CN1247642C - Unimodal radial block copolymer possessing random graded chain and its preparation method - Google Patents
Unimodal radial block copolymer possessing random graded chain and its preparation method Download PDFInfo
- Publication number
- CN1247642C CN1247642C CN 03146385 CN03146385A CN1247642C CN 1247642 C CN1247642 C CN 1247642C CN 03146385 CN03146385 CN 03146385 CN 03146385 A CN03146385 A CN 03146385A CN 1247642 C CN1247642 C CN 1247642C
- Authority
- CN
- China
- Prior art keywords
- conjugated diene
- monomorphism
- monovinylarene
- mixture
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a monomorphism radial block copolymer comprising random gradual changing chain segments, and a preparation method thereof. The monomorphism radial block copolymer has the following structural formula: R-X-[-B3-(B2-S3)B1/S2-S1]3; in the copolymer, the weight portion of single vinyl aromatic hydrocarbon monomers is from 30% to 95%; the weight portion of conjugated dialkene monomers is from 5% to 70%; the molecular weight of polymers is from 160000 to 220000; the random gradual changing chain segments of the polymers are obtained at the polymerization temperature of 65 DEG C to 100 DEG C; the charging speed of the mixtures of the single vinyl aromatic hydrocarbon and the conjugated dialkene metered by the weight percentage is from 4.6% to 9.5%/min; the charging speed of the single vinyl aromatic hydrocarbon is lower than the reaction rate; and the charging speed of the conjugated dialkene is higher than the reaction rate. The polymer has very high transmittance and excellent shock strength and has good elasticity and environmental cracking resistance of products at normal temperature, the polymer can be plasticized and formed at high temperature and can be used in the fields of food packing, medical devices, children's toys, etc.
Description
Technical field
The present invention relates to a kind of radial segmented copolymer of monomorphism that contains random graded chain segment and preparation method thereof, specifically a kind of high transparent, shock resistance monomorphism, have the radial of random graded chain segment or claim star block copolymer and preparation method thereof.
Background technology
In the prior art, the relevant documents and materials of report butadiene-styrene block copolymer are more, as EP0492490, US 4925899, US 5130377, CN 85100418 etc.Patent CN 1073950 has reported a kind of preparation method of butadiene-styrene block copolymer, for once adding initiator, obtains multipolymer through linked reaction, but does not contain transition in the copolymer molecule chain, thereby coupling efficiency is low, and the coupled reaction time is long.The butadiene-styrene block copolymer of US 4925899, US 5130377, CN 85100418 reports is polymorphic or claims multi-modal, during preparation not only initiator divide more than 2 times and to add, monomer divides 4～9 addings especially, the polymerization stage time is long, complex technical process, and can bring impurity into to paradigmatic system because of repeatedly adding monomer and initiator, make part living chain inactivation, the quality of impact polymer and performance. unavoidablely
In order to simplify synthesis technique, improve polymer quality, CN 1241582A discloses a kind of by once adding initiator, adding the method that monomer is prepared the monomorphism three arm star butadiene-styrene block copolymers that contain a random transition 4 times.Adopt the multipolymer of method for preparing to have very high shock strength, good transmittance and the ESCR of goods, be particularly suitable for packaging field.But the synthetic employing thermograde polymerization of transition promptly at high temperature forms random section, forms transition at a lower temperature.The service temperature of this technology is too high, side reaction takes place easily and produce gel.
Transition is synthetic in monovinylarene and the conjugated diene copolymer, the formation of WO96/25442 report transition is by prolonging the reinforced time of divinyl, become discontinuous by the divinyl continuously feeding, vinylbenzene discontinuous charging becoming continuously feeding and controlled polymerization method of temperature obtain, the reinforced time of this method is long, realize alternately control, be unfavorable for suitability for industrialized production.Synthetic middle vinylbenzene and divinyl that patent EP761704A1, US5399628 etc. relate to transition mix, once add, react under steady temperature with certain proportion, the transition randomization degree that obtains in this way is low, progressive formation is not obvious, has influenced product performance.
Summary of the invention
The object of the present invention is to provide a kind of radial segmented copolymer of monomorphism that contains random graded chain segment and preparation method thereof, make polymkeric substance that very high transmittance and resistance to impact shock be arranged, the ESCR of high temperature resistant preferably, hot-air aging resistance and goods is also arranged simultaneously, can be used for packaging field.
A kind of radial segmented copolymer of monomorphism that contains random graded chain segment of the present invention, its structural formula is expressed as follows:
S wherein
1, S
2And S
3Equal representation class monovinylarene, B
1, B
2And B
3All represent conjugated diene; R is the saturated fatty alkyl that contains 1～6 carbon atom, is preferably methyl; X=Si, Sn are preferably the Si atom.
