CN1421471A - Preparation method of conjugated diene and monovinylarene block copolymer - Google Patents
Preparation method of conjugated diene and monovinylarene block copolymer Download PDFInfo
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- CN1421471A CN1421471A CN 02158793 CN02158793A CN1421471A CN 1421471 A CN1421471 A CN 1421471A CN 02158793 CN02158793 CN 02158793 CN 02158793 A CN02158793 A CN 02158793A CN 1421471 A CN1421471 A CN 1421471A
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Abstract
The invention discloses a preparation method of a conjugated diene and monovinyl aromatic hydrocarbon block copolymer. The method comprises the step of carrying out anion living polymerization on conjugated diene and monovinyl aromatic hydrocarbon in an inert solvent at the temperature of 0-150 ℃ by using a high-efficiency chain transfer agent shown in a general formula and using organic lithium as an initiator to obtain a block copolymer. Wherein: r1、R2May be the same or different from each other and are each independently hydrogen or an alkyl group having 1 to 16 carbon atoms; n is 0 or a positive integer from 1 to 6; m is 0 or a positive integer from 1 to 6; n + m is a positive integer of 3 to 7.
Description
Technical field
The present invention relates to the preparation method of a kind of conjugated diolefine and monovinylarene block copolymers, particularly relate to the efficient chain-transfer agent that uses a kind of living anion polymerization to use, prepare the method for conjugated diolefine and monovinylarene block copolymers.
Background technology
At conjugated diolefine and monovinylarene when active anionic polymerization prepares segmented copolymer, the normal method that adopts portion-wise addition conjugated diolefine and/or monovinylarene, when preparation has the mixture of the conjugated diolefine of different block length and quantity and monovinylarene block copolymers, need portion-wise addition conjugated diolefine and/or the mono vinyl arenes monomer except above-mentioned, also need the portion-wise addition organic lithium initiator to prepare, for example when the mixture of synthesizing styrene-butadiene-styrene three embedding multipolymers and styrene-butadiene-styrene-butadiene-styrene five segmented copolymers, normally add first section styrene monomer earlier, by first part's organic lithium initiator initiated polymerization, add first section divinylic monomer afterwards again, treat to add second section organic lithium initiator and second section styrene monomer again after the polymerization fully, add second section divinylic monomer then, add the 3rd section styrene monomer at last, after stopping, obtain the mixture of styrene-butadiene-styrene triblock copolymer and styrene-butadiene-styrene-butadiene-styrene five segmented copolymers, because being the branch secondary, organolithium adds, and in view of the high reactivity of organolithium and need accurate measurement second section add-on, so there is complicated operating process in this kind method and is difficult for the accurately problem of control in industrial implementation.
United States Patent (USP) U.S.P 5,329,005, U.S.P 5,332,810, U.S.P 5,393, and 721 and U.S.P5,616,704 disclose a kind of aminated compounds, react with this type of aminated compounds and organolithium to prepare the functionalized organic lithium initiator that contains nitrogen-atoms in the molecule.
Summary of the invention
The objective of the invention is 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 efficient chain-transfer agent that a class is new, thereby provide a kind of employing new and effective chain-transfer agent, with the organolithium is initiator, and polymerized conjugated diene and monovinylarene prepare the method for segmented copolymer in inert solvent.
The preparation method of conjugated diolefine provided by the invention and monovinylarene block copolymers is included in the high-purity nitrogen atmosphere, with the organolithium is initiator, in inert solvent, under 0-150 ℃ of temperature, adopt the new chain-transfer agent (a) of following general formula, wherein the mol ratio of chain-transfer agent and organolithium is 0.01: 1-1: 1, be preferably 0.05: 1-1: and 1, carry out living anion polymerization conjugated diolefine and monovinylarene and obtain block copolymer.
Wherein: R
1, R
2Each other can be identical or different, and be hydrogen or the alkyl that contains 1-16 carbon atom independently of one another; N is 0 or the positive integer of 1-6; M is 0 or the positive integer of 1-6; N+m is the positive integer of 3-7.
