base sodium, eicosane oxygen base potassium, eicosane oxygen base sodium, butenyloxy potassium, butenyloxy sodium, hexene oxygen base potassium, hexene oxygen base sodium, 4-methyl cyclohexane oxygen base potassium, 4-methyl cyclohexane oxygen base sodium, 3-tetrahydrobenzene oxygen base potassium, 3-tetrahydrobenzene oxygen base sodium, benzyloxy potassium, benzyloxy sodium, phenoxy group potassium, phenoxy group sodium, be preferably tert.-butoxy potassium, uncle's pentyloxy potassium, more preferably uncle's pentyloxy potassium.
In method for producing polymer of the present invention, described inert solvent can be aromatic hydrocarbon, aliphatic hydrocrbon or naphthenic hydrocarbon, and wherein aromatic hydrocarbon is benzene,toluene,xylene and ethylbenzene or its mixture etc.; Aliphatic hydrocrbon is for example raffinating oil etc. of refinery by product such as hydrogenated gasoline, reformer of butane, hexane and heptane or the aliphatic hydrocrbon mixture with different carbonatomss; Naphthenic hydrocarbon is pentamethylene, cyclohexane and methyl cyclohexanol etc.These varsols can use separately, also can mix use, and the aliphatic hydrocrbon that can be in varing proportions and the mixture of naphthenic hydrocarbon such as hexane fraction and cyclohexane are pressed the mixture of 1/10-5/5.
In method for producing polymer of the present invention, if desired, reactive polymer of the present invention can carry out coupling with coupling agent, and forms the polymkeric substance with long chain branching, and its degree of branching generally can be controlled at 10%-100% by end-use.Known coupling agent in the prior art all can be used for the present invention.Described coupling agent has many vinyl-arenes such as Vinylstyrene etc.The organo-siloxane compounds.Single polyester compounds such as ethyl acetate, adipic acid diethyl ester, adipic acid dimethyl ester, phthalate esters.Polydentate compound such as dichlorosilane, silicon tetrachloride, tin tetrachloride etc., preferred star-like coupling agent is tin tetrachloride and silicon tetrachloride, and many branching coupling agent is DVB, and non-halogen-type is carboxylic acid ester compound and organo-siloxane compounds.The method of adding coupling agent adopts currently known methods, is for example for example reacting in beginning and the process or is adding coupling agent after finishing in any stage of polyreaction and carrying out linked reaction.The add-on of coupling agent can change in very wide scope, with coupling agent and organolithium molar ratio computing, is preferably 0.05-0.50, more preferably 0.1-0.3.
Polymeric reaction temperature is 0-150 ℃, is preferably 30-120 ℃, more preferably 40-90 ℃.
It is liquid that the pressure of polyreaction should keep polymerization system, generally between 0.05-1.2Mpa, is preferably 0.1-0.6Mpa.Polymerization reaction time is 0.2-4 hour.
Must cause initiator or the active impurity of holding inactivation in advance except that deenergizing for monomer above-mentioned and solvent, as compound, alcohols, carbonyl compound and the acetylene compound etc. of water, oxygen, carbonic acid gas, sulphur.
In method for producing polymer of the present invention, also available terminator, anti-aging agent etc. are for known, general Virahol and the water of using is made terminator, uses Hinered phenols itself and and the phosphoric acid ester mixture be anti-aging agent, as 2,6-di-tert-butyl-4-methy phenol anti-aging agent (being called for short 2,6,4 anti-aging agent).
In conjugated diolefine of the present invention and/or embodiment of monovinyl arene polymer preparation method
Conjugated diolefin homopolymerization closes in the process by the kind of selecting structure regulator of the present invention and regulates its consumption or be used with other conditioning agent, can synthesize to have diverse microcosmic structure or stereoblock or line style and branching type homopolymer.For example in the equal polymerization process of divinyl, can add structure regulator of the present invention such as 2-(N, the N-diethyl) the amino-ethyl n-butyl ether is come the microtexture of telomerized polymer, the ratio height of structure regulator and organic single-lithium, then 1 of polyhutadiene, the 2-structural content is just high, can synthesize high by 1, the polyhutadiene line style and the branching type of 2-structure (＞70%) line style and branching type; And the ratio of structure regulator and organic single-lithium is low, then 1 of polyhutadiene, the 2-structural content is just low, can synthesize low by 1, the polyhutadiene of 2-structure (＜20%); The feed way of appropriate change conditioning agent also can synthesize have simultaneously low by 1,2-structure block and high by 1, the polyhutadiene of upright structure two blocks of 2-structure block.In the equal polymerization process of isoprene, it is high by 3 to adopt above-mentioned method also can synthesize, 4-structure, low by 3,4-structure and upright structure two blocks or line style and branching type polyisoprene.This base polymer is the automobile radial tyre tread mix that a kind of low-rolling-resistance and anti-slippery are held concurrently excellent.Adopt structure regulator of the present invention to be used for the vinylbenzene homopolymerization, then can improve its velocity of initiation greatly, and obtain narrow distribution linetype and the branching type polystyrene of molecular weight distributing index at 1.05-1.1.
In conjugated diolefine of the present invention and/or another embodiment of monovinyl arene polymer preparation method, kind by selecting structure regulator of the present invention in conjugated diene and monovinylarene and the different conjugated diolefine copolymerization process and conditioning agent consumption or be used with other conditioning agent, adopt suitable feed way, can synthesize multipolymer and segmented copolymer with grading structure or desirable random structure.