Promptly be by the anionic polymerization synthetic, contain a monovinylarene homopolymerization section, a monovinylarene in the single armed molecular chain. the radial segmented copolymer of monomorphism of a random graded chain segment of conjugated diene and a conjugated diolefin homopolymerization section.The parts by weight of the mono vinyl arenes monomer that contains in the multipolymer of the present invention are 30%～95% (wt), be preferably 35%～85% (wt), the parts by weight of conjugated diene monomer are 5%～70% (wt), be preferably 15%～65% (wt), the molecular weight of polymkeric substance is 160000～220000; The acquisition of the random graded chain segment of this polymkeric substance is that the employing polymerization temperature is 65 ℃～100 ℃, and the method for the feed rate of control monovinylarene and conjugated diolefine hydrocarbon mixture realizes.Monovinylarene and conjugated diolefine hydrocarbon mixture add in two batches, wherein the first batch of feed rate of mixture is that will to be lower than the remaining mixture feed rate be transition synthetic feed rate to random section synthetic feed rate of monovinylarene and conjugated diene, feed rate is with the weight percent meter of mixture, be 4.6%～9.5%/min, difference according to polymerization temperature, the former is lower than speed of reaction at feed rate, and latter's feed rate is higher than speed of reaction.
Specifically, multipolymer of the present invention can obtain in the following way: initiator is once added, and monomer divides and joins paradigmatic system in certain sequence four times, after polymerization finishes, adds coupling agent again and carries out linked reaction and make.The method of the synthetic employing control feed rate of the random graded chain segment of multipolymer of the present invention realizes.The polymerization monomer is conjugated diene and mono vinyl arenes monomer, and its order of addition(of ingredients) is as follows:
The I step: mono vinyl arenes monomer S
1With initiator L, form S
1-Me (Me is the metal ion of initiator);
The II step: mono vinyl arenes monomer S
2With conjugated diene monomer B
1, form S
1-B
1/ S
2-Me:
The III step: mono vinyl arenes monomer S
3With conjugated diene monomer B
2, form S
1-B
1/ S
2(B
2→ S
3)-Me;
The IV step: conjugated diene monomer B
3, form living chain P:S
1-B
1/ S
2(B
2→ S
3)-B
3-Me;
V step: functionalized coupling C forms:
In the formula, R is the saturated fatty alkyl that contains 1～6 carbon atom, is preferably methyl; X=Si, Sn are preferably the Si atom.
In each step, when polyreaction is performed until essentially no free monomer and exists till, polymerization temperature is 60 ℃～120 ℃, preferably scope is 65 ℃～95 ℃.
Continuously feeding under the relatively mild temperature is adopted in the formation of random graded chain segment in the polymkeric substance of the present invention, thereby segmentation control input speed obtains having random section random graded chain segment that closely links to each other with transition of certain-length with inlet amount.Adopt the randomization degree of random graded chain segment of this prepared higher, fully realized from the randomization to the divinyl to cinnamic gradual transition, avoided forming under the pyroreaction generation of gel or other side reaction effectively, guaranteed that polymkeric substance has good light transmittance and excellent mechanics mechanical property.
Polymkeric substance of the present invention can be a thermoplastic elastomer, also can be thermoplastic resin, the polymer performance characteristics be determined by the total proportioning of monovinylarene in the polymkeric substance and conjugated diolefine and length, monomer ratio and the mix monomer input speed of random graded chain segment.
In order to make polymkeric substance have excellent performance, the invention provides its best preparation method.
When the radial segmented copolymer of monomorphism that contains random graded chain segment of the present invention is thermoplastic elastomer copolymer, the parts by weight of monovinylarene are 30%～60% in the multipolymer, be preferably 35%～55%, the parts by weight of conjugated diene monomer are 40%～70%, are preferably 45%～65%.
