CN103374109A - Star-shaped isoprene-styrene copolymer and preparation method thereof - Google Patents
Star-shaped isoprene-styrene copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a star-shaped isoprene-styrene copolymer containing a random transition section and a preparation method thereof. The star-shaped isoprene-styrene copolymer is characterized in that the structural formula is [I1-S1-I2/S2]n-Y,], wherein Y is Si or Sn, n is a branching degree, n is more than or equal to 2.5 and less than or equal to 4, and I1-S1 is a transition section copolymer of polystyrene and polyisoprene; I2/S2 is a random section copolymer of the polystyrene and the polyisoprene, the mass fractions of transition sections of the polystyrene and the polyisoprene are 40-75wt%, and the mass fractions of random sections of the polystyrene and the polyisoprene are 25-60wt%. High styrene rubber disclosed by the invention has the characteristics of high hardness and good intensity and elasticity; when the high styrene rubber is used simultaneously with multiple synthetic rubber or natural rubber, the properties of rigidity, hardness, wearing resistance, tear resistance, dielectricity and the like of rubber products can be improved, and the high styrene rubber can be widely applied to the rubber processing fields of tires, tapes, rubber tubes, rubber overshoes and the like and other industries and can be further used for modifying synthetic plastics.
Description
Technical field
The present invention relates to a kind of isoprene that contains random transition-vinylbenzene star copolymer and preparation method thereof, the polymkeric substance characteristics of being synthesized are the star high styrene rubbers of high rigidity, high abrasion, good springiness.
Background technology
The multipolymer that isoprene and vinylbenzene form, combined styrene is generally 23～30%, if combined styrene content is high, the multipolymer plasticity that obtains is larger; Otherwise then the elasticity of multipolymer is larger.Usually the multipolymer of styrene in the molecular structure between 45%～70% called high styrene rubber, the combined styrene amount is called high styrene resin 70% above person.Because the combined styrene amount of high styrene rubber is higher, so its physical property is different from universal styrene-butadiene rubber(SBR).High styrene rubber generally uses seldom separately, with various synthetic rubber or natural rubber and time spent, can improve the performance such as rigidity, hardness, wear resistance, tear strength, dielectricity of rubber item, can be widely used in tire industry, shoemaking industry, Printing industry and other industry, also can be used for the modification of synthetic plastics, and extremely pay attention to.
CN1271740A disclosed " production method of high styrene rubber ", its product high styrene resin is a kind of Plastic Rubber Products, as elastomeric strengthening agent, can with the various synthetic rubber except isoprene-isobutylene rubber, natural rubber is also used, improve the tensile strength of rubber, tear strength, improve the hardness of rubber, wear resistance and electrical insulating property, for the manufacture of high rigidity, the goods that relative density is little, the high styrene resin emulsion is got through letex polymerization by divinyl, vinylbenzene, and itself and SBR-1502 latex are carried out common cohesion, dehydration, granulation by the combined styrene content requirement.The advantages such as this product has the hardness height, and mooney viscosity is large, the production technology operation of this invention, easily control.CN1544522A described " preparation method of high styrene rubber " produces with high styrene resin and high styrene latex blending to make.Patent is take fatty acid soaps, RA rosin acid, alkyl-sulphate, phenylbenzimidazole sulfonic acid salt etc. as emulsifying agent, take superoxide as initiator, take mercaptan as conditioning agent, add ionogen commonly used, under 40～80 ℃, make 5～25% divinyl and 75～95% styrene emulsion copolymerization, in 5～12h, prepared high styrene resin under the condition of transformation efficiency＞98.5%; Again with the synthetic high styrene resin emulsion of aforesaid method, with the SBR-1502 latex that contains vinylbenzene 23.5 ± 1% or SBR-1500 latex blending, altogether cohesion, be prepared into high styrene rubber.It is short to have the reaction times, easily control, constant product quality, the distinguishing feature such as energy consumption is low.CN1865301A has reported a kind of take vinylbenzene and divinyl as monomer, add water, activation phase, molecular weight regulator, deionized water, adding initiator initiated polymerization, polymerization generates SBR emulsion or high styrene resin emulsion, adopt the mode of the multistage polymerization of normal temperature emulsion to add monomer and molecular weight regulator, continue reaction, directly synthesize the high styrene rubber emulsion, emulsion makes high styrene rubber through cohesion, drying.CN1224733A has announced a kind of " graft-blending high-phenylethylene rubber and manufacture method thereof ", it is main raw material that waste polystyrene foam and styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber are adopted in this invention, blend graft under the effects such as linking agent, initiator, form high styrene rubber, have cost low, improve environmental pollution, the advantage such as manufacturing process is simple.