In the copolymerization process of divinyl and isoprene, can add structure regulator of the present invention makes it carry out copolymerization, because the polymerization activity of divinyl and isoprene monomer is different, the synthetic multipolymer has that butadiene structure unit content reduces gradually and grading structure or line style and branching type that isoprene structural unit content raises gradually like this; As add alkoxyl group potassium or sodium alkylate and structure regulator of the present invention and be used, then can realize the random copolymerization of divinyl and isoprene, thereby the divinyl of synthetic desirable random structure and isoprene copolymer are special in having line style and branching type random copolymers; As making polymerizing butadiene earlier, after make isoprene polymerization or opposite order, by changing the consumption of structure regulator of the present invention, can synthesize divinyl and isoprene block copolymer with diverse microcosmic structure.
In divinyl (or isoprene) and cinnamic copolymerization process, can add structure regulator of the present invention makes it carry out copolymerization, because the polymerization activity of divinyl (or isoprene) and styrene monomer is different, the synthetic multipolymer has that divinyl (or isoprene) structural unit content reduces gradually and grading structure that styrol structural unit content raises gradually like this when the structure regulator usage quantity is low; When structure regulator usage quantity of the present invention is higher or suitably add alkoxyl group potassium or sodium alkylate and structure regulator of the present invention and be used, then can realize divinyl (or isoprene) and cinnamic random copolymerization, thus divinyl (or isoprene) styrol copolymer of synthetic desirable random structure; As making divinyl (or isoprene) and styrene polymerization respectively, the order and the number of fragments of consumption, divinyl (or isoprene) and styrene polymerization by changing structure regulator of the present invention and make the reactive polymer coupling can be synthesized the polyhutadiene (or polyisoprene) with diverse microcosmic structure and divinyl (or isoprene) vinylbenzene two blocks, styrene butadiene (or isoprene) vinylbenzene three blocks and styrene butadiene (or isoprene) the many blocks line style and the star copolymer of polystyrene.
In divinyl, isoprene and cinnamic terpolymerization process, can add structure regulator of the present invention makes it carry out copolymerization, because the polymerization activity of divinyl, isoprene and styrene monomer is different, the synthetic multipolymer has that butadiene structure unit content reduces gradually and grading structure that isoprene, styrol structural unit content raise gradually like this; As add alkoxyl group potassium or sodium alkylate and structure regulator of the present invention and be used, then can realize divinyl, isoprene and cinnamic random copolymerization, thus the butadiene-isoprene styrene copolymer of synthetic desirable random structure line style and branching type; As making the independent polymerization of vinylbenzene earlier, after divinyl and isoprene copolymer are closed, make styrene polymerization (or making the reactive polymer coupling) again, can synthetic polystyrene-divinyl, isoprene (having grading structure)-cinnamic three blocks (or star block) multipolymer; As add alkoxyl group potassium or sodium alkylate and structure regulator of the present invention and be used, then can synthetic polystyrene-divinyl, isoprene (random structure)-cinnamic three blocks (or star block) multipolymer.As adopt structure regulator of the present invention, before organolithium adds and behind Vinylstyrene and many lithiums of the diene monomers process chelating processing formation initiator system, add reactor again and carry out divinyl or isoprene homopolymerization or diolefine and vinylbenzene binary or terpolymer, then can prepare and have the above polymkeric substance in molecular weight distribution three peaks or three peaks, this type of many lithiums initiated polymerization thing has the wide dispersion index of 1.8-2.5, and its processibility and physicomechanical properties are better than the same base polymer of general single lithium, dilithium initiator preparation.
The present invention will further specify the present invention with following embodiment, but protection domain of the present invention is not limited to embodiment, and those of ordinary skill in the art does according to the present invention to change in protection domain of the present invention.
Initiator concentration records with two volumetrys among the embodiment, the microtexture of polymkeric substance adopts determination of infrared spectroscopy, combined styrene content is measured by ultraviolet spectrometer in the polymkeric substance, the second-order transition temperature of polymkeric substance is measured by difference formula scanning calorimeter (DSC), the mechanical property of polymkeric substance is measured by the universal electrical drawing machine, and the coupling efficiency of polymkeric substance and two block content are measured by gel chromatography permeability testing machine (GPC).Embodiment 1-4
Under the high pure nitrogen protection; by following ratio of components amount, with hexanaphthene, 1,3-butadiene, 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing, be warming up to 50 ℃, behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportioning in the still fast; feed the temperature 50-90 ℃ of polymerization 90 minutes that hot water guarantees required control with the still chuck, after polyreaction finishes, add SiCl
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains having the polybutadiene polymers that different contents of ethylene contains line style and nearly 1/2 long chain branched after condensing laggard vacuum drying oven drying through ethanol.This base polymer is the automobile radial tyre tread mix that a kind of low-rolling-resistance and anti-slippery are held concurrently excellent.1,2 structure and the coupling efficiency of resulting polymers see Table 1.
Ratio of components is as follows:
Hexane (gram) 2200
1,3-butadiene (gram) 300
Butyllithium (mmole) 2.6
I/Li (mol ratio) changes (seeing Table 1)
SiCl
4/ Li (mol ratio) 0.13 embodiment 5-8
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 1-4 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), other operation and condition are with embodiment 1-4.Embodiment 9-12
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 1-4 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), other operation and condition are with embodiment 1-4.Embodiment 13-16
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 1-4 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation and condition are with embodiment 1-4.Comparative example 1-4
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 1-4 with tetrahydrofuran (THF) (THF), other operation and condition are with embodiment 1-4.Comparative example 5-8
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 1-4 with diethylene glycol dimethyl ether (2G), other operation and condition are with embodiment 1-4.