Preparation process is described below: (total monomer weight all refers to all total monomer weights in the literary composition)
At first will account for 12.6%～44.30% of total monomer weight, preferably 15.0%～40.5% monovinylarene adds polymerized unit, adds the organic single-base metal initiator then, thereby forms the non-resilient segment with active alkali metal end group, and structural formula is S
1-Me: the mixture that adds monovinylarene and conjugated diene afterwards to paradigmatic system, feed rate is with the weight percent meter of mixture, be 4.6%～8.4%/min, monovinylarene accounts for 15.7%～47.4% (Wt) of total monomer weight in the mixture, 18.5%～42.0% (Wt) preferably, conjugated diene accounts for 32.6%～67.9% (wt) of total monomer weight, preferably 44.7%～61.2% (Wt).Random section synthetic feed rate will be lower than transition synthetic feed rate, and according to the difference of polymerization temperature, the former is lower than speed of reaction at feed rate, and latter's feed rate is higher than speed of reaction.The feed way that the present invention recommends is: it is slower that mixture begins injection speed, is 4.6%～6.5%/min, when injecting mixture 70%～85% left and right sides, improves injection speed to 6.7%～8.4%/min, and temperature of reaction is at 65～100 ℃.After adding, continues monomer mixture to keep reaction 10～30min.The random transition that the transition that can synthesize like this has random section of certain-length and certain-length closely links to each other, and the randomization degree is higher in this segment, has finished effectively from the randomization to the divinyl to cinnamic gradual transition.This moment, polymkeric substance can be expressed as S
1-B
1/ S
2(B
2→ S
3)-Me; To account for 2.1%～7.4% (Wt) of total monomer weight again, preferably the conjugated diene of 2.5%～6.4% (Wt) adds paradigmatic system, make the end of each polymer chain form a very little conjugated diolefine hydrocarbon segment like this, the steric effect that aryl brings during with the minimizing coupling, guarantee link coupled validity, this moment, polymer chain can be expressed as S
1-B
1/ S
2(B
2→ S
3)-B
3-Me; Use a kind of alkoxyl silicone (or tin) alkane coupling agent to carry out coupling at last, linked reaction is lasted 30～65min and can be finished under 70～90 ℃.If no coupling step obtains linear block copolymers, then can't reach purpose of the present invention.In order to improve the transparency of polymkeric substance, with the polymers soln water treatment after the coupling, the consumption of water is generally 100～300 times of initiator amount, be preferably 150～250 times, use pH value to 7.0 ± 0.5 of CO2 telomerized polymer solution simultaneously, the polymkeric substance that obtains like this has good transparency.Take this just to have made the high-phenylethylene content that contains a random graded chain segment, high transparent, shock resistance, the radial segmented copolymer thermoplastic elastomer of monomorphism.
When the radial segmented copolymer of monomorphism that contains random graded chain segment of the present invention is the thermoplastic resin resin copolymer, the parts by weight of monovinylarene are 60%～95% in the multipolymer, be preferably 70%～85%, the parts by weight of conjugated diene monomer are 5%～40%, are preferably 15%～30%.
Preparation process is described below:
At first will account for 17.30%～92.80% (Wt) of total monomer weight, preferably the monovinylarene of 25.0%～74.5% (Wt) adds polymerized unit, add the organic single-base metal initiator then, thereby form the non-resilient segment with active alkali metal end group, structural formula is S
1-Me; The mixture that adds monovinylarene and conjugated diene afterwards to paradigmatic system continuously, feed rate is with the weight percent meter of mixture, be 5.4%～9.5%/min, monovinylarene accounts for 2.20%～77.70% (Wt) of total monomer in the mixture, 10.5%～60.0% (Wt) preferably, conjugated diene accounts for 1.00%～39.75% (wt) of total monomer weight, preferably 12.0%～29.25% (Wt).Mixture is to inject continuously, and random section synthetic feed rate will be lower than transition synthetic feed rate, and according to the difference of polymerization temperature, the former is lower than speed of reaction at feed rate, and latter's feed rate is higher than speed of reaction.The feed way that the present invention recommends is: it is slower that mixture begins injection speed, feed rate is counted 5.4%～7.8%/min with the weight percent of mixture, when injecting mixture 70%～85% left and right sides, improve injection speed to 7.2%～9.5%/min, temperature of reaction is at 65～100 ℃.The random transition that the transition that can synthesize like this has random section of certain-length and certain-length closely links to each other, and the randomization degree is higher in this segment, has finished effectively from the randomization to the divinyl to cinnamic gradual transition.This moment, polymkeric substance can be expressed as S
1-B
1/ S
2(B
2→ S
3)-Me.Random graded chain segment adopts this kind method synthetic, can guarantee effectively that polymkeric substance has excellent mechanics, optical property.
To account for 0.25%～4.00% (Wt) of total monomer weight again, preferably the conjugated diene of 0.75%～3.00% (Wt) adds paradigmatic system, make the end of each polymer chain form a very little conjugated diolefine hydrocarbon segment like this, the steric effect that aryl brings during with the minimizing coupling guarantees link coupled validity; Carry out coupling with a kind of many active centre silicon (or tin) alkane coupling agent that contains one or more functional groups at last.If no coupling step obtains linear block copolymers, then can't reach purpose of the present invention.So just, made with the radial multi-arm segmented copolymer of the monomorphism of a random graded chain segment.In order to improve the transparency of polymkeric substance, with the polymers soln water treatment after the coupling, the consumption of water is generally 100～300 times of initiator amount, is preferably 150～250 times, uses CO simultaneously
2The pH value to 7.0 of telomerized polymer solution ± 0.5, the polymkeric substance that obtains like this has good transparency.
Polymers soln adds oxidation inhibitor before solvent steams, oxidation inhibitor can be with 1076,1010,264, TNP, tri-isopropanolamine etc.Above-mentioned substance can use separately, also can multiple compound use, and add-on is 1～5phm (phm is the parts by weight of the material in per 100 weight part total monomers, and is as follows), is preferably 1～2phm.
The separation of polymkeric substance from solution can be adopted traditional steam stripping coacervation method, also available devolatilization type screw extrusion press.