From result for retrieval, produce high styrene rubber both at home and abroad and all adopt divinyl and styrene monomer to react, all do not adopt isoprene and styrene monomer to react.The isoprene structural unit is very similar to the structural unit of natural rubber, use the isoprene monomer synthetic polymer can make the characteristics of the performance of product and purposes and natural gum more approaching, in application, can partly or completely substitute the natural rubber that needs blend.And mostly adopt altogether condensation technique of latex in the prior art, although this technological process can access the high styrene rubber of better performances, but this method Main Problems is: at first on technique, need to synthesize respectively first SBR-1500 or SBR-1502 latex and high styrene resin emulsion, mix again by a certain percentage analyzing two kinds of qualified emulsions, then obtain high styrene rubber through condensing drying, its technical process is relatively long to need preparation and the synthesis procedure such as degassed of twice water, oil phase, initiator; Secondly on production cost, because synthetic SBR-1500 or SBR-1502 latex monomer transformation efficiency only 70%, unreacted monomer accounts for 30%, and this part monomer is difficult to reclaim in the production equipment of middle and small scale, causes production cost is higher and polymerization process is required equipment, auxiliary material, personnel, time, the energy relatively many; On the production cycle, because the synthesis temperature of high styrene resin emulsion is high temperature polymerization, polymeric kettle inner structure gel is more in addition, and used polymeric kettle is usually produced 10 batches of needs and carried out once clear still operation, so plant factor is lower.
Adopt the synthetic high styrene rubber of method of solution polymerization, compare with emulsion polymerization technology, have manufacturing process simple, improve environmental pollution, low cost and other advantages.CN00100847.1 has reported an isoprenoid, divinyl, styrene triblock copolymer and preparation method thereof, segmented copolymer has following symmetrical structure: SBR-I-SBR, wherein SBR is divinyl, styrene random multipolymer, I is polyisoprene blocks, and product is the block structure multipolymer.CN96118387.X has reported styrene-butadiene block copolymer and manufacture method thereof, and it mainly is preparation SBS thermoplastic elastomer, and product is block structure, without transition, does not also have the variation of contents of ethylene simultaneously.Patent CN1264714A has reported by the method that contains many huge legendary turtles type organolithium, alkoxyl group potassium or sodium alkylate, low 1, the 2-structure Conjugated Diolefin of polar additive initiation preparation and single ethene aromatic hydrocarbons random copolymers.Wherein the Conjugated Diolefin hydrocarbon monomer is 1,3-butadiene, and single ethene aromatic monomer is vinylbenzene, and the content of Conjugated Diolefin hydrocarbon monomer is 50～85%, and the content of single ethene aromatic monomer is 15～50%.Alkoxyl group potassium is 0.01～0.6 with the mol ratio that adds the initiator system organic single-lithium, is 0.025～0.5 preferably, and polar additive is 0～1 with the mol ratio that adds the initiator system organic single-lithium.Polar additive is tetrahydrofuran (THF), and polymerization temperature is 0～150 ℃, is preferably 50～80 ℃, uses tin tetrachloride to carry out linked reaction as coupling agent, and coupling agent is 0.1～0.2 with the mol ratio of the organic single-lithium that adds initiator system.This product is block structure, does not have random section.CN200810226626.9 has reported a kind of take divinyl and styrene monomer as raw material, and the coupling of solution polymerization coupling agent prepares the method for star high styrene rubber.Structural formula is expressed as follows: Y-[B
1→ S
1-B
2/ S
2]
4, wherein Y is silicon or tin; B
1→ S