Table 1
| The embodiment sequence number | The structure regulator kind | Structure regulator/butyllithium (mol ratio) | 1,2-structure (%) | Coupling efficiency (%) |
| ????1 ????2 ????3 ????4 | ????I ????I ????I ????I | ????0.2 ????0.5 ????2.0 ????5.0 | ????36.89 ????54.22 ????64.90 ????72.86 | ????52.2 ????50.5 ????54.2 ????48.9 |
| ????5 ????6 ????7 ????8 | ????II ????II ????II ????II | ????0.5 ????1.0 ????2.0 ????5.0 | ????26.17 ????38.01 ????55.19 ????68.76 | ????53.4 ????52.5 ????51.2 ????49.2 |
| The embodiment sequence number | The structure regulator kind | Structure regulator/butyllithium (mol ratio) | 1,2-structure (%) | Coupling efficiency (%) |
| 9 10 11 12 | ????III ????III ????III ????III | ????0.2 ????0.5 ????2.0 ????5.0 | ????18.30 ????33.77 ????45.09 ????50.40 | ????51.7 ????53.6 ????54.2 ????49.9 |
| 13 14 15 16 | ????IV ????IV ????IV ????IV | ????0.2 ????0.5 ????2.0 ????5.0 | ????38.75 ????58.15 ????70.43 ????74.93 | ????54.2 ????51.5 ????53.2 ????47.9 |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | ????THF ????THF ????THF ????THF | ????1 ????10 ????20 ????40 | ????15.6 ????30.2 ????36.7 ????38.9 | ????53.2 ????51.5 ????53.2 ????50.9 |
| Comparative example 5 comparative examples 6 comparative examples 7 comparative examples 8 | ????2G ????2G ????2G ????2G | ????0.2 ????0.5 ????2.0 ????5.0 | ????30.2 ????52.3 ????67.5 ????70.1 | ????45.3 ????14.3 ????0 ????0 |
As can be seen from Table 1, the structure regulator among the present invention is stronger than THF regulating power, under consumption seldom, just can synthesize have high by 1, the polyhutadiene of 2-structure; While and 2G are relatively, the 2G consumption increases, linked reaction can not be carried out, can not get the polymkeric substance of the part long chain branching of high ethylene content, and use structure regulator of the present invention to have the growth activity of spike and the linked reaction of spike and coupling agent are not had the advantage of influence, and can synthesize line style and long chain branching polyhutadiene or its multipolymer of middle high-vinyl-content.Embodiment 17
Under the high pure nitrogen protection; by following ratio of components; with hexanaphthene; 1; the 3-divinyl; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; 50-90 ℃ of polymerization 120 minutes; after polyreaction finished, being dissolved in volume ratio with 4 gram antioxidant 264s was to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains the line style butylbenzene copolymer after condensing the vacuum drying oven drying through ethanol; can be used as the base polymer of hydrogenation styrene-butadiene polymer, is that a class can be used as vapour; the thickening material of diesel motor multigrade lubricating oil.1,2 structure of resulting polymers sees Table 2.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
1,3-butadiene (gram) 240
Vinylbenzene (gram) 60
Butyllithium (mmole) 3.75
I/Li (mol ratio) 0.4 embodiment 18
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 17 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=1.5, other operation and condition are with embodiment 17.Embodiment 19
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 17 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=2.0, other operation and condition are with embodiment 17.Embodiment 20
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 17 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.35 and condition are with embodiment 17.
Table 2
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.Embodiment 21
| The embodiment sequence number | ????17 | ????18 | ????19 | ????20 |
| Combined styrene content, (%) | ????20 | ????20 | ????20 | ????20 |
| 1,2-structural content, (% 1) | ????50 | ????50 | ????50 | ????53 |
Under the high pure nitrogen protection; make a gesture of measuring by following batching, with hexane fraction, 1,3-butadiene, vinylbenzene, 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing, be warming up to 50 ℃, behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; 50-90 ℃ of polymerization 90 minutes, after polyreaction finishes, add SnCl
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, vinyl randomly solution polymerized butadiene-styrene rubber with low during glue obtains after through ethanol cohesion vacuum and heating drying.Its molecular weight distribution is bimodal, and a part is a line polymer, and another part is four arm star macromole of coupling, and this polymkeric substance is a kind of good high-speed tire tread rubber.The structure and the rerum natura of resulting polymers see Table 3.
Ratio of components is as follows:
Hexane fraction (gram) 2800
1,3-butadiene (gram) 225
Vinylbenzene (gram) 75
Butyllithium (mmole) 2.72
I/Li (mol ratio) 0.15
SnCl
4/ Li (mol ratio) 0.18 embodiment 22
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 21 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.8, other operation and condition are with embodiment 21.Embodiment 23
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 21 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.5, other operation and condition are with embodiment 21.Embodiment 24
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 21 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.15 and condition are with embodiment 21.