Mono vinyl arenes monomer refers generally to contain 8～18 carbon atoms among the present invention, and substituting group can be alkyl, cycloalkyl, aromatic substituent and their compound substituent material, and wherein substituent the total number of carbon atoms generally is no more than 12.Mainly comprise vinylbenzene, alpha-methyl styrene, 4-n-propylbenzene ethene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 1-vinyl naphthalene, 2,4-dimethyl styrene etc., perhaps their mixture.The most frequently used is vinylbenzene, and this is determined in industrial practical value by it.
Conjugated diene generally contains 4～12 carbon atoms among the present invention, and preferably 4～8 carbon atoms comprise 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1, the 3-octadiene, 2-phenyl-1,3-butadiene etc., or their mixture.What industrial value was arranged is 1,3-butadiene, isoprene, and the most frequently used is 1,3-butadiene.
The length of the mol ratio of monovinylarene and conjugated diene and random section is that random section per-cent that accounts for random transition can be determined by the mechanical property that polymkeric substance requires among the present invention.In general the mol ratio of monovinylarene and conjugated diene is big more, and the notched Izod impact strength of polymkeric substance is low more and tensile strength is big more, and random section long more, and then the notched Izod impact strength of polymkeric substance is big more and tensile strength polymkeric substance is more little.The mol ratio recommendation of the phenylethylene/butadiene of random graded chain segment is 0.2～1.5 among the present invention, and better scope is 0.3～1.2, and the monomer total amount of random graded chain segment accounts for 28.6%～61.8% of polymkeric substance total monomer weight.
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 compound 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 by the molecular weight decision of the polymkeric substance of design.The molecular weight of the polymkeric substance that the present invention recommends is 160000～220000.
The used coupling agent of the present invention can be expressed as with general formula: R-X-(OR ')
3, wherein R is the saturated fatty alkyl that contains 1～6 carbon atom, is preferably methyl; R ' is preferably the saturated fatty alkyl that contains 1～2 carbon atom for containing the saturated fatty alkyl of 1～4 carbon atom; X=Si, Sn are preferably the Si atom.Certainly, coupling agent can also be many ketones of containing a plurality of reactive centers, many carbonyls ester class, polyepoxy compound class etc.The consumption of coupling agent is decided according to the amount of initiator, is generally 1/4～1/3 of initiator amount.
Polyreaction of the present invention is preferably in the rare gas element Ar environment and carries out in anaerobic, anhydrous basically.Polymerization process is finished in hydrocarbon diluent, and hydrocarbon diluent comprises straight-chain paraffin and naphthenic hydrocarbon preferably, as pentane, and hexane, octane, heptane, hexanaphthene and their mixture, preferably hexanaphthene.
Need in the paradigmatic system of the present invention to add the small amount of polar organic compound, improve the reactive behavior of positive alkyl lithium initiator such as n-Butyl Lithium on the one hand, randomization degree and the gradual change degree that can regulate random transition on the other hand as randomizer.This class polar organic compound comprise tetrahydrofuran (THF) (THF), ether, ethyl methyl ether, methyl-phenoxide, phenyl ether,, glycol dimethyl ether (DME), diethylene glycol dimethyl ether, triethylamine, 6-methyl phosphonic triamide etc.Wherein the result of use of tetrahydrofuran (THF) is best, and its amount ranges is 0.01～0.1phm, preferably 0.02～0.08phm.
After radial segmented copolymer of monomorphism multi-arm of the present invention and polystyrene 50% blend, its transmittance has kept original optical property, still can reach more than 87%.The radial segmented copolymer of monomorphism that has random graded chain segment of the present invention can be made have cracking resistance (high impulse strength being arranged, yield strength, tensile strength), almost colourless and transparent product, is particularly suitable for packaging field.It is simple that the method for this segmented copolymer of preparation provided by the present invention has technology, and polymerization time is short, the characteristics that product performance are stable.
Description of drawings
Fig. 1 is the gel permeation chromatography figure of embodiment 1 polymkeric substance.
Fig. 2 is the gel permeation chromatography figure of the bimodal star block copolymer of Comparative Examples 3.
Fig. 3 is the gel permeation chromatography figure of the multi-modal star block copolymer of Comparative Examples 5.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment and Comparative Examples below, but should not be so limited.
Embodiment 1～10 has described the radial segmented copolymer of radial multi-arm that has random graded chain segment of using preparation method's synthetic macromolecule amount monomorphism of the present invention.
Embodiment 1～10
In having the 14L stainless steel cauldron of chuck, in varsol, carry out polyreaction under the protection of argon gas.Need continuous stirred reaction mixture in polymerization and the coupling process.Addition step is as follows:
(1) mono vinyl arenes monomer and initiator;
(2) mixture of mono vinyl arenes monomer and conjugated diene monomer (mixture total weight amount 70%～85%);
(3) mixture of mono vinyl arenes monomer and conjugated diene monomer (remaining 15%～30% mixture);
(4) conjugated diene monomer;
(5) coupling agent.