1Be polystyrene and polyhutadiene transition multipolymer; B
2/ S
2Be polystyrene and random section multipolymer of polyhutadiene, initiator once adds in the polymerization process, and monomer joins paradigmatic system at twice in certain sequence, after polymerization finishes, adds coupling agent again and carries out linked reaction and make.This technique is the same with emulsion polymerisation process to prepare high styrene rubber take divinyl and styrene monomer as raw material, because divinyl is compared the former with isoprene with the styrene monomer reactivity ratio with the styrene monomer reactivity ratio and is differed larger in the polymerization process, so be difficult for forming random transition, polymer architecture heterogeneity in the polymer architecture.CN200910118517.X has reported a kind of star block copolymer that is formed by isoprene, divinyl and vinylbenzene, utilize lithium alkylide to cause the polymerization of isoprene, obtain active polyisoprene section, in the presence of polar modifier, utilize active polyisoprene section to cause divinyl and cinnamic copolymerization, obtain segmented copolymer, add coupling agent and carry out coupling, obtain star block copolymer.This product is block structure, does not have transition.US4367325 has reported the preparation method of a kind of high-vinyl-content divinyl, styrenerubber, the synthetic high-vinyl styrene-butadiene rubber(SBR) with gradual change vinyl structure of the method for alternating temperature is adopted in polymerization, divinyl microscopic units medium vinyl content 〉=70%, product has preferably dynamic properties, but this polymkeric substance is without transition.Patent US4519431 has reported a kind of preparation method of solution method high styrene rubber, adopt monomer once to add, initiator once adds the high styrene rubber of the synthetic hub-and-spoke configuration of method of then coupling, this technique charging times is less, simple to operate, but the divinyl microscopic units is homogeneous structural in the product, without transition.Above-mentioned polymkeric substance all exists product tensile strength and the not high enough shortcoming of hardness.
Summary of the invention
The problem that exists in order to solve prior art, the invention provides a kind of isoprene-styrene copolymerized method for preparing star high styrene rubber, product of the present invention has that hardness height, tensile strength are good, the characteristics of good springiness, be fit to do reinforcement and high hardness material, can be widely used in numerous rubber processings and other industry such as tire, adhesive tape, sebific duct, rubber overshoes, also can be used for the modification of synthetic plastics.
A kind of star high styrene rubber, its structural formula is expressed as follows: [I
1→ S
1-I
2/ S
2]
n-Y, wherein Y is Si or Sn; N is the degree of branching, and n is more than or equal to 2.5 less than or equal to 4, take n more than or equal to 3 as preferred number.I
1→ S
1Be polystyrene and polyisoprene transition multipolymer; I
2/ S
2Be polystyrene and random section multipolymer of isoprene, polystyrene and polyisoprene transition massfraction are 40～75% in the structural formula, and random section massfraction of polystyrene and polyisoprene is 25～60%; Take total monomer weight as 100%, styrene content is 45～75wt% in this star high styrene rubber polymkeric substance, and isoprene content is 25～55wt%.
Wherein in polystyrene and the polyisoprene transition multipolymer in the isoprene unit 1,2-structure and 3,4-structural content are 5～15wt%; In the isoprene unit 1,2-structure and 3,4-structural content are 20～50wt% in random section multipolymer of polystyrene and polyisoprene.
Cinnamic parts by weight are preferably 50～70wt% in the star high styrene rubber multipolymer of the present invention, and the parts by weight of isoprene are preferably 30～50wt%.
The number-average molecular weight of star high styrene rubber of the present invention is 100000～400000, and molecular weight distributing index is 1.2～5.