3
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.Embodiment 25
| Embodiment sequence number 21 22 23 24 |
| Combined styrene content, (%) 25 25 25 25 1,2-structural content, (% 1) 33 32 31 35 crude rubber Mooney viscosities, 54 55 53 55 Shao Er hardness, 69 70 68 69 tear strengths, (kN/m) 37 35 36 34 tension sets, (%) 9 10 11 9 300% tensile modulus, (Mpa) 10.1 10.2 10.5 10.3 tensile strength at yields, (Mpa) 18.8 18.5 18.9 18,1 specific elongation rate, (%) 496 495 490 492 |
Under the high pure nitrogen protection; make a gesture of measuring by following batching; with hexanaphthene; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system, the butyllithium of following proportional quantity is added in the still fast, polyase 13 is after 0 minute; add the divinyl of removing impurity; after the polymerization 90 minutes, add the vinylbenzene of removing impurity, polyase 13 0 minute again; after polyreaction finishes; add 4 gram antioxidant 264s and obtain styrene-butadiene-styrene three block linear copolymers (SBS), its divinyl partly contains higher 1,2 structure; do not contain halogen compounds again; glue can behind this type of hydrogenation of polymer, be a kind of weatherable thermoplastic elastomer directly as the base polymer of hydrogenation SBS without cohesion; can be used as the compatilizer of polyblend, purposes is very extensive.The structure and the rerum natura of resulting polymers see Table 4.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Vinylbenzene (gram) 45
Butyllithium (mmole) 3.75
I/Li (mol ratio) 0.4
1,3-butadiene (gram) 210
Vinylbenzene (gram) 45 embodiment 26
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 25 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=1.5, other operation and condition are with embodiment 25.Embodiment 27
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 25 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=4.0, other operation and condition are with embodiment 25.Embodiment 28
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 25 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.35 and condition are with embodiment 25.Comparative example 9
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 25 with diethylene glycol dimethyl ether (2G), 2G/Li=0.5, other operation and condition are with embodiment 25.
Table 4
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.Annotate 2 this be because after final stage vinylbenzene adds, fail well due to the polymerization reaction take place.
| Embodiment sequence number 25 26 27 28 comparative examples 9 |
| Combined styrene content, (%) 30 30 30 30 202 1,2-structural content, (% 1) 50 50 50 50 50 Shao Er hardness 75 75 75 75- |
| Tension set, (%) 38 37 36 38-300% tensile modulus, (Mpa) 2.8 2.9 2.9 2.7-tensile strength at yield, (Mpa) 23.3 23.5 23.4 23.4-specific elongation rates, (%) 770 760 750 780- |
Synthesize highly by 1 as can be seen with 2G by table 2-4, during three block SBSs of 2-structure, owing to the existence of 2G has bigger influence to the growth activity of spike, the 3rd section styrene conversion rate is low, thereby can not synthesize required three block simple linear polymers.Adopting structure regulator of the present invention then not have this problem occurs.Embodiment 29
Under the high pure nitrogen protection; make a gesture of measuring by following batching, hexanaphthene, vinylbenzene, 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) are joined in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃, behind the impurity in a spot of butyllithium elimination system, add the butyllithium of following proportional quantity in the still fast; behind the polyase 13 0 minute; add the divinyl of removing impurity, polymerization added SiCl after 90 minutes
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, glue obtains styrene-butadiene-styrene star block copolymer (SBS) after condensing drying through water vapor, can be used for the base polymer of hydrogenation star-shaped sbs.The solution of this base polymer and molten thing, viscosity is hanged down the processing characteristics excellence, is suitable for doing solvent-borne type and the ageing-resistant tackiness agent of hot-melting type.The structure and the rerum natura of resulting polymers see Table 5.
Ratio of components is as follows:
Hexanaphthene (gram) 2500
Vinylbenzene (gram) 90
Butyllithium (mmole) 5.0
I/Li (mol ratio) 0.4
1,3-butadiene (gram) 210
SiCl
4/ Li (mol ratio) 0.25 embodiment 30
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 29 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=1.5, other operation and condition are with embodiment 29.Embodiment 31
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 29 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=2.0, other operation and condition are with embodiment 29.Embodiment 32
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 29 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.35 and condition are with embodiment 29.Comparative example 10
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 29 with diethylene glycol dimethyl ether (2G), 2G/Li=0.5, other operation and condition are with embodiment 29.
Table 5
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.
| Embodiment sequence number 29 30 31 32 comparative examples 10 |
| Combined styrene content, (%) 30 30 30 30 30 1,2-structural content, (% 1) 50 49 48 52 51 SB, two block content, (%)＜5＜5＜5＜5＞80 Shao Er hardness 75 75 75 75-tension set, (%) 28 30 29 32-300% tensile modulus, (Mpa) 3.5 3.5 3.4 3.3-tensile strength at yield, (Mpa) 19.3 19.5 19.7 19.4-specific elongation rates, (%) 650 670 640 680- |
Synthesize highly by 1 as can be seen with 2G, during the star block SBS of 2-structure,, thereby can not perform well in synthesizing required polymkeric substance because the existence of 2G has bigger influence to the linked reaction of spike and coupling agent.Adopting structure regulator of the present invention then not have this problem occurs.Embodiment 33
Under the high pure nitrogen protection; make a gesture of measuring by following batching; with hexanaphthene; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; behind the polyase 13 0 minute; add the isoprene of removing impurity, polymerization adds the vinylbenzene of removing impurity after 90 minutes again; polyase 13 0 minute; after polyreaction finished, being dissolved in volume ratio with 4 gram antioxidant 264s was to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains being fit to the styrene-isoprene-phenylethene triblock copolymer (SIS) of making nontoxic binding material after through water vapor cohesion drying.The rerum natura of resulting polymers sees Table 6.
Ratio of components is as follows:
Hexanaphthene (gram) 2500
Vinylbenzene (gram) 22.5
Butyllithium (mmole) 3.75
I/Li (mol ratio) 0.15
Isoprene (gram) 210
Vinylbenzene (gram) 22.5 embodiment 34
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 33 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.8, other operation and condition are with embodiment 33.Embodiment 35
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 33 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.5, other operation and condition are with embodiment 33.Embodiment 36
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 33 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.15 and condition are with embodiment 33.