Among the preparation method according to conjugated diolefine provided by the invention and monovinylarene block copolymers, described efficient, new chain-transfer agent of the present invention is to have a compound shown in the following general formula (a),
Wherein: R
1, R
2Each other can be identical or different, and be hydrogen or the alkyl that contains 1-16 carbon atom independently of one another; N is 0 or the positive integer of 1-6; M is 0 or the positive integer of 1-6; N+m is the positive integer of 3-7.The alkyl of a described 1-16 carbon atom is for example methyl, ethyl, propyl group, butyl, n-pentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl, undecyl, tridecyl or pentadecyl etc., more preferably methyl, ethyl, propyl group, butyl or cyclohexyl etc.
The compound of above-mentioned general formula (a) expression is preferably Pyrrolidine, 2-methyl Pyrrolidine, 2-ethyl Pyrrolidine, 2-propyl group Pyrrolidine, 2-butyl Pyrrolidine, 2-hexyl Pyrrolidine, 2-nonyl Pyrrolidine, 2-decyl Pyrrolidine, 2-undecyl Pyrrolidine, 2-tridecyl Pyrrolidine, 2-pentadecyl Pyrrolidine, 2,2-dimethyl tetrahydro pyrroles, 2,2-diethyl Pyrrolidine, 2,2-dipropyl Pyrrolidine, 2,2-dibutyl Pyrrolidine, 2,2-dihexyl Pyrrolidine, 2,2-dinonyl Pyrrolidine, 2,2-didecyl Pyrrolidine, hexamethylene imine, 3-methyl hexamethylene imine, 3-ethyl hexamethylene imine, 3-propyl group hexamethylene imine, 3-butyl hexamethylene imine, 3-hexyl hexamethylene imine, 3-nonyl hexamethylene imine, 3-decyl hexamethylene imine, 3-undecyl hexamethylene imine, 3-tridecyl hexamethylene imine, 3-pentadecyl hexamethylene imine, 3,3-dimethyl hexamethylene imine, 3,3-diethyl hexamethylene imine, 3,3-dipropyl hexamethylene imine, 3,3-dibutyl hexamethylene imine, 3,3-dihexyl hexamethylene imine, 3,3-dinonyl hexamethylene imine or 3,3-didecyl hexamethylene imine etc.
More preferably Pyrrolidine, 2-methyl Pyrrolidine, 2-butyl Pyrrolidine, hexamethylene imine, 3-methyl hexamethylene imine, 3-butyl hexamethylene imine, 3-hexyl hexamethylene imine, 3-nonyl hexamethylene imine or 3,3-dimethyl hexamethylene imine.
In conjugated diolefine provided by the invention and monovinylarene block copolymer preparation method, described conjugate diene monomer is the conjugated diolefine of 4-20 carbon atom, be preferably the conjugated diolefine of 4-12 carbon atom, the conjugated diolefine of 4-8 carbon atom more preferably, divinyl or replace divinyl for example is as 1,3-divinyl, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene etc.; Isoprene, pentadiene or replace pentadiene is as 1,3-pentadiene etc.The conjugated diolefine that wherein is more preferably is 1,3-butadiene or isoprene.Conjugated diolefine can be used separately, also can mix use, and its blending ratio requires to decide according to multipolymer, is not strict with.The conjugate diene monomer consumption is counted 15-60% (weight) with total monomer weight, and it is determined by polymer property and kind.Described mono vinyl arenes monomer is a 8-20 carbon atom, is preferably the monovinylarene of 8-12 carbon atom, and for example vinylbenzene or alkyl-substituted styrene are as a vinyl toluene, p-methylstyrene, to t-butyl styrene, alpha-methyl styrene etc.Mono vinyl arenes monomer can use separately, also can mix use, and its ratio of mixture is not strict with, but arbitrary proportion is actual from obtaining complexity and industrialization, is preferably vinylbenzene or p-methylstyrene, more preferably vinylbenzene.The mono vinyl arenes monomer consumption is counted 40-85% (weight) with total monomer weight, is determined by polymer property and kind.The polymer solution concentration scope is 10-60% (weight), the co-polymer excessive concentration, and viscosity is excessive, makes troubles for stirring, conveying and aftertreatment, is preferably 10-30% (weight).