Specifically, multipolymer of the present invention can obtain in the following way: initiator is once added, and monomer joins paradigmatic system at twice in certain sequence, after polymerization finishes, adds coupling agent again and carries out linked reaction and make, and its order of addition(of ingredients) is as follows:
The I step: add the vinylbenzene that accounts for monomer total amount 27～45wt% and the isoprene monomer mixture that accounts for monomer total amount 15～33wt%, polymerization under the effect of organic lithium initiator, because vinylbenzene is different from the reactivity ratio of isoprene, form isoprene and cinnamic transition in the polymerization process: polymkeric substance can be expressed as: I
1→ S
1-Me, (Me is the metal ion of initiator), temperature of reaction is 50 ℃～80 ℃, reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 20min～80min, in the product in the isoprene unit 1,2-structure and 3, the 4-structural content is 5～15wt%, at this moment, exists without free monomer in the polyreaction;
The II step: add the vinylbenzene that accounts for monomer total amount 18～30wt% and the isoprene monomer mixture that accounts for monomer total amount 10～22wt%, add simultaneously polar activator, the reactivity ratio that act as adjusting vinylbenzene and isoprene of polar activator, make the two random copolymerization, regulate simultaneously in the isoprene unit 1,2-structure and 3,4-structural content form living chain P:I
1→ S
1-I
2/ S
2-Me; Temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～100min, and in the isoprene unit 1,2-structure and 3,4-structural content are 20～50wt%, at this moment, exist without free monomer in the polyreaction in the product;
The III step: after monomer reaction is complete, add coupling agent Y, form: [I
1→ S
1-I
2/ S
2]
n-Y, the mol ratio of coupling agent consumption and initiator organolithium is 0.1～1.0, coupling temperature 60 C～100 ℃, time 40min～80min.
After reacting completely, with the polymers soln water treatment, the consumption of water is generally 100～300 times of initiator amount, is preferably 150～250 times.Taken this to make the star high styrene rubber of high-phenylethylene content, high rigidity, wear-resisting, good springiness.
In order to make polymkeric substance have excellent performance, the invention provides its best preparation method, preparation process is described below:
At first will account for monomer total amount 30～40wt% vinylbenzene and join polymerization system, initiation reaction under the initiator effect with the mixture that accounts for monomer total amount 18～30wt% isoprene monomer mixture and varsol.Temperature of reaction is at 50～80 ℃, and the reaction times is 30～80min, and exist without free monomer this moment, and polymkeric substance can be expressed as I
1→ S
1-Me, in this section isoprene unit 1,2-structure and 3,4-structural content are 5～15wt%; The vinylbenzene that will account for again monomer total amount 20～30wt% adds paradigmatic system with the isoprene monomer mixture that accounts for monomer total amount 12～20wt%, adds simultaneously polar activator, forms living chain P:I
1→ S
1-I
2/ S
2-Me, in this section isoprene unit 1,2-structure and 3,4-structural content are 20～50wt%, and temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～80min; Carry out coupling with a kind of tin or silicide as coupling agent at last, linked reaction is lasted 40～80min and can be finished under 60～100 ℃.
Need in the paradigmatic system of the present invention to add the polar organic compound of 0.01～0.1phm as promoting agent, make alkyl lithium initiator produce polarization or solvation effect, reduce its degree of association, improve the initiation reaction speed of positive initiator such as n-Butyl Lithium, activator can also be regulated the reactivity ratio of vinylbenzene and isoprene, makes the two random copolymerization, and simultaneously activator can improve in the isoprene unit 1,2-structure and 3,4-structural content.This class polar organic compound comprises diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF) (THF), ether, ethyl methyl ether, methyl-phenoxide, phenyl ether, glycol dimethyl ether (DME), triethylamine, 6-methyl phosphonic triamide etc., preferred diethylene glycol dimethyl ether, tetrahydrofuran (THF).The consumption of promoting agent is 0.02～0.08phm preferably.
Polymers soln can add oxidation inhibitor before solvent steams, such as 1076,1010,264, and TNP, one or more in the tri-isopropanolamine, add-on is the 0.5～5wt% that accounts for the monomer total amount, is preferably 0.5～2wt%.
The separation of polymkeric substance from solution can be adopted traditional steam stripping coacervation method, also available devolatilization type screw extrusion press.
The initiator that uses among the present invention is preferably the organic single-lithium compound, and commonly used is alkyl list lithium compound, i.e. RLi, and wherein R is the composite base that contains representative examples of saturated aliphatic alkyl, alicyclic alkyl, aryl or the above-mentioned group of 1～20 carbon atom.This organolithium compound comprises n-Butyl Lithium, s-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium etc.The most frequently used is n-Butyl Lithium and s-butyl lithium.The add-on of organolithium is determined by the molecular weight of the polymkeric substance of design.
The used coupling agent of the present invention is the coupling agents such as tin tetrachloride, silicon tetrachloride, and adopting the dynamics model coupling agent is the effective measure of preparation star high styrene rubber.The consumption of coupling agent is decided according to the amount of initiator, and the mol ratio of general coupling agent consumption and organolithium is 0.1～1.0.