Water and CO after linked reaction is finished
2Reaction mixture after the processing coupling, and obtaining adding oxidation inhibitor before the polymer dry glue of the present invention.Table 1 is the kind of the raw materials used and auxiliary agent of embodiment 1～10, and table 2 is the prescription and the processing condition of the preparation multipolymer of the present invention of embodiment 1～10.Among the embodiment, the multipolymer of embodiment 1～5 is a thermoplastic resin, and the multipolymer of embodiment 6～10 is a thermoplastic elastomer.Fig. 1 is the gel permeation chromatography figure of embodiment 1 polymkeric substance.
Comparative Examples 1
Comparative Examples 1 contains the line-type block polymer of a random transition for a kind of monomorphism of preparation and the difference of embodiment 1 is that the coupling agent of (5) step adding is (CH
3)
2SiCl
2, the kind and the processing condition of all the other starting material and auxiliary agent are identical with embodiment 1.
Comparative Examples 2
Comparative Examples 2 contains the star block copolymer of a random graded chain segment for a kind of monomorphism of preparation and the difference of embodiment 1 is that the coupling agent of (5) step adding is SiCl
4, the kind and the processing condition of used starting material and auxiliary agent are identical with embodiment 1.
Comparative Examples 3
Comparative Examples 3 commercially belongs to the KR-03 of a grade with multipolymer of the present invention for a kind of, but is the bimodal star block copolymer.Fig. 2 is the gel permeation chromatography figure of its bimodal star block copolymer.
Comparative Examples 4
Comparative Examples 4 contains the star block copolymer of a graded chain segment for a kind of monomorphism of reporting among the patent CN1241582A.Be the synthetic employing gradient temperature control polymerization of graded chain segment with the difference of embodiment 1, polymerization at high temperature earlier, promptly the polymerization temperature in II step is 139 ℃, mix monomer is for once adding, reduce the temperature of reaction polymerization then, promptly the polymerization temperature in III step is 75 ℃, and mix monomer is for once adding, and all the other conditions are identical with embodiment 1.
Comparative Examples 5
Comparative Examples 5 commercially belongs to the SBS-2504 of styrene analog thermoplastic elastomer together with multipolymer of the present invention for a kind of, but is multi-modal star-like triblock copolymer.Fig. 3 is the gel permeation chromatography figure of this multi-modal star block copolymer.
Comparative Examples 6
Comparative Examples 6 is the star block copolymer thermoplastic elastomer that a kind of monomorphism contains a graded chain segment, but the synthetic employing thermograde polymerization of its random graded chain segment.Polymerization at high temperature earlier, promptly the polymerization temperature in II step is 150 ℃, and mix monomer reduces the temperature of reaction polymerization then for once adding, and promptly the polymerization temperature in III step is 72 ℃, and mix monomer is for once adding, and all the other conditions are identical with embodiment 6.
The physical and mechanical properties test result of the multipolymer of embodiment 1～10 and Comparative Examples 1～6 is listed in the table 3.The test of tensile strength is carried out according to GB/T528-92; The test of notched Izod impact strength is carried out according to GB1043-93; Yield strength is tested according to GB/T528-92; Transmittance and mist degree are tested according to GB3410-80; Weight-average molecular weight adopts gel permeation chromatography (GPC) method to measure.
Fig. 1 and Fig. 2, Fig. 3 comparative illustration utilize the radial segmented copolymer of functionalized multi-arm that contains a random graded chain segment of the method for the invention preparation to be monomorphism, and Comparative Examples 2, Comparative Examples 4 multipolymers then are polymorphic (claiming multi-modal again).
The physical and mechanical properties comparative illustration of listed embodiment 1～5 polymkeric substance and Comparative Examples 1～4 in the table 3 adopts the notched Izod impact strength of the radial block copolymer thermoplastic resins of monomorphism multi-arm that contains a random graded chain segment of method preparation of the present invention, yield strength to compare the raising that all has in various degree with the polymer phase of Comparative Examples 1,2,4.The transmittance of embodiment multipolymer and Comparative Examples near but mist degree is lower than Comparative Examples.Embodiment 1～5 adopts the shock strength thermograde polymerization multipolymer of feed rate and feeding quantity controlled polymerization method gained thermoplastic resin of the present invention to improve about 10% with the random transition of Comparative Examples 4 comparative descriptions, transmittance has improved about 1 percentage point, and mist degree has descended about 10%.
The physical and mechanical properties comparative illustration of listed embodiment 6～10 polymkeric substance and Comparative Examples 1,5,6 in the table 3 adopts tensile strength, notched Izod impact strength, the yield strength of the radial segmented copolymer thermoplastic elastomer of monomorphism multi-arm that contains a random graded chain segment of method preparation of the present invention to compare the raising that all has in various degree with the polymer phase of Comparative Examples.Be similarly styrene analog thermoplastic elastomer, the transmittance of embodiment 6～10 multipolymers exceeds more than 10%～15% than Comparative Examples 5, and mist degree descends about 15% than Comparative Examples 5.The random transition of embodiment multipolymer adopts feeding quantity and the shock strength raising about 10% of feed rate control method than the thermograde polymerization multipolymer of Comparative Examples 6.