Table 6
Embodiment 37
| Embodiment sequence number 33 34 35 36 |
| Shao Er hardness 41 42 40 39 tension sets, (%) 14 15 13 17 300% tensile modulus, (Mpa) 0.9 0.9 0.9 0.9 tensile strength at yields, (Mpa) 20.3 20.6 20.4 20.8 specific elongation rates, (%) 1,420 1,450 1,400 1480 |
Under the high pure nitrogen protection; by following ratio of components amount, hexanaphthene, vinylbenzene, 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) are joined in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃, behind the impurity in a spot of butyllithium elimination system, add the butyllithium of following proportional quantity in the still fast; behind the polyase 13 0 minute; add the isoprene of removing impurity, polymerization added SiCl after 90 minutes
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains styrene-isoprene-phenylethene star block copolymer (SIS) after through water vapor cohesion drying.The rerum natura of resulting polymers sees Table 7.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Vinylbenzene (gram) 45
Butyllithium (mmole) 5.0
I/Li (mol ratio) 0.15
Isoprene (gram) 255
Si-Cl
4/ Li (mol ratio) 0.25 embodiment 38
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 37 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.8, other operation and condition are with embodiment 37.Embodiment 39
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 37 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.5, other operation and condition are with embodiment 37.Embodiment 40
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 37 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.15 and condition are with embodiment 37.
Table 7
Embodiment 41
| Embodiment sequence number 37 38 39 40 |
| Shao Er hardness 40 43 42 44 tension sets, (%) 17 15 14 16 300% tensile modulus, (Mpa) 1.0 1.0 1.0 1.0 tensile strength at yields, (Mpa) 21.0 21.0 21.0 21.0 specific elongation rates, (%) 1,460 1,440 1,480 1400 |
Under the high pure nitrogen protection; by following ratio of components amount; hexanaphthene, divinyl, vinylbenzene, tetrahydrofuran (THF) (THF) are joined in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; after the polymerization 60 minutes; add divinyl, vinylbenzene, 2-(N, N-diethyl) the amino-ethyl n-butyl ether (I) of removing impurity, polymerization 60 minutes; after polyreaction finishes, add SnCl
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with the 4g antioxidant 264 is to stop polyreaction in 1: 1 Virahol and the toluene solution, glue obtains solution polymerized butadiene styrene rubber after condensing drying through water vapor, this is a kind of random butylbenzene binary segmented copolymer, first random section styrene content and divinyl 1,2 structure are low, help reducing rolling resistance.Second random section styrene content is high and have the high vinyl structure of content, and favourable anti-slippery improves, for the radial-ply tyre tyre surface with glue ideal raw material comparatively.The structure and the rerum natura of resulting polymers see Table 8.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
1,3-butadiene (gram) 135
Vinylbenzene (gram) 15
Butyllithium (mmole) 3.0
THF/Li (mol ratio) 5.0
1,3-butadiene (gram) 90
Vinylbenzene (gram) 60
I/Li (mol ratio) 2.0
SnCl
4/ Li (mol ratio) 0.18 embodiment 42
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 41 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=5.0, other operation and condition are with embodiment 41.Embodiment 43
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 41 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=1.6 and condition are with embodiment 41.
Table 8
| Embodiment sequence number 41 42 43 |
| Combined styrene content, (%) 25 25 25 two sections average 1,2-structural content, (% 1) 42 43 41 Shao Er hardness, 62 61 60 tear strengths, (Mpa) 30 29 30 tension sets, (%) 12 12 12 300% tensile modulus, (Mpa) 9.7 9.5 9.6 tensile strength at yields, (Mpa) 19.1 18.9 18.8 specific elongation rates, (%) 520 516 540 tan δ 0 (℃) 0.285 0.342 0.302 50 (℃) 0.0908 0.1078 0.1007 |
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.Embodiment 44
Under the high pure nitrogen protection; by following ratio of components amount, with hexanaphthene, 1,3-butadiene, vinylbenzene, 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing, be warming up to 50 ℃, behind the impurity in a spot of butyllithium elimination system; add many chelatings lithium of following proportional quantity in the still fast; 50-90 ℃ of polymerization 120 minutes, after polyreaction finishes, add SnCl
4Carry out coupling, after 30 minutes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, add 37.5 parts of aromatic hydrocarbon oil by 100 parts of polymkeric substance (weight), continue to stir after 30 minutes, glue obtain after through water vapor cohesion drying GPC present the above wide distribution in three peaks or three peaks molecular weight contain intermingle with oil-extended styrene-butadiene rubber.This type of random oil-extended styrene-butadiene rubber, processing characteristics is good, has good physicomechanical properties, suitable tire and the industrial rubber articles done.The structure and the rerum natura of resulting polymers see Table 9.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
1,3-butadiene (gram) 225
Vinylbenzene (gram) 75
Many chelas lithium
Annotate(mmole) 3.0
I/Li (mol ratio) 0.15
SnCl
4/ Li (mol ratio) 0.18
Annotate: this many chelatings lithium be by 1 mole of n-Butyl Lithium and 0.3 mole of Vinylstyrene in hexanaphthene in the presence of few butadiene polymerization obtain, its concentration is in the amount of active lithium.Embodiment 45
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 44 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.8, other operation and condition are with embodiment 44.Embodiment 46
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 44 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.5, other operation and condition are with embodiment 44.Embodiment 47
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 44 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.15 and condition are with embodiment 44.