In the polymerization process of the present invention, coupling agent can once add, and also can add in batches.
Polyreaction of the present invention is preferably in the inert gas environment and carries out in anaerobic, anhydrous.Polymerization process is finished in varsol, and varsol comprises straight-chain paraffin, aromatic hydrocarbons and naphthenic hydrocarbon preferably, such as pentane, and hexane, octane, heptane, hexanaphthene, benzene, toluene, ethylbenzene and their mixture, preferably hexanaphthene.Add-on is not particularly limited, and uses common polyreaction aequum to get final product, as being 300～800wt% of total monomer weight.
The mechanical property of high styrene rubber is relevant with monomer ratio and the molecular weight product of vinylbenzene, isoprene among the present invention.In general, styrene content is high, and its hardness is high, and tensile yield is little; Isoprene content is high, and its hardness is low, and tensile yield is high.Simultaneously, the single armed molecular weight of high styrene rubber determines molecular weight product to a certain extent, thereby affects product performance.It is 50000～150000 that the present invention recommends the single armed number-average molecular weight.
The present invention adopts that the method for twice adding of monomer is synthetic to have in the distinct isoprene unit 1,2-structure and 3, the high styrene rubber of 4-structural content, because these different gradual changes-random composition is common and interaction, can promote the cooperate optimization of the various performances of product, improve hardness and the dynamic properties of product.The polyisoprene rubber that isoprene monomer makes, similar to natural rubber because of its structure properties, " natural synthetic rubber " is otherwise known as.In view of characteristics such as anionic polymerization polyisoprene rubber synthesis technique are relatively ripe, product performance and purposes and natural gum are more approaching, the present invention can substitute natural rubber take isoprene and vinylbenzene as raw material prepares high styrene rubber better in product application.And by structure design in the polymerization process, isoprene and styrene monomer homogeneous in polymer molecular structure is distributed, polymer architecture is evenly distributed mutually at microcosmic.When having avoided high styrene rubber and natural rubber mechanically milling, skewness, the shortcoming such as product quality and performances are relatively poor, and energy consumption is large.Star high styrene rubber of the present invention has high rigidity, intensity is good, and the physicals that has again rubber, simultaneously in application, can partially or completely substitute the natural rubber that needs blend, with various synthetic rubber or natural rubber and time spent, the performance such as rigidity, hardness, wear resistance, tear strength, dielectricity of rubber item be can improve, numerous rubber processings and other industry such as tire, adhesive tape, sebific duct, rubber overshoes are widely used in.It is simple that the method for this star high styrene rubber of preparation provided by the present invention has technique, and polymerizing condition is gentle, and product performance are stable, the characteristics that over-all properties is good.
Embodiment
In order to further specify details of the present invention, lower picture is for some embodiment, but should not be so limited.Raw material used among the embodiment all adopts industrial polymerization-grade, and purified rear use is without other special requirement.The results are shown in Table 1 for embodiment and Comparative Examples.
Embodiment 1:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 4315g, vinylbenzene 420g (account for monomer total amount 35%), isoprene 280g (account for monomer total amount 23.3%), the n-Butyl Lithium that adds 12.1mmol, be warming up to 50 ℃, polymerization 80min, again with 4.32g THF, the mixture of 2194g hexanaphthene and 300g vinylbenzene (account for monomer total amount 25%), 200g isoprene (account for monomer total amount 16.7%) is pressed into polymeric kettle and continues reaction 60min, be warming up to 70 ℃ after monomer transforms fully, add 3.1mmolSncl
4Coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add entry 100g after linked reaction is finished, antioxidant 1010 [four-(4-hydroxyl-3,5-t-butyl-phenyl propionic acid) pentaerythritol esters] 12g stirs.Glue is through wet method cohesion, oven dry.
Comparative Examples 1:
Other processing condition and raw material add-on are identical with embodiment 1, and difference is: monomer once adds, and react to polyreaction to exist without free monomer, finally make the star copolymer with random structure.