Table 1 embodiment experimental raw and auxiliary agent kind
Table 2 Example formulations and processing condition
Table 3 embodiment, Comparative Examples performance of copolymer
Claims (18)
1. radial segmented copolymer of monomorphism that contains random graded chain segment, its structural formula is expressed as follows: R-X-[B
3-(B
2→ S
3) B
1/ S
2-S
1]
3
S wherein
1, S
2And S
3All represent monovinylarene, B
1, B
2And B
3All represent conjugated diene; R is the saturated fatty alkyl that contains 1～6 carbon atom; X is Si, Sn; Promptly be by containing the radial segmented copolymer of monomorphism of a monovinylarene homopolymerization section, a random graded chain segment of monovinylarene-conjugated diene and a conjugated diolefin homopolymerization section in the anionic polymerization synthetic single armed molecular chain; The parts by weight of the mono vinyl arenes monomer that contains in the multipolymer are 30%～95%, the parts by weight of conjugated diene monomer are 5%～70%, the molecular weight of polymkeric substance is 160 000～220 000, the acquisition of the random graded chain segment of polymkeric substance is that the employing polymerization temperature is 65 ℃～100 ℃, initiator is once added, monovinylarene and conjugated diolefine hydrocarbon mixture add in two batches, feed rate is with the weight percent meter of mixture, be 4.6%～9.5%/min, the first batch of feed rate of mixture is lower than speed of reaction, and the remaining mixture feed rate is higher than speed of reaction.
2. the radial segmented copolymer of monomorphism according to claim 1 is characterized in that copolymer structure formula R-X-[B
3-(B
2-S
3) B
1/ S
2-S
1]
3In, R is a methyl, X is Si.
3. the radial segmented copolymer of monomorphism according to claim 1, it is characterized in that mono vinyl arenes monomer is meant vinylbenzene, alpha-methyl styrene, 4-n-propylbenzene ethene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, the 1-vinyl naphthalene, 2,4-dimethyl styrene, or their mixture.
4. the radial segmented copolymer of monomorphism according to claim 1 is characterized in that conjugated diene is meant 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1, the 3-octadiene, 2-phenyl-1,3-butadiene, or their mixture.
5. the radial segmented copolymer of monomorphism according to claim 1, it is characterized in that the shared parts by weight of mono vinyl arenes monomer are 35%～85% in the radial segmented copolymer of monomorphism, the shared parts by weight of conjugated diene monomer are 15%～65%.
6. the preparation method of the radial segmented copolymer of the described monomorphism of claim 1, initiator is once added, monomer divides and joins paradigmatic system in certain sequence four times, after polymerization finishes, adding coupling agent again carries out linked reaction and makes, the polymerization monomer is conjugated diene and mono vinyl arenes monomer, and its order of addition(of ingredients) is as follows:
The I step: mono vinyl arenes monomer S
1With initiator L, form S
1-Me, wherein Me is the metal ion of initiator;
The II step: mono vinyl arenes monomer S
2With conjugated diene monomer B
1, form S
1-B
1/ S
2-Me;
The III step: mono vinyl arenes monomer S
3With conjugated diene monomer B
2, form S
1-B
1/ S
2(B
2→ S
3)-Me;
The IV step: conjugated diene monomer B
3, form living chain P:S
1-B
1/ S
2(B
2→ S
3)-B
3-Me;
V step: functionalized coupling C forms: R-X-[B
3-(B
2→ S
3) B
1/ S
2-S
1]
3
Form random segment S in the II step
1-B
1/ S
2-Me, III form random graded chain segment S in the step
1-B
1/ S
2(B
2→ S
3)-Me is that the employing polymerization temperature is 65 ℃～100 ℃, the feed rate of monovinylarene and conjugated diolefine hydrocarbon mixture is with the weight percent meter of mixture, be 4.6%～9.5%/min, the former is lower than speed of reaction at feed rate, and latter's feed rate is higher than speed of reaction;
In each step, when polyreaction is performed until no free monomer and exists till; Polymerization temperature is 60 ℃～120 ℃ except that III goes on foot.
7. the preparation method of the radial segmented copolymer of monomorphism according to claim 6, polymerization temperature is 65～95 ℃ to it is characterized in that going on foot in addition by III.