Table 9
Annotate 11, the 2-structural content is partly to be that benchmark calculates with polyhutadiene.Embodiment 48
| Embodiment sequence number 44 45 46 47 |
| Combined styrene content, (%) 25 25 25 25 1,2-structural content, (% 1) 32 33 32 33 crude rubber Mooney viscosities 160 155 161 160 fill mooney viscosity 47 48 46 47 Shao Er hardness 60 60 60 60 tear strengths behind 37.5 parts of aromatic hydrocarbon oil, (kN/m) 28 28 28 28 tension sets, (%) 11 12 12 11 300% tensile modulus, (Mpa) 8.2 8.3 8.2 8.4 tensile strength at yields, (Mpa) 17 17.2 17.1 17.4 specific elongation rates, (%) 590 589 600 593 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexane; isoprene; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; 50-90 ℃ of polymerization 120 minutes; after polyreaction finished, being dissolved in volume ratio with 4 gram antioxidant 264s was to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains isoprene and styrene random multipolymer after condensing drying through water vapor.This base polymer can partly replace natural rubber, is used for various rubber items.The structure and the rerum natura of resulting polymers see Table 10.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Isoprene (gram) 270
Vinylbenzene (gram) 30
Butyllithium (mmole) 1.2
I/Li (mol ratio) 2.0 embodiment 49
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 48 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=4.0, other operation and condition are with embodiment 48.Embodiment 50
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 48 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=1.7 and condition are with embodiment 48.
Table 10
Annotate 1: with polyisoprene partly is that benchmark calculates.Embodiment 51
| Embodiment sequence number 48 49 50 |
| Combined styrene content, (%) 10 10 10 3,4-structural content, (% 1) 51 50 52 1,2-structural content, (% 1) 656 mooney viscosities, 83 84 82 Tg, (℃)-13-13-12 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene; isoprene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; after the polymerization 60 minutes; add the vinylbenzene of removing impurity, polyase 13 added Vinylstyrene (DVB) and carries out coupling after 0 minute; after 30 minutes; being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains isoprene-vinylbenzene multi-arm radial pattern segmented copolymer after through ethanol cohesion vacuum drying oven drying, can be used as the novel viscosity index improver of lubricating oil behind this hydrogenation of polymer.The microtexture of resulting polymers sees Table 11.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Isoprene (gram) 210
Butyllithium (mmole) 3.0
I/Li (mol ratio) 0.4
Vinylbenzene (gram) 90
DVB/Li (mol ratio) 5.0 embodiment 52
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 51 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=1.5, other operation and condition are with embodiment 51.Embodiment 53
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 51 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=2.0, other operation and condition are with embodiment 51.Embodiment 54
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 51 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.35 and condition are with embodiment 51.
Table 11
Annotate 1: with polyisoprene partly is that benchmark calculates.Embodiment 55
| Embodiment sequence number 51 52 53 54 |
| Combined styrene content, (%) 30 30 30 30 3,4-structural content, (% 1) 48 48 48 48 1,2-structural content, (% 1)???4?????4?????4?????4 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene; 1; the 3-divinyl; isoprene; uncle's pentyloxy potassium; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; the butyllithium of following proportional quantity is added in the still fast, 50-90 ℃ of polymerization 240 minutes, after polyreaction finishes; being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains divinyl and isoprene random copolymers after through water vapor cohesion drying.The structure of resulting polymers sees Table 12.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
1,3-butadiene (gram) 210
Isoprene (gram) 90
Butyllithium (mmole) 3
I/Li (mol ratio) 0.05
Uncle's pentyloxy potassium/Li (mol ratio) 0.1 embodiment 56
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 55 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.05, other operation and condition are with embodiment 55.Embodiment 57
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 55 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.1, other operation and condition are with embodiment 55.Embodiment 58
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 55 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.05 and condition are with embodiment 55.
Table 12
Annotate 1: with polyhutadiene partly is that benchmark calculates; Annotate 2: with polyisoprene partly is that benchmark calculates.Embodiment 59-61
| Embodiment sequence number 55 56 57 58 |
| Polybutadiene content, (%) 70 70 70 70 polyisoprene content, (%) 30 30 30 30 polyhutadiene 1, the 2-structural content, (% 1) 14 13 13 15 polyisoprene 3,4-structural content, (% 2) 8888 polyisoprene 1,2-structural content, (% 2)?0????0?????0?????0 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; behind the polyase 13 0 minute; add divinyl and the isoprene mixture of removing impurity; after the polymerization 120 minutes, add the vinylbenzene of removing impurity, polyase 13 0 minute again; after polyreaction finishes; being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains styrene butadiene after through water vapor cohesion drying; isoprene-styrol copolymer, wherein divinyl; isoprene block is divinyl and isoprene gradual change copolymerization section; its butadiene structure unit content reduces gradually, and isoprene structural unit content raises gradually.This base polymer can be used for making nontoxic hot melt adhesive, and character and styrene-isoprene-phenylethene are close, and former section cost is low.The structure and the rerum natura of resulting polymers see Table 13.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Vinylbenzene (gram) 22.5
Butyllithium (mmole) 2.3
I/Li (mol ratio) 0.1
1,3-butadiene (gram) changes
Isoprene (gram) changes
Vinylbenzene (gram) 22.5 embodiment 62-64
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 59-61 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.30, other operation and condition are with embodiment 59-61.Embodiment 65-67
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 59-61 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.20, other operation and condition are with embodiment 59-61.Embodiment 68-70
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 59-61 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.1 and condition are with embodiment 59-61.
Table 13
Annotating 1 partly is that benchmark calculates with poly-conjugated-diolefin.Embodiment 71-73
| Embodiment is in conjunction with benzene second polybutadiene content/poly-different tensile strength elongation sequence number alkene content, (%) pentadiene content, 1?(％/％)???(Mpa)????(％) |
| 59??????15???????????????????5/95??????????????17.8?????1300 60??????15???????????????????15/85?????????????17.6?????1300 61??????15???????????????????30/70?????????????17.4?????1300 62??????15???????????????????5/95??????????????17.8?????1300 63??????15???????????????????15/85?????????????17.6?????1300 64??????15???????????????????30/70?????????????17.4?????1300 65??????15???????????????????5/95??????????????17.8?????1300 66??????15???????????????????15/85?????????????17.6?????1300 67??????15???????????????????30/70?????????????17.4?????1300 68??????15???????????????????5/95??????????????17.8?????1300 69??????15???????????????????15/85?????????????17.6?????1300 70??????15???????????????????30/70?????????????17.4?????1300 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene; vinylbenzene; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I); uncle's pentyloxy potassium joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; behind the polyase 13 0 minute; add divinyl and the isoprene mixture of removing impurity; after the polymerization 120 minutes; add the vinylbenzene of removing impurity again; after polyase 13 0 minute, polyreaction finished, restraining antioxidant 264s with 4, to be dissolved in volume ratio be to stop polyreaction in 1: 1 Virahol and the toluene solution; glue obtains styrene butadiene after condensing drying through water vapor; isoprene-styrene triblock copolymer, wherein divinyl; isoprene block is the random copolymerization section of divinyl and isoprene.This type of triblock copolymer, except that being fit to do the basestocks of the various nontoxic binding materials of soft type, weather and ageing-resistant performance get very big improvement behind its hydrogenation, make the compatilizer and the toughner of model engineering plastic.The structure and the rerum natura of resulting polymers see Table 14.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
Vinylbenzene (gram) 22.5
Butyllithium (mmole) 2.3
I/Li (mol ratio) 0.1
1,3-butadiene (gram) changes
Isoprene (gram) changes
Vinylbenzene (gram) 22.5
Uncle's pentyloxy potassium/Li (mol ratio) 0.1 embodiment 74-76
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 71-73 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=0.30, other operation and condition are with embodiment 71-73.Embodiment 77-79
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 71-73 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.20, other operation and condition are with embodiment 71-73.Embodiment 80-82
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 71-73 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.1 and condition are with embodiment 71-73.
Table 14
Annotating 2 partly is that benchmark calculates with poly-conjugated-diolefin.Embodiment 83
| Embodiment is in conjunction with benzene second polybutadiene content/poly-different tensile strength elongation sequence number alkene content, (%) pentadiene content, 1(％/％)??(Mpa)????(％) |
| 71??????15?????????????????????5/95??????????18.0?????1250 |
| 72?????15????????15/85?????17.8???1250 73?????15????????30/70?????17.6???1250 74?????15????????5/95??????18.0???1250 75?????15????????15/85?????17.8???1250 76?????15????????30/70?????17.6???1250 77?????15????????5/95??????18.0???1250 78?????15????????15/85?????17.8???1250 79?????15????????30/70?????17.6???1250 80?????15????????5/95??????18.0???1250 81?????15????????15/85?????17.8???1250 82?????15????????30/70?????17.6???1250 |
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene; 1; the 3-divinyl; isoprene; vinylbenzene; uncle's pentyloxy potassium; 2-(N; the N-diethyl) amino-ethyl n-butyl ether (I) joins in the stainless steel polymeric kettle of 5 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of following proportional quantity in the still fast; 50-90 ℃ of polymerization 240 minutes; after polyreaction finishes; being dissolved in volume ratio with the 4g antioxidant 264 is to stop polyreaction in 1: 1 Virahol and the toluene solution, and glue obtains divinyl after through water vapor cohesion drying; isoprene and polystyrene ternary random copolymers.This analog copolymer has low-styrene and high-vinyl structural content, has shown the huge superiority that is used for tire tread glue as a kind of " integrated rubber ".Also available SnCI
4Carry out part coupling branching or use the ammoniac compounds end-blocking, and further reduce rolling resistance.The structure of resulting polymers sees Table 15.
Ratio of components is as follows:
Hexanaphthene (gram) 2800
1,3-butadiene (gram) 120
Isoprene (gram) 120
Vinylbenzene (gram) 60
Butyllithium (mmole) 3
I/Li (mol ratio) 0.2
Uncle's pentyloxy potassium/Li (mol ratio) 0.1 embodiment 84
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 83 with 2-(N, N-diethyl) amino-ethyl sec-butyl ether (II), II/Li=1.0, other operation and condition are with embodiment 83.Embodiment 85
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 83 with 2-(N, N-diethyl) amino-ethyl isobutyl ether (III), III/Li=0.5, other operation and condition are with embodiment 83.Embodiment 86
Replace 2-(N, N-diethyl) amino-ethyl n-butyl ether (I) among the embodiment 83 with 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether (IV), other operation of IV/Li=0.2 and condition are with embodiment 83.
Table 15
Annotate 1: with polyhutadiene partly is that benchmark calculates; Annotate 2: with polyisoprene partly is that benchmark calculates.
| Embodiment sequence number 83 84 85 86 |
| Combined styrene content, (%) 20 20 20 20 polybutadiene content, (%) 40 40 40 40 polyisoprene content, (%) 40 40 40 40 polyhutadiene 1, the 2-structural content, (% 1) 39 40 38 41 polyisoprene 3,4-structural content, (% 2) 40 41 39 42 polyisoprene 1,2-structural content, (% 2)?3???4????3???5 |
Proved absolutely by the foregoing description data: the anionoid polymerization that is used for conjugated diolefine and/or monovinylarene by novel texture conditioning agent provided by the present invention has the characteristic of unique adjusting polymeric chain microtexture.