Embodiment 2:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 4444g, vinylbenzene 330g (account for monomer total amount 27.5%), isoprene 300g (account for monomer total amount 25%), the n-Butyl Lithium that accurately adds 24.1mmol, be warming up to 60 ℃, polymerization 50min, again with 8.64g THF, the mixture of 2088g hexanaphthene and 330g vinylbenzene (account for monomer total amount 27.5%), 240g isoprene (account for monomer total amount 20%) is pressed into polymeric kettle and continues reaction 70min, be warming up to 80 ℃ after monomer transforms fully, add at twice 6.6mmolSncl
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add 1076 oxidation inhibitor 15g after linked reaction is finished, stir.Glue is through wet method cohesion, oven dry.
Comparative Examples 2:
Other processing condition and raw material add-on are identical with embodiment 2, difference is: feed way is different, styrene monomer adds at twice, isoprene once adds, namely add first the part styrene monomer, the rear adding isoprene monomer that reacts completely adds residual styrene at last, makes segmented copolymer.
Embodiment 3:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 324g (account for monomer total amount 27%), isoprene 396g (account for monomer total amount 33%), the n-Butyl Lithium that adds 8.1mmol, be warming up to 60 ℃, polymerization 50min, again with 2.16g THF, the mixture of 3777g hexanaphthene and 216g (account for monomer total amount 18%) vinylbenzene, 264g (account for monomer total amount 22%) isoprene is pressed into polymeric kettle and continues reaction 70min, be warming up to 80 ℃ after monomer transforms fully, add at twice 2.2mmolSncl
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is finished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Comparative Examples 3:
Commercial high styrene rubber on the market, the polyreaction raw material adopts vinylbenzene, divinyl, difference is: polymerization process is different, polymerization high styrene resin (phenylethylene/butadiene=80/20) at first, then with styrene-butadiene rubber(SBR) (phenylethylene/butadiene=23/77) blending, make at last high styrene rubber.
Embodiment 4:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 540g (account for monomer total amount 45%), isoprene 180g (account for monomer total amount 15%), the n-Butyl Lithium that adds 12.1mmol, be warming up to 60 ℃, polymerization 50min, again with 2.16g THF, the mixture of 3777g hexanaphthene and 360g (account for monomer total amount 30%) vinylbenzene, 120g (account for monomer total amount 10%) isoprene is pressed into polymeric kettle and continues reaction 70min, be warming up to 80 ℃ after monomer transforms fully, add at twice 2.2mmolSncl
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is finished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Comparative Examples 4:
Other processing condition and raw material addition sequence are identical with embodiment 4, difference is: styrene monomer accounts for the 27wt% of monomer total amount, vinylbenzene adds 195g for the first time, isoprene adds 526g for the first time, residual monomer adds for the second time, makes at last to contain intermingle with isoprene-styrol copolymer.
Embodiment 5:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 480g (account for monomer total amount 40%), isoprene 240g (account for monomer total amount 20%), stirring the n-Butyl Lithium that adds 12.1mmol, be warming up to 80 ℃, polymerization 20min, again with 0.68g diethylene glycol dimethyl ether (2G), the mixture of 3777g hexanaphthene and 300g (account for monomer total amount 25%) vinylbenzene, 180g (account for monomer total amount 15%) isoprene is pressed into polymeric kettle and continues reaction 40min, it is 60 ℃ that monomer transforms rear control temperature fully, adds 2.2mmolSncl
4Coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is finished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Embodiment 6:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 360g (account for monomer total amount 30%), isoprene 240g (account for monomer total amount 20%), stirring the n-Butyl Lithium that adds 12.1mmol, be warming up to 60 ℃, polymerization 60min, again with 0.68g diethylene glycol dimethyl ether (2G), 3777g hexanaphthene and 360g (account for monomer total amount 30%) vinylbenzene, the mixture of 240g (account for monomer total amount 20%) isoprene is pressed into polymeric kettle and continues reaction 40min, it is 80 ℃ that monomer transforms rear control temperature fully, minute three adding 2.2mmolSncl
4(add Sncl for the first time
450% of total amount adds behind the 2min behind 20%, the 4min and adds remaining 30%) coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add 1010 oxidation inhibitor 12g after linked reaction is finished, stir, glue is through wet method cohesion, oven dry.
Embodiment 7:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 420g, isoprene 280g, add the n-Butyl Lithium of 12.1mmol, be warming up to 80 ℃, polymerization 40min, again with 4.32g THF, the mixture of 3777g hexanaphthene and 360g vinylbenzene, 240g isoprene is pressed into polymeric kettle and continues reaction 60min, and it is 80 ℃ that monomer transforms rear control temperature fully, and minute secondary adds 2.2mmolSicl
4(add Sicl for the first time
480% of total amount adds remaining 20% behind the 15min) coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add 1010 oxidation inhibitor 12g after linked reaction is finished, stir, glue is through wet method cohesion, oven dry.
Embodiment 8:
In the 15L stainless steel cauldron with chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add pentane 2044g, vinylbenzene 480g (account for monomer total amount 40%), isoprene 240g (account for monomer total amount 20%), the n-Butyl Lithium that adds 12.1mmol, be warming up to 80 ℃, polymerization 20min, again with 4.32g THF, the mixture of 3777g pentane and 300g vinylbenzene (account for monomer total amount 25%), 180g isoprene (account for monomer total amount 15%) is pressed into polymeric kettle and continues reaction 40min, it is 60 ℃ that monomer transforms rear control temperature fully, minute three adding 2.2mmolSncl
4(add Sncl for the first time
450% of total amount adds behind the 2min behind 20%, the 4min and adds remaining 30%) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1010 oxidation inhibitor 15g after linked reaction is finished, stir, glue is through wet method cohesion, oven dry.
Table 1 embodiment and Comparative Examples physical and mechanical properties
Upper table shows, in the building-up process of high styrene rubber, adopt casings in twice, regulate the method for isoprene microtexture when feeding in raw material for the second time, high styrene rubber has transition and random section, simultaneously in random section in the isoprene unit 3, the 4-structural content is higher than in the transition in the isoprene unit 3, the 4-structural content, among the present invention take isoprene and vinylbenzene as reaction monomers, the isoprene structural unit is very similar to the structural unit of natural rubber in the polymkeric substance, makes product have the more approaching characteristics of performance and purposes and natural gum, can partly or completely substitute the natural rubber that needs blend in application.And by structure design in the building-up process, isoprene monomer and styrene monomer are evenly distributed in polymkeric substance, make polymkeric substance better in microcosmic phase consistency, macroscopical comprehensive mechanical property is better.High styrene rubber of the present invention has the hardness height, the characteristics that tensile strength is good, the comprehensive mechanical property balance, δ/0 ℃ of value is larger for tan simultaneously, the anti-slippery that shows rubber is better, tan δ/60 ℃ value is less, shows that the rolling resistance of rubber is less, can find out that synthetic high styrene rubber has good dynamic properties.
Claims (14)
1. star high styrene rubber, its structural formula is expressed as follows: [I
1→ S
1-I
2/ S
2] n-Y, wherein Y is Si or Sn; N is the degree of branching, 2.5≤n≤4, I
1→ S
1Be polystyrene and polyisoprene transition multipolymer; I
2/ S
2Be polystyrene and random section multipolymer of polyisoprene, polystyrene and polyisoprene transition massfraction are 40～75% in the structural formula, and random section massfraction of polystyrene and polyisoprene is 25～60%; Take total monomer weight as 100%, styrene content is 45～75% in this star high styrene rubber polymkeric substance, and isoprene content is 25～55%.
2. high styrene rubber as claimed in claim 1 is characterized in that in polystyrene and the polyisoprene transition multipolymer in the isoprene unit 1, and 2-structure and 3,4-texture quality content are 5～15%; In the isoprene unit 1,2-structure and 3,4-structural content are 20～50wt% in random section multipolymer of polystyrene and polyisoprene.
3. high styrene rubber as claimed in claim 1 is characterized in that cinnamic parts by weight are 50～70% in the described star high styrene rubber multipolymer, and the parts by weight of isoprene are 30～50%.
4. high styrene rubber as claimed in claim 1, the number-average molecular weight that it is characterized in that described star high styrene rubber is 100000～400000, molecular weight distributing index is 1.2～5.
5. the preparation method of a high styrene rubber as claimed in claim 1 is characterized in that preparation process is:
The I step: add the vinylbenzene that accounts for total monomer weight 27～45% and the isoprene monomer mixture that accounts for total monomer weight 15～33%, polymerization under the effect of organic lithium initiator, form isoprene and cinnamic transition: polymkeric substance is expressed as: I
1→ S
1-Me, Me is the metal ion of initiator, temperature of reaction is 50 ℃～80 ℃, reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 20min～80min, in the product in the isoprene unit 1,2-structure and 3, the mass content of 4-structure is 5～15%, at this moment, exists without free monomer in the polyreaction;
The II step: add the vinylbenzene that accounts for total monomer weight 18～30% and the isoprene monomer mixture that accounts for total monomer weight 10～22%, add simultaneously polar activator, make the two random copolymerization, form living chain P:I
1→ S
1-I
2/ S
2-Me; Temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～100min, in the isoprene unit 1, the mass content of 2-structure and 3,4-structure is 20～50% in the product, at this moment, exist without free monomer in the polyreaction;
The III step: after monomer reaction is complete, add coupling agent Y, form: [I
1→ S
1-I
2/ S
2]
n-Y, the mol ratio of coupling agent consumption and initiator organolithium is 0.1～1.0, coupling temperature 60 C～100 ℃, time 40min～80min; After reacting completely, with the polymers soln water treatment, the consumption of water is 100～300 times of initiator amount, takes this to make star high styrene rubber.
6. preparation method as claimed in claim 5 is characterized in that preparation process is as follows:
At first will account for the vinylbenzene of total monomer weight 30～40% and account for the isoprene monomer mixture of total monomer weight 18～30% and the mixture of varsol joins polymerization system, initiation reaction under the initiator effect, temperature of reaction is at 50～80 ℃, reaction times is 30～80min, exist without free monomer this moment, and polymkeric substance is expressed as I
1→ S
1-Me, in this section isoprene unit 1, the mass content of 2-structure and 3,4-structure is 5～15%; The vinylbenzene that will account for again total monomer weight 20～30% adds paradigmatic system with the isoprene monomer mixture that accounts for total monomer weight 12～20%, adds simultaneously polar activator, forms living chain P:I
1→ S
1-I
2/ S
2-Me, in this section isoprene unit 1, the mass content of 2-structure and 3,4-structure is 20～50%, and temperature of reaction is 50 ℃～80 ℃, and reaction pressure side is 0.1MPa～0.25MPa, and the reaction times is 30min～80min; Carry out coupling with coupling agent at last, the linked reaction temperature is 60 ℃～100 ℃, and reaction 40min～80min can finish.
7. such as claim 5 or 6 described preparation methods, it is characterized in that described polar activator comprises diethylene glycol dimethyl ether, tetrahydrofuran (THF), ether, ethyl methyl ether, methyl-phenoxide, phenyl ether, glycol dimethyl ether, triethylamine, 6-methyl phosphonic triamide, add-on is 0.01～0.1phm.
8. such as claim 5 or 6 described preparation methods, it is characterized in that polymers soln adds the oxidation inhibitor that accounts for total monomer weight 0.5～5% before solvent steams, be selected from 1076,1010,264, TNP, one or more in the tri-isopropanolamine.
9. preparation method as claimed in claim 8 is characterized in that described added quantity of antioxidant is to account for 0.5～2% of total monomer weight.
10. such as claim 5 or 6 described preparation methods, it is characterized in that described initiator is alkyl list lithium compound, i.e. RLi, wherein R is the composite base that contains representative examples of saturated aliphatic alkyl, alicyclic alkyl, aryl or the above-mentioned group of 1～20 carbon atom.
11. such as claim 5 or 6 described preparation methods, it is characterized in that described initiator is selected from n-Butyl Lithium, s-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium.
12. such as claim 5 or 6 described preparation methods, it is characterized in that described coupling agent is tin tetrachloride, silicon tetrachloride, the mol ratio of coupling agent consumption and initiator is 0.1～1.0.
13. such as claim 5 or 6 described preparation methods, it is characterized in that described coupling agent is once to add or add in batches.
14. such as claim 5 or 6 described preparation methods, it is characterized in that described polyreaction carries out in varsol, varsol is straight-chain paraffin, aromatic hydrocarbons or naphthenic hydrocarbon, add-on is 300～800% of total monomer weight.
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