8. the preparation method of the radial segmented copolymer of monomorphism according to claim 6, the parts by weight that it is characterized in that monovinylarene in the multipolymer are 30%～60%, the parts by weight of conjugated diene monomer are 40%～70%, during polymerization, 12.6%～44.30% the monovinylarene that at first will account for all total monomer weights adds polymerized unit, add the polymerization of organic single-base metal initiator then, form non-resilient segment S with active alkali metal end group
1-Me; The mixture that adds monovinylarene and conjugated diene afterwards to paradigmatic system, monovinylarene accounts for 15.7%～47.4% of all total monomer weights in the mixture, conjugated diene accounts for 32.6%～67.9% of all total monomer weights, mixture is to inject continuously, random transition synthetic feed rate is with the weight percent meter of mixture, be 4.6%～8.4%/min, wherein random section synthetic feed rate is lower than speed of reaction, transition synthetic feed rate is higher than speed of reaction, forms polymer chain S
1-B
1/ S
2(B
2→ S
3)-Me; 2.1%～7.4% the conjugated diene that will account for all total monomer weights again adds paradigmatic system, forms polymer chain S
1-B
1/ S
2(B
2→ S
3)-B
3-Me; Carry out coupling with alkoxyl silicone or stannane coupling agent at last, form the radial segmented copolymer R-X-[B of monomorphism
3-(B
2→ S
3) B
1/ S
2-S
1]
3
9. the preparation method of the radial segmented copolymer of monomorphism according to claim 7, the parts by weight that it is characterized in that monovinylarene in the multipolymer are 35%～55%, the parts by weight of conjugated diene monomer are 45%～65%, in the polymerization, it is to account for 15.0%～40.5% of all total monomer weights that monovinylarene adds fashionable add-on separately, monovinylarene and conjugated diene mixing add fashionable, monovinylarene accounts for 18.5%～42.0% of all total monomer weights in the mixture, conjugated diene accounts for 44.7%～61.2% of all total monomer weights, and it is to account for 2.5%～6.4% of all total monomer weights that conjugated diene adds fashionable add-on separately.
10. the preparation method of the radial segmented copolymer of monomorphism according to claim 7, when it is characterized in that forming random transition polymer chain, weight percent meter with monovinylarene and conjugated diolefine hydrocarbon mixture, feed rate with 4.6%～6.5%/min adds mixture earlier, form random section, when injecting mixture 70%～85%, the feed rate of remaining mixture with 6.7%～8.4%/min added, form transition.
11. the preparation method of the radial segmented copolymer of monomorphism according to claim 6, the parts by weight that it is characterized in that monovinylarene in the multipolymer are 60%～95%, the parts by weight of conjugated diene monomer are 5%～40%, during polymerization, 17.30%～92.80% the monovinylarene that at first will account for all total monomer weights adds polymerized unit, add the polymerization of organic single-base metal initiator then, form non-resilient segment S with active alkali metal end group
1-Me; The mixture that adds monovinylarene and conjugated diene afterwards to paradigmatic system, monovinylarene accounts for 2.20%～77.70% of all total monomer weights in the mixture, conjugated diene accounts for 1.00%～39.75% of all total monomer weights, mixture is to inject continuously, random transition synthetic feed rate is counted 5.4%～9.5%/min with the weight percent of mixture, wherein random section synthetic feed rate is lower than speed of reaction, transition synthetic feed rate is higher than speed of reaction, forms polymer chain S
1-B
1/ S
2(B
2→ S
3)-Me; 0.25%～4.00% the conjugated diene that will account for all total monomer weights again adds paradigmatic system, forms polymer chain S
1-B
1/ S
2(B
2→ S
3)-B
3-Me; Carry out coupling with alkoxyl silicone or stannane coupling agent at last, form the radial segmented copolymer of monomorphism
R-X-[B
3-(B
2→S
3)B
1/S
2-S
1]
3。
12. according to claim 1] preparation method of the radial segmented copolymer of described monomorphism, the parts by weight that it is characterized in that monovinylarene in the multipolymer are 70%～85%, the parts by weight of conjugated diene monomer are 15%～30%, in the polymerization, it is to account for 25.0%～74.5% of all total monomer weights that monovinylarene adds fashionable add-on separately, monovinylarene and conjugated diene mixing add fashionable, monovinylarene accounts for 10.5%～60.0% of all total monomer weights in the mixture, conjugated diene accounts for 12.0%～29.25% of all total monomer weights, and it is to account for 0.75%～3.00% of all total monomer weights that conjugated diene adds fashionable add-on separately.
13. the preparation method of the radial segmented copolymer of monomorphism according to claim 11, when it is characterized in that forming random transition polymer chain, weight percent meter with monovinylarene and conjugated diolefine hydrocarbon mixture, feed rate with 5.4%～7.8%/min adds mixture earlier, form random section, when injecting mixture 70%～85%, improve feed rate, the feed rate of remaining mixture with 7.2%～9.5%/min added, form transition.
14. preparation method according to claim 6 or the radial segmented copolymer of 8 or 11 described monomorphism, it is characterized in that initiator is organic single-lithium compound R Li, wherein R is the compound base that contains representative examples of saturated aliphatic alkyl, alicyclic alkyl, aryl or the above-mentioned group of 1～20 carbon atom.