In conjugated diolefine provided by the invention and monovinylarene block copolymer preparation method, described organic lithium initiator can be organic single-lithium and two 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 or 2-phenyl lithium etc.; Described organic pair of lithium such as ethyl two lithiums, four methynes, two lithiums, five ylmethyl two lithiums, six methynes, two lithiums, 1, two (the 1-lithium base-3-aminomethyl phenyl) benzene, 1 of 3-, 4-two lithiums-1,4-phenyl butane or 1,4-two lithium butane etc. are preferably n-Butyl Lithium or s-butyl lithium.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.
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 butane, hexane and heptane or the aliphatic hydrocrbon mixture with different carbonatomss, and for example refinery by product such as hydrogenated gasoline, reformer raffinates oil etc.; Naphthenic hydrocarbon is pentamethylene, hexanaphthene and methylcyclohexane or its mixture 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 hexanaphthene are pressed the mixture of 1/10-5/5.
Described polymeric reaction temperature is 0-150 ℃, is preferably 30-120 ℃, more preferably 40-90 ℃.
It is liquid that the pressure of described polyreaction should keep polymerization system, generally between 0.05-1.2Mp, is preferably 0.1-0.6Mpa.
Polymerization reaction time is 0.2-6 hour.
Must cause initiator or the active impurity of holding inactivation in advance except that deenergizing for monomer recited above and solvent, as compound, alcohols, carbonyl compound and the acetylene compound etc. of water, oxygen, carbonic acid gas, sulphur.
In conjugated diolefine provided by the invention and monovinylarene block copolymer preparation method, also available terminator, anti-aging agent etc. all are known, generally use Virahol and water to make terminator; Use Hinered phenols itself and be anti-aging agent with the phosphoric acid ester mixture, as 2,6 di tert butyl 4 methyl phenol anti-aging agent (be called for short 2,6,4).
In conjugated diolefine provided by the invention and monovinylarene block copolymer preparation method, if desired, the present invention can adopt conditioning agent that the microtexture of the polymerization degree and conjugated diolefine is regulated in polymerization process.These conditioning agents are known, for example tetrahydrofuran (THF) (THF), glycol dimethyl ether (1G), diethylene glycol dimethyl ether (2G), N, N '-Tetramethyl Ethylene Diamine (TMEDA) etc.The consumption of conditioning agent depends on the kind of selected conditioning agent and determines.
Preparation method's another program of conjugated diolefine provided by the invention and monovinylarene block copolymers, if desired, can adopt coupling agent coupling activity polymeric chain to get conjugated diolefine and monovinylarene block copolymers, this method is included in the high-purity nitrogen atmosphere, with the organolithium is initiator, in inert solvent, in 0-150 ℃ of temperature range, adopt the chain-transfer agent shown in the following general formula (a), wherein the mol ratio of chain-transfer agent and organolithium is 0.01: 1-1: 1, be preferably 0.05: 1-1: 1.Carry out living anion polymerization and get the living polymerization chain, carry out coupling with coupling agent again and get segmented copolymer, wherein the mol ratio of coupling agent and organolithium is 0.01-10, is preferably 0.1-6,
Wherein: R
1And R
2Each other can be identical or different, and be hydrogen or the alkyl that contains 1-16 carbon atom independently of one another; N is 0 or the positive integer of 1-6; M is 0 or the positive integer of 1-6; N+m is the positive integer of 3-7.
In conjugated diolefine provided by the invention and monovinylarene block copolymer preparation method another program, carry out coupling with coupling agent, and forming star-type polymer with long chain branching, its degree of branching generally can be controlled at 10%-80% 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, diethylene adipate, dimethyl adipate, Bisphthalate, polydentate compound such as dichlorosilane, silicon tetrachloride, tin tetrachloride etc., epoxy compounds such as epoxidation oleum gossypii seminis, epoxidised soybean oil, epoxidized liquid polyhutadiene etc.Preferred star-like coupling agent is tin tetrachloride, silicon tetrachloride, Vinylstyrene, epoxidised soybean oil or epoxidized liquid polyhutadiene.The method that adds coupling agent adopts currently known methods, for example finishes back adding coupling agent in polyreaction and carries out linked reaction.The add-on of coupling agent can change in very wide scope, with coupling agent and organolithium molar ratio computing, and preferred 0.01-10, more preferably 0.1-6.
Among the preparation method according to conjugated diolefine provided by the invention and monovinylarene block copolymers, as everyone knows, because the characteristics of living anion polymerization can have various diverse microcosmic structures and content as 1 by the method preparation of living anion polymerization, 2 structural contents, 1,4 structural contents etc., different blocks such as asymmetric transition block and random block etc., different block length, the line style of quantity and block sequence arrangement etc. or the segmented copolymer of hub-and-spoke configuration, it also is the multipolymer of indication preparation in the inventive method, the mixture of styrene-butadiene di-block copolymer and styrene-butadiene one styrene triblock copolymer for example, the mixture of vinylbenzene one isoprene di-block copolymer and vinylbenzene one isoprene one styrene triblock copolymer, the mixture of styrene-butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and styrene-butadiene one vinylbenzene star block copolymer, the mixture of styrene-butadiene one styrene triblock copolymer and styrene-butadiene one styrene-butadiene one vinylbenzene five segmented copolymers, the mixture of vinylbenzene one isoprene, one styrene triblock copolymer and vinylbenzene one isoprene one vinylbenzene one isoprene one vinylbenzene five segmented copolymers, the mixture of styrene-butadiene one styrene triblock copolymer and star block copolymer, the mixture of vinylbenzene one isoprene, one styrene triblock copolymer and star block copolymer, the mixture of styrene-butadiene one isoprene block copolymer and styrene-butadiene one isoprene one benzene diene block copolymer, wherein divinyl and isoprene block can be the multipolymer of asymmetric gradual change or random mid-block, the mixture of styrene-butadiene one isoprene, one styrene block copolymer and styrene-butadiene one isoprene one styrene-butadiene one isoprene one styrene block copolymer, wherein divinyl and isoprene block can be asymmetric gradual change or random mid-block multipolymer, or the mixture of styrene-butadiene one isoprene block copolymer and star block copolymer, wherein divinyl and isoprene block can be multipolymer of asymmetric gradual change or random mid-block etc.
Owing to adopt efficient, new chain-transfer agent among the preparation method of conjugated diolefine provided by the invention and vinyl aromatic (co) hydrocarbon block copolymer, this chain-transfer agent chain transfer ability is strong, can react with organolithium or polymer lithium as quick as thought, and the lithium compound that generates has the activity suitable with organic lithium initiator, can continue initiated polymerization conjugated diolefine and/or monovinylarene, can be used to the mixture of synthetic above-mentioned segmented copolymer; The accurately weighing and directly joining in conjugated diolefine or the mono vinyl arenes monomer of this especially chain-transfer agent, simplified operation process and be convenient to control the content of different block things.
Method provided by the invention can extensively be used to make all kinds, the thermoplastic elastomer with excellent specific property, transparent resin, rubber etc.
Embodiment
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 some and changes in protection domain of the present invention according to 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 mechanical property of polymkeric substance is measured by the universal electrical drawing machine, and polymer blocks content is measured by gel chromatography permeability testing machine (GPC).
Embodiment 1
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene (2200 gram); vinylbenzene (60 gram); tetrahydrofuran (THF) (0.20 gram) 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 3 mmoles in the still fast; feed hot water with the still chuck and guarantee that temperature 50-90 ℃ of polyase 13 of required control is after 0 minute; add the divinyl (90 gram) of removing impurity; after the polymerization 60 minutes; add the divinyl (90 gram) of removing impurity and containing 0.6 mmole hexamethylene imine again; after the polymerization 60 minutes; add the vinylbenzene (60 gram) of removing impurity at last; after the polymerization 40 minutes; after polyreaction finishes; being dissolved in volume ratio with 3 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution; obtain the mixture of styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and styrene-butadiene-styrene triblock copolymer after the glue process water vapor cohesion drying, this polymkeric substance can be used for modifying material.The structure and the rerum natura of resulting polymers see Table 1.
Embodiment 2
With the hexamethylene imine among the Pyrrolidine replacement embodiment 1, other operation and condition are with embodiment 1.
Embodiment 3
With the divinyl among the isoprene replacement embodiment 1, other operation and condition are with embodiment 1.
Embodiment 4
With the hexamethylene imine among the Pyrrolidine replacement embodiment 1, with the divinyl among the isoprene replacement embodiment 1, other operation and condition are with embodiment 1.
Comparative example 1
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene (2200 gram); vinylbenzene (48 gram); tetrahydrofuran (THF) (0.24 gram) 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 2.4 mmoles in the still fast; feed hot water with the still chuck and guarantee that temperature 50-90 ℃ of polyase 13 of required control is after 0 minute; add the divinyl (90 gram) of removing impurity; after the polymerization 60 minutes; add 0.4 mmole butyllithium again; add the divinyl (90 gram) of removing impurity after 5 minutes; after the polymerization 60 minutes; add the vinylbenzene (72 gram) of removing impurity at last; after the polymerization 40 minutes; after polyreaction finishes; being dissolved in volume ratio with 3 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution; obtain the mixture of styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and styrene-butadiene-styrene triblock copolymer after the glue process water vapor cohesion drying, this polymkeric substance can be used for tackiness agent and toughening modifying material.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Combined styrene content % (weight) | ????40 | ????40 | ????40 | ????40 |
| Diblock polymer content % (weight) | ????20 | ????20 | ????20 | ????20 |
| Mw×10 -4 | ????9.0 | ????9.0 | ????9.0 | ????9.0 |
| Mn×10 -4 | ????8.3 | ????8.3 | ????8.3 | ????8.3 |
Can find out synthetic same block polymer from comparative example 1, how compare the step of step interpolation butyllithium with embodiment 1, it is complicated that operation becoming.
Embodiment 5
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene (2200 gram); vinylbenzene (120 gram); tetrahydrofuran (THF) (0.50 gram) 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 3.75 mmoles in the still fast; feed hot water with the still chuck and guarantee that temperature 50-90 ℃ of polyase 13 of required control is after 0 minute; add the divinyl (45 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (45 gram) of removing impurity again; after the polymerization 40 minutes; add the vinylbenzene (45 gram) of removing impurity and containing 0.75 mmole hexamethylene imine again; after the polymerization 40 minutes; add the divinyl (45 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (150 gram) of removing impurity at last; after the polymerization 60 minutes; after polyreaction finishes; being dissolved in volume ratio with 5 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution; obtain the mixture of styrene-butadiene-styrene triblock copolymer and styrene-butadiene-styrene-butadiene-styrene five block copolymers after the glue process water vapor cohesion drying; this polymkeric substance is transparent butadiene styrene resin; energy injection moulding and extrusion molding can be used for medicine equipment; food product pack and toy etc.The structure and the rerum natura of resulting polymers see Table 2.
Embodiment 6
With the hexamethylene imine among the Pyrrolidine replacement embodiment 5, other operation and condition are with embodiment 5.
Comparative example 2
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene (2200 gram); vinylbenzene (100 gram); tetrahydrofuran (THF) (0.50 gram) 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 3 mmoles in the still fast; feed hot water with the still chuck and guarantee that temperature 50-90 ℃ of polyase 13 of required control is after 0 minute; add the divinyl (36 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (44 gram) of removing impurity again; after the polymerization 40 minutes; the butyllithium that adds 1.5 mmoles again; add the vinylbenzene (66 gram) of removing impurity after 5 minutes; after the polymerization 40 minutes; add the divinyl (54 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (150 gram) of removing impurity at last; after the polymerization 60 minutes; after polyreaction finishes; being dissolved in volume ratio with 5 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution; obtain the mixture of styrene-butadiene-styrene triblock copolymer and styrene-butadiene-styrene-butadiene-styrene five block copolymers after the glue process water vapor cohesion drying; this polymkeric substance is transparent butadiene styrene resin; energy injection moulding and extrusion molding can be used for medicine equipment; food product pack and toy etc.
Table 2
| Embodiment 5 | Embodiment 6 | |
| Combined styrene content, % (weight) | ????80 | ????80 |
| Triblock polymer content, % (weight) | ????20 | ????20 |
| 1, the 2-structural content 1, % (weight) | ????10 | ????10 |
| Mw，??×10 -4 | ????10.8 | ????10.8 |
| Mn，??×10 -4 | ????10 | ????10 |
| Tensile strength, Mpa | ????32 | ????32 |
| Flexural strength, Mpa | ????42 | ????42 |
| Elongation, % | ????20 | ????20 |
| Unnotched impact strength, J/m | ????310 | ????310 |
| Transmittance, % | ????88 | ????88 |
Annotate 1: with polyhutadiene partly is benchmark.
Can find out synthetic same block polymer from comparative example 2, how compare the step of step interpolation butyllithium with embodiment 5, it is complicated that operation becoming.
Embodiment 7
Under the high pure nitrogen protection; by following ratio of components amount; with hexanaphthene (2200 gram); vinylbenzene (90 gram); tetrahydrofuran (THF) (0.80 gram) 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 6 mmoles in the still fast; feed hot water with the still chuck and guarantee that temperature 50-90 ℃ of polyase 13 of required control is after 0 minute; add the divinyl (45 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (45 gram) of removing impurity again; after the polymerization 40 minutes; add again and remove impurity and contain 2 mmole hexamethylene imine vinylbenzene (105 gram); after the polymerization 40 minutes; add the divinyl (55 gram) of removing impurity; after the polymerization 40 minutes; add the vinylbenzene (60 gram) of removing impurity at last; after the polymerization 60 minutes; add the 1.2 gram epoxidized liquid polyhutadiene (epoxidized liquid polyhutadiene Mn is 1000, on average contains 4 epoxide groups on each molecular chain) that are dissolved in 10 milliliters of toluene.Coupling 30 minutes, after reaction finishes, being dissolved in volume ratio with 4 gram antioxidant 264s is to stop polyreaction in 1: 1 Virahol and the toluene solution, obtain the mixture of styrene-butadiene-styrene triblock copolymer and star type block co-polymer after the glue process water vapor cohesion drying, this polymkeric substance is transparent butadiene styrene resin, energy injection moulding and blown film can be used for container, displaying property packing and sheet material etc.The structure and the rerum natura of resulting polymers see Table 3.
Table 3
| Embodiment 7 | |
| Combined styrene content, % (weight) | ????75 |
| 1, the 2-structural content 1, % (weight) | ????10 |
| Tensile strength, Mpa | ????25 |
| Flexural strength, Mpa | ????32 |
| Elongation, % | ????120 |
| Unnotched impact strength, J/m | ????400 |
| Transmittance, % | ????88 |
Annotate 1: with polyhutadiene partly is benchmark.
By the foregoing description data declaration: be used for the anionoid polymerization of conjugated diolefine and monovinylarene, the mixture of the segmented copolymer of synthesis of conjugate diene and monovinylarene easily by chain-transfer agent provided by the present invention.
Claims (10)
1. the preparation method of conjugated diolefine and monovinylarene block copolymers, be included in the high-purity nitrogen atmosphere, with the organolithium is initiator, in inert solvent, in 0-150 ℃ of temperature range, adopt the chain-transfer agent shown in the following general formula (a), wherein the mol ratio of chain-transfer agent and organolithium is 0.01: 1-1: 1, carry out living anion polymerization conjugated diolefine and monovinylarene and obtain segmented copolymer
Wherein: R
1And R
2Each other can be identical or different, and be hydrogen or the alkyl that contains 1-16 carbon atom independently of one another;
N is 0 or the positive integer of 1-6;
M is 0 or the positive integer of 1-6;
N+m is the positive integer of 3-7.
2. according to the preparation method of described a kind of conjugated diolefine of claim 1 and monovinylarene block copolymers, wherein said chain-transfer agent is Pyrrolidine or hexamethylene imine.
3. according to the preparation method of described a kind of conjugated diolefine of claim 1 and monovinylarene block copolymers, wherein said organolithium is lithium ethide, n-Butyl Lithium, s-butyl lithium, isobutyl-lithium or 1,4-two lithium butane.
4. according to the preparation method of described a kind of conjugated diolefine of claim 1 and monovinylarene block copolymers, wherein said conjugate diene monomer is 1,3-butadiene or isoprene; Monovinylarene is vinylbenzene or vinyl toluene.
5. according to the preparation method of described a kind of conjugated diolefine of claim 1 and monovinylarene block copolymers, wherein said inert solvent is the mixture of aromatic hydrocarbon, aliphatic hydrocarbon, naphthenic hydrocarbon or naphthenic hydrocarbon and aliphatic hydrocarbon.
6. according to the preparation method of described a kind of conjugated diolefine of claim 1 and monovinylarene block copolymers, wherein said polymeric reaction temperature scope is 30-120 ℃.
7. the preparation method of conjugated diolefine and monovinylarene block copolymers, be included in the high-purity nitrogen atmosphere, with the organolithium is initiator, in inert solvent, in 0-150 ℃ of temperature range, adopt the chain-transfer agent shown in the following general formula (a), wherein the mol ratio of chain-transfer agent and organolithium is 0.01: 1-1: 1, carry out living anion polymerization conjugated diolefine and monovinylarene and get the living polymerization chain, carry out coupling with coupling agent again and obtain segmented copolymer, the mol ratio 0.01 of coupling agent and organolithium
Wherein: R
1And R
2Each other can be identical or different, and be hydrogen or the alkyl that contains 1-16 carbon atom independently of one another;
N is 0 or the positive integer of 1-6;
M is 0 or the positive integer of 1-6;
N+m is the positive integer of 3-7.
8. according to the preparation method of claim 1 or 7 described a kind of conjugated diolefines and monovinylarene block copolymers, wherein the molar ratio range of chain-transfer agent and organolithium is 0.05: 1-1: 1
9. according to the preparation method of described a kind of conjugated diolefine of claim 7 and monovinylarene block copolymers, wherein said coupling agent is tin tetrachloride, silicon tetrachloride, Vinylstyrene, epoxidation oleum gossypii seminis, epoxidised soybean oil and epoxidized liquid polyhutadiene; The molar ratio range of coupling agent and organolithium is 0.1-6.
10. the mixture for preparing styrene butadiene di-block copolymer and styrene-butadiene-styrene triblock copolymer according to the preparation method of described a kind of conjugated diolefine of each claim of claim 1-9 and monovinylarene block copolymers; The mixture of styrene-isoprene di-block copolymer and styrene-isoprene-phenylethene triblock copolymer; The mixture of styrene-butadiene-styrene triblock copolymer and styrene-butadiene-styrene-butadiene-styrene five segmented copolymers; The mixture of styrene-isoprene-phenylethene triblock copolymer and styrene-isoprene-phenylethene-isoprene-vinylbenzene five segmented copolymers; The mixture of styrene-butadiene-styrene triblock copolymer and star block copolymer; The mixture of styrene-isoprene-phenylethene triblock copolymer and star block copolymer; The mixture of styrene butadiene-isoprene block copolymer and styrene butadiene-isoprene-styrene block copolymer, wherein divinyl and isoprene block can be the multipolymer of asymmetric gradual change or random mid-block; The mixture of styrene butadiene-isoprene-styrene block copolymer and styrene butadiene-isoprene-styrene butadiene-isoprene-styrene block copolymer, wherein divinyl and isoprene block can be the multipolymer of asymmetric gradual change or random mid-block; The mixture of styrene butadiene-isoprene block copolymer and star block copolymer, wherein divinyl and isoprene block can be the multipolymer of asymmetric gradual change or random mid-block.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027063A (en) * | 2008-07-21 | 2011-04-20 | Lg化学株式会社 | Asphalt modifier compositions and asphalt compositions containing same |
| CN105218766A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) |
| CN106414529A (en) * | 2014-05-16 | 2017-02-15 | 科腾聚合物美国有限责任公司 | Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom |
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2002
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027063A (en) * | 2008-07-21 | 2011-04-20 | Lg化学株式会社 | Asphalt modifier compositions and asphalt compositions containing same |
| US9328235B2 (en) | 2008-07-21 | 2016-05-03 | Lg Chem, Ltd. | Asphalt modifier composition and asphalt composition comprising the same |
| CN106414529A (en) * | 2014-05-16 | 2017-02-15 | 科腾聚合物美国有限责任公司 | Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom |
| CN106414529B (en) * | 2014-05-16 | 2019-05-10 | 科腾聚合物美国有限责任公司 | Polyalkenyl coupling agent and conjugated diolefin polymer prepared therefrom |
| CN105218766A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) |
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