Claims (15)
1, the preparation method of a kind of conjugated diolefine and/or monovinyl arene polymer, this method is included in the structure regulator shown in the following general formula (a) and exists down, with the organolithium is initiator, in inert solvent, in 0-150 ℃ of temperature range, initiated polymerization conjugated diolefine and/or monovinylarene get polymkeric substance
Wherein:
R
1, R
2, R
3Each other can be identical or different, and be alkyl independently of one another;
N is the positive integer of 1-4; Wherein the molar ratio range of structure regulator and organolithium is 0.01: 1-40: 1.
2, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, R in the structure regulator of wherein said general formula a
1, R
2Be the identical or different alkyl that contains 1-10 carbon atom, R
3For containing the alkyl of 1-16 carbon atom.
3, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein said structure regulator is 2-(N, the N-diethyl) amino-ethyl n-butyl ether, 2-(N, the N-diethyl) amino-ethyl sec-butyl ether, 2-(N, the N-diethyl) amino-ethyl isobutyl ether and 2-(N, N-diethyl) amino-ethyl normal-butyl glycol ether.
4, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein said organolithium is ethyl, n-Butyl Lithium, s-butyl lithium, isobutyl-lithium, ethyl two lithiums, 1,4 two lithium butane, the many lithiums of many chelating types.
5, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein said conjugated diolefine is divinyl, isoprene, monovinylarene is vinylbenzene, vinyl toluene.
6, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein said inert solvent is aromatic hydrocarbon, aliphatic hydrocrbon, naphthenic hydrocarbon or naphthenic hydrocarbon and aliphatic hydrocrbon mixture.
7, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein polymeric reaction temperature is 30-120 ℃.
8, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, wherein said coupling agent is tin tetrachloride, dichlorosilane, silicon tetrachloride, organo-siloxane class, Vinylstyrene, phenylformic acid diester and monoester class; The mol ratio of coupling agent and organolithium is 0.05-0.5.
9, the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer, the mol ratio of wherein said structure regulator and organolithium is 0.02: 1-1.0: 1.
10, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation is 1, the polyhutadiene of 2 structural content 12-75%, the polyisoprene of height 3,4 structures and the line style and the branching type polystyrene of the narrow distribution of molecular weight.
11, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation is the multipolymer with grading structure of vinylbenzene and divinyl, benzene diene and isoprene, styrene butadiene-isoprene, divinyl and isoprene.
12, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation is the random copolymers of vinylbenzene and divinyl, vinylbenzene and isoprene, divinyl and isoprene and styrene butadiene-isoprene.
13, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation is styrene butadiene, styrene-isoprene, butadiene-isoprene di-block copolymer; Styrene-butadiene-styrene, styrene-isoprene-phenylethene three blocks or star copolymer.
14, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation is styrene butadiene-isoprene-vinylbenzene, and wherein divinyl and isoprene block can be the multipolymer of asymmetric transition or random mid-block.
15, the polymkeric substance of the preparation method of a kind of conjugated diolefine according to claim 1 and/or monovinyl arene polymer preparation be the many lithiums of many chelating types cause have an above wide distribution polymer in molecular weight distribution three peaks or three peaks.
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| WO2004014966A1 (en) * | 2002-07-25 | 2004-02-19 | Walter Hellermann | Microstructure chain transfer agents for anionic polymerization |
| CN100448906C (en) * | 2006-08-10 | 2009-01-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN101638450B (en) * | 2008-07-29 | 2011-01-19 | 中国石油化工股份有限公司 | Method for preparing solution-polymerized conjugated diene homopolymer or conjugated diene/monovinyl aromatic hydrocarbon copolymer with high vinyl content |
| CN102952363A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Wide-distribution block copolymer mixture and its preparation method |
| CN104628898A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Olefin polymerization termination method |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
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| CN112552451A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Random butadiene-isoprene copolymer, synthesis method thereof and low-rolling-resistance automobile tire tread rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004014966A1 (en) * | 2002-07-25 | 2004-02-19 | Walter Hellermann | Microstructure chain transfer agents for anionic polymerization |
| CN100448906C (en) * | 2006-08-10 | 2009-01-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN101638450B (en) * | 2008-07-29 | 2011-01-19 | 中国石油化工股份有限公司 | Method for preparing solution-polymerized conjugated diene homopolymer or conjugated diene/monovinyl aromatic hydrocarbon copolymer with high vinyl content |
| CN108409926A (en) * | 2011-01-30 | 2018-08-17 | 戴纳索尔伊莱斯托米罗斯公司 | Alternation triblock copolymer |
| CN108559288B (en) * | 2011-01-30 | 2020-10-27 | 戴纳索尔伊莱斯托米罗斯公司 | Tapered triblock copolymers |
| CN108559288A (en) * | 2011-01-30 | 2018-09-21 | 戴纳索尔伊莱斯托米罗斯公司 | Alternation triblock copolymer |
| CN102952363A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Wide-distribution block copolymer mixture and its preparation method |
| CN102952363B (en) * | 2011-08-19 | 2016-12-14 | 中国石油天然气股份有限公司 | A kind of wide distribution block copolymer mixture and preparation method thereof |
| CN104628898A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Olefin polymerization termination method |
| CN105175659B (en) * | 2015-07-23 | 2017-11-03 | 湖南博瑞康新材料有限公司 | A kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN112552451A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Random butadiene-isoprene copolymer, synthesis method thereof and low-rolling-resistance automobile tire tread rubber |
| CN113956411A (en) * | 2020-07-20 | 2022-01-21 | 中国石油天然气股份有限公司 | Regulator of conjugated diene and application thereof |
| CN113956411B (en) * | 2020-07-20 | 2024-03-01 | 中国石油天然气股份有限公司 | Regulator of conjugated diene and application thereof |
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