15., it is characterized in that initiator is n-Butyl Lithium, s-butyl lithium according to the preparation method of claim 6 or the radial segmented copolymer of 8 or 11 described monomorphism.
16. the preparation method according to claim 6 or the radial segmented copolymer of 8 or 11 described monomorphism is characterized in that coupling agent can be expressed as with general formula: R-X-(OR ')
3, wherein R is the saturated fatty alkyl that contains 1～6 carbon atom; R ' is for containing the saturated fatty alkyl of 1～4 carbon atom; X is Si, Sn.
17. the preparation method of the radial segmented copolymer of monomorphism according to claim 6 is characterized in that the monomer total amount of random graded chain segment accounts for 28.6%～61.8% of polymkeric substance total monomer weight.
18. the preparation method of the radial block copolymerization of monomorphism according to claim 6 is characterized in that the mol ratio of monovinylarene and conjugated diene is 0.2～1.5 in the random graded chain segment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146385 CN1247642C (en) | 2003-07-11 | 2003-07-11 | Unimodal radial block copolymer possessing random graded chain and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146385 CN1247642C (en) | 2003-07-11 | 2003-07-11 | Unimodal radial block copolymer possessing random graded chain and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569914A CN1569914A (en) | 2005-01-26 |
| CN1247642C true CN1247642C (en) | 2006-03-29 |
Family
ID=34471695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03146385 Expired - Fee Related CN1247642C (en) | 2003-07-11 | 2003-07-11 | Unimodal radial block copolymer possessing random graded chain and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1247642C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234358B (en) * | 2010-04-23 | 2013-12-25 | 中国石油化工集团公司 | Star styrene-butadiene-styrene (SBS) copolymer for sealing strip as well as preparation and application thereof |
| CN108587535B (en) * | 2011-01-30 | 2020-05-05 | 戴纳索尔伊莱斯托米罗斯公司 | Tapered triblock copolymers |
| CN106397696B (en) * | 2016-08-31 | 2019-03-22 | 广东众和化塑有限公司 | It is a kind of to be provided simultaneously with high saturating, highly resistance tortuosity and SBS elastomer of high-foaming efficiency and preparation method thereof |
-
2003
- 2003-07-11 CN CN 03146385 patent/CN1247642C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1569914A (en) | 2005-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1274734C (en) | Unimodal radial block copolymer with functional group and its preparation method | |
| CN1142957C (en) | Transparent, impact-resistant polystyrene on styrene-butadiene block copolymer basis | |
| CN1643016B (en) | Novel block copolymers and method for making same | |
| CN87100183A (en) | The polymorphic linear block copolymers that has terminal transition of cracking resistance | |
| CN1865294A (en) | Hydrogenated styrene analog thermoplastic elastomer and its preparation method | |
| CN1596285A (en) | Transparent styrol-butadiene block copolymer mixtures | |
| CN101456938A (en) | Star-shaped comb type butadiene/phenylethylene block copolymers and preparation method thereof | |
| CN1130391C (en) | Polymerizing method for conjugate diene monomer | |
| CN102887980B (en) | Styrene-butadiene copolymer as well as preparation method and application thereof | |
| CN1065547C (en) | Star block copolymer of a vinylaromatic monomer and of a conjugated diene | |
| CN1745116A (en) | Conjugated diene polymers and copolymer blocks and process for preparing same | |
| CN1247642C (en) | Unimodal radial block copolymer possessing random graded chain and its preparation method | |
| CN105732921A (en) | Double-end-functionalized ternary copolymer rubber and preparation method thereof | |
| CN1432586A (en) | Conjugated diene copolymer rubber and its prepn process | |
| CN1274735C (en) | Functionalized unimodal radial block copolymer and its preparation method | |
| CN102924838A (en) | High-glossiness high-impact-strength polystyrene resin composition and preparation method thereof | |
| CN1148053A (en) | Multi-functional group organic alkali metal initiator, and synthesis method therefor | |
| CN1247641C (en) | Unimodal radial block copolymer thermalplastic elastomer and its preparation method | |
| CN1117108C (en) | Process for preparing randomly solution polymerized butadiene-styrene rubber with low 1,2-structure and wide molecular weight distribution | |
| CN1069656C (en) | Fragmentation-resisting simplicial spider block copolymer and its preparation | |
| CN1069906C (en) | Multi-chelate organolithium initiator and its method in synthesizing polymer with wide molecular weight distribution and high Mooney viscosity with the same | |
| CN103665281B (en) | A kind of four arm radiation star random copolymerss and preparation method thereof | |
| CN110128606B (en) | Block copolymer, block copolymer composition, vulcanized rubber, application of vulcanized rubber, and preparation method of block copolymer | |
| CN1165556C (en) | Process for preparing thermoplastic phenylethylene elastomer | |
| CN1118493C (en) | Process for preparing atactic copolymer of conjugated diene and monovinyl arylhydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060329 Termination date: 20210711 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |