CN1274735C - Functionalized unimodal radial block copolymer and its preparation method - Google Patents
Functionalized unimodal radial block copolymer and its preparation method Download PDFInfo
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Abstract
The present invention relates to a functional monomorphism radial block copolymer which has the following structural formula: A-[-Y-(-B3-(B2-S3)B1/S2-S1)3]n; in the structural formula, S represents styrene single ethene aromatic hydrocarbons; B represents butadiene conjugated dialkene; Y is Si and Sn; n is equal to 1 or 2; A is hydrocarbyl or a polymer chain P with hydroxy, imino, benzene imino, sulfhydryl functional groups; the single arm molecular weight of the polymer is not less than 60000; the molecular weight of the polymer is not less than 180000; the number of arms is not less than 3; in the copolymer, the weight portion of single vinyl aromatic hydrocarbon monomers is from 30% to 95%; and the weight portion of conjugated butadiene monomers is from 5% to 70%. Because the copolymer comprises one or a plurality of functional groups, the copolymer shows good high temperature resistance and heat resisting oxygen aging resistance, the copolymer can simultaneously improve the color and luster of polymers and keep low haze degree, and the copolymer is especially suitable for the packaging field.
Description
Technical field
The present invention relates to radial segmented copolymer of a kind of functionalized monomorphism and preparation method thereof, specifically a kind of high transparent, shock resistance monomorphism end has in random graded chain segment and each polymer molecule and contains radial segmented copolymer of a functional group and preparation method thereof at least.
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 polymericular weight is less relatively is 150000～220000, and polymkeric substance does not contain functional group.
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.Patent EP761704A1, US5399628 etc. relate in transition synthetic vinylbenzene and divinyl to be mixed once to be added under the steady temperature with certain proportion and reacts, the transition randomization degree that obtains in this way is low, progressive formation is not obvious, has influenced product performance.
For anionoid polymerization prepares star-type polymer, the size of polymkeric substance single armed molecular weight and the arm number of polymer molecule are directly determining the size of polymericular weight, and the molecular weight of polymkeric substance is two important factors of impact polymer physical and mechanical properties and processed and applied characteristic.Thereby selection contains the molecular weight that many active centre coupling agent of different functional groups not only can significantly improve polymkeric substance makes polymer performance that certain improvement be arranged, but also has introduced functional group in the polymer molecular chain and give polymkeric substance some property because of giving.
Summary of the invention
The object of the present invention is to provide a kind of monomorphism that contains one or more functional groups and random graded chain segment, have relative higher molecular weight and than the radial segmented copolymer of multi-arm number, this polymkeric substance will have very high transmittance and resistance to impact shock, the ESCR of high temperature resistant preferably, hot-air aging resistance and goods also to be arranged simultaneously, can be used for packaging field.
The invention provides a kind of radial segmented copolymer of monomorphism that contains functional group, its structural formula is expressed as follows:
S wherein
1, S
2And S
3All represent the styrenic monovinylarene, B
1, B
2And B
3All represent the butadiene type conjugated diene; Y=Si, Sn; N=1,2; A is the alkyl that has functional groups such as hydroxyl, imido grpup, phenyl imido, sulfydryl.
Promptly be by the anionic polymerization synthetic, contain the radial segmented copolymer of functionalized monomorphism of a monovinylarene homopolymerization section, a random graded chain segment of monovinylarene-conjugated diene and a conjugated diolefin homopolymerization section in the single armed molecular chain.This polymkeric substance single armed molecular weight is not less than 60000, and polymericular weight is not less than 180000, and the arm number is no less than 3.The parts by weight of the mono vinyl arenes monomer that contains in the multipolymer of the present invention are 30%～95% (wt), are preferably 35%～85% (wt), and the parts by weight of conjugated diene monomer are 5%～70% (wt), are preferably 15%～65% (wt).
In order to realize the object of the invention better, the present invention also provides a kind of method for preparing this multipolymer.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 the coupling agent that contains functional group again and carries out linked reaction and make.The random graded chain segment of multipolymer of the present invention can adopt the thermograde polymerization of recommendation to form.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-M (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, S represents benzene
Vinyl monovinylarene, B are represented the butadiene type conjugated diene; Y=Si, Sn; N=1,2;
A is the alkyl that has functional groups such as hydroxyl, imido grpup, phenyl imido, sulfydryl.
In each step, when polyreaction is performed until essentially no free monomer and exists till, polymerization temperature is 60 ℃～160 ℃, preferably scope is 65 ℃～150 ℃.
Polymkeric substance of the present invention can be a thermoplastic resin, also can be thermoplastic elastomer.This is 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.
The molecular weight size of polymkeric substance has confidential relation with the physical and mechanical properties and the processed and applied characteristic of polymkeric substance.The present invention guaranteeing under the constant situation of subject polymer molecular chain structure, prepares by the single armed molecular weight that improves star-type polymer that the high-molecular weight height is transparent, the functionalized radial segmented copolymer of shock resistance monomorphism.The single armed molecular weight of polymkeric substance of the present invention is preferably 60 000～100 000.
Many active centre (the active centre number is no less than 3) coupling agent that employing contains one or more functional groups is that preparation high-molecular weight height is transparent, the effective measure of the functionalized radial segmented copolymer of shock resistance monomorphism equally.The present invention reaches in 60 000～100 000 it at raising polymkeric substance single armed molecular weight, uses functionalized many active centre coupling agent further to improve polymericular weight, can make it reach 600000 or higher.
For the random transition of the monovinylarene-conjugated diolefin copolymer generation type of transition particularly, the present invention is not limited, as adopting the different feeding manner of control monovinylarene, conjugated diene etc.Recommend a kind of generation type of transition among the present invention, promptly in polymerization process II goes on foot, the mixture that in paradigmatic system, adds a part of monovinylarene and conjugated diene earlier, rapid polymerization certain hour under comparatively high temps, be generally 5～15min, get random section S of monovinylarene and conjugated diene
1-B
1/ S
2-Me carries out the polyreaction III step then, reduces to lesser temps, once injects the residue mix monomer, makes feed rate be higher than speed of reaction, thereby at transition S of the terminal formation of living chain
1-B
1/ S
2(B
2→ S
3)-Me.Adopt the random graded chain segment of this prepared can guarantee effectively that together with other technological measure and condition polymkeric substance has good light transmittance and excellent mechanics mechanical property.
In order to make polymkeric substance have excellent performance, the invention provides its best preparation method.
When the radial segmented copolymer of functionalized monomorphism of the present invention is the thermoplastic resin resin copolymer, the total content of monovinylarene is 60%～95% (wt) in the multipolymer, be preferably 70%～85% (wt), the parts by weight of conjugated diene monomer are 5%～40% (wt), are preferably 15%～30% (wt).
Preparation process is described below: (total monomer weight all refers to all total monomer weights in the literary composition)
At first will account for 17.30%～92.80% (Wt) of total monomer weight, preferably the monovinylarene of 25.2%～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, monovinylarene accounts for 2.20%～77.70% (Wt) of total monomer weight 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).With said mixture weight 60%～80% at 130 ℃～160 ℃ following rapid polymerization 5～15min, monovinylarene and conjugated diene random section, but this following residence time of temperature is unsuitable long, be advisable to be no more than 15min, to prevent that molecular weight distribution from broadening, this contains random segmental polymer chain and is expressed as S
1-B
1/ S
2-Me; Be cooled to 65 ℃～75 ℃, once inject the residue mix monomer, make feed rate be higher than speed of reaction, thereby at transition of the terminal formation of living chain, polymkeric substance can be expressed as S this moment
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 again, preferably the conjugated diene of 0.75%～3.00% (Wt) adds paradigmatic system, makes the end of each polymer chain form a very little conjugated diolefine hydrocarbon segment S like this
1-B
1/ S
2(B
2→ S
3)-B
3-Me, 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, form the radial block copolymer thermoplastic resins of functionalized monomorphism of the present invention
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, 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.
When the radial segmented copolymer of functionalized monomorphism of the present invention is thermoplastic elastomer, the total content of monovinylarene is 30%～60% (wt) in the multipolymer, be preferably 35%～55% (wt), the parts by weight of conjugated diene monomer are 40%～70% (wt), are preferably 45%～65% (wt).Preparation process is described below:
At first will account for total monomer 12.6%～44.30% (Wt), preferably the monovinylarene of 15.0%～40.5% (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 at twice to paradigmatic system, 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 40.0%～67.9% (wt) of total monomer weight, preferably 44.7%～61.2% (Wt).Earlier with mixture 60%～80% at 130 ℃～160 ℃ following rapid polymerization 5～15min, monovinylarene and conjugated diene random section, but this following residence time of temperature is unsuitable long, be advisable to be no more than 15min, best 10min, to prevent that molecular weight distribution from broadening, this contains random segmental polymer chain and is expressed as S
1-B
1/ S
2-Me; Be cooled to 65 ℃～75 ℃, inject the residue mix monomer continuously, make feed rate be higher than speed of reaction, thereby at transition of the terminal formation of living chain, polymkeric substance can be expressed as S this moment
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 total monomer 2.1%～7.4% (Wt) again, preferably the conjugated diene of 2.5%～6.4% (Wt) adds paradigmatic system, makes the end of each polymer chain form a very little conjugated diolefine hydrocarbon segment like this, to reduce
The steric effect that aryl brings during coupling guarantees link coupled validity, and this moment, polymer chain can be expressed as S
1-B
1/ S
2(B
2→ S
3)-B
3-Me; 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, form the radial segmented copolymer thermoplastic elastomer of functionalized monomorphism of the present invention
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, is preferably 150～250 times, uses CO simultaneously
2Telomerized polymer solution pH value to 7.0 ± 0.5, the polymkeric substance that obtains like this have high-phenylethylene content, good transparency and shock resistance.
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 polymkeric substance of the present invention is for being not less than 180 000, and better scope is 180 000～600 000.
The used coupling agent of the present invention is alkoxyl silicone, the tin compound that contains one or more epoxy group(ing), amino or imido grpup, sulfydryl, and its general formula is: X-R
1-Y-(OR
2)
3Wherein X for containing epoxy group(ing), amino or functional groups such as imido grpup, sulfydryl can be
Or HS-; R
1For alkylidene group or the cycloalkylidene that contains 1～8 carbon atom, as CH
2, CH
2CH
2, (CH
2)
3, CH
2CH (CH
3),
Deng; R
2For containing the alkyl of 1～4 carbon atom; Y is Siliciumatom or tin atom.When X is
The time, this coupling agent can be expressed as:
The two silicon compounds that promptly contain six active centre.Because R
1, R
2Volume big more, coupling efficiency is low more, so R
1Better for the straight-chain alkyl-sub-that contains 1～6 carbon atom, be preferably the straight-chain alkyl-sub-of 2～4 carbon atoms, R
2It is better to contain 1～3 carbon atom, is preferably methyl.Y is preferably Siliciumatom.The coupling agent and the living chain P reaction that contain above-mentioned functional group can be introduced functional groups such as hydroxyl, imido grpup, phenyl imido, sulfydryl in multipolymer, thereby obtain functionalized polymeric.Certainly, coupling agent can also be many ketones of containing 6 or 6 above reactive centers, many carbonyls ester class, polyepoxy compound class etc.Adopting above-mentioned many active centre coupling agent is that preparation high-molecular weight height is transparent, the effective measure of the radial multi-arm star-shaped segmented copolymer of shock resistance monomorphism equally.The consumption of coupling agent is decided according to the amount of initiator, is generally 1/3～1/6 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 comprises 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 multi-arm star-shaped segmented copolymer of monomorphism 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 functionalized monomorphism 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.Multipolymer of the present invention shows high temperature resistant preferably, hot-air aging resistance because of containing one or more functional groups, also can improve the color and luster of polymkeric substance simultaneously and keep low mist degree.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 6.
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 and has used the functionalized radial multi-arm star-shaped segmented copolymer that has a random graded chain segment of 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 functionalized thermoplastic resin, and the multipolymer of embodiment 6～10 is functionalized 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
4And polymkeric substance does not contain functional group, and 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, does not contain any functional group.Fig. 2 is the gel permeation chromatography figure of its multi-modal 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.Coupling agent is that the difference of methyltrimethoxy silane and embodiment 1 is that this polymkeric substance does not contain functional group, 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, and it is 25% that vinylbenzene contains, and does not contain any functional group.Fig. 3 is the gel permeation chromatography figure of this multi-modal star block copolymer.
Comparative Examples 6
Comparative Examples 6 contains the star block copolymer thermoplastic elastomer of a graded chain segment for a kind of monomorphism.Be that with the difference of embodiment 6 Comparative Examples 6 used coupling agents are methyltrimethoxy silane, polymkeric substance does not contain functional group, 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 1～5 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; The conclusive evidence of functional groups such as hydroxyl, imido grpup and sulfydryl utilizes Fourier transform infrared spectroscopy (FTIR) method to measure in the embodiment polymkeric substance.
Embodiment and Comparative Examples polymkeric substance are under the situation that same substance and add-on are 2phm at contained oxidation inhibitor and measure its heat aging performance and yellowness index.The heat aging performance test is carried out in thermal ageing constant temperature experimental box, and temperature is 160 ℃, takes out behind the constant temperature 72h, measures the notched Izod impact strength of sizing material.Polymeric aggregate is measured its yellowness index with color difference meter extrude 5 times repeatedly in screw diameter is the single screw extrusion machine of 20mm after.Experimental result is listed in the table 4.
Fig. 1 and Fig. 2, Fig. 3 comparative illustration utilize the functionalized multi-arm star-shaped segmented copolymer that contains a random graded chain segment of the method for the invention preparation to be monomorphism, and Comparative Examples 3, Comparative Examples 5 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 1,2,4 in the table 3, when adopting the molecular weight of method of the present invention preparation to be not less than 180 000 the radial segmented copolymer of functionalized monomorphism that contains a random graded chain segment to be thermoplastic resin, tensile strength, notched Izod impact strength, yield strength compare the raising that all has in various degree with the polymer phase of Comparative Examples, and along with the increase of molecular weight, above-mentioned physical strength also increases thereupon.The transmittance of embodiment multipolymer and Comparative Examples near but mist degree is lower slightly than Comparative Examples.
The physical and mechanical properties comparative illustration of listed embodiment 6～10 polymkeric substance and Comparative Examples 5,6 in the table 3, when adopting the molecular weight of method of the present invention preparation to be not less than 180 000 the radial segmented copolymer of functionalized monomorphism that contains a random graded chain segment to be thermoplastic elastomer, the polymer phase of notched Izod impact strength, yield strength and Comparative Examples is than the raising that all has in various degree, transmittance near and mist degree has certain decline.The transmittance of embodiment 6 multipolymers is compared with Comparative Examples 5 and is significantly improved, and mist degree obviously descends, and the amount of combined styrene is than Comparative Examples 5 height.
Experimental result comparative analysis in the table 4 as can be seen, the embodiment polymkeric substance is no matter be that thermoplastic resin or thermoplastic elastomer all make it have remarkable advantages aspect high temperature resistant, the heatproof air aging performance because of containing one or more functional groups, especially with the polymkeric substance that contains amino, anilino for very.The notched Izod impact strength of embodiment 3,4,5,7,10 polymkeric substance is more about 16% than having reduced before aging under same experiment condition, and Comparative Examples 3,6 polymkeric substance have then reduced by 26.8%; Also to compare the Comparative Examples polymkeric substance that does not contain functional group low because of containing functional group for the yellowness index of embodiment polymkeric substance.
Table 1 embodiment experimental raw and auxiliary agent kind
Table 2 Example formulations and processing condition
Table 3 embodiment, Comparative Examples performance of copolymer
The multipolymer high thermal resistance of table 4 embodiment and Comparative Examples and thermal-oxidative aging property contrast
| Multipolymer | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 7 | Embodiment 10 | Comparative Examples 3 | Comparative Examples 6 | |
| Before aging | Notched Izod impact strength (KJ/m 2) | 7.1 | 8.4 | 9.7 | 7.8 | 10.3 | 4.1 | 5.7 |
| After aging | Notched Izod impact strength (KJ/m 2) | 5.9 | 7.0 | 8.2 | 6.4 | 8.6 | 3.0 | 4.5 |
| Yellowness index | 6.4 | 6.6 | 6.2 | 6.5 | 6.3 | 7.5 | 13.1 | |
Claims (18)
1. radial segmented copolymer of functionalized monomorphism, its structural formula is expressed as follows:
S wherein
1, S
2And S
3All represent the styrenic monovinylarene, B
1, B
2And B
3All represent the butadiene type conjugated diene; Y=Si, Sn; N=1,2; A is the alkyl that has hydroxyl, imido grpup, phenyl imido, mercapto functional group; It promptly is the radial segmented copolymer of functionalized monomorphism that contains a monovinylarene homopolymerization section, a random graded chain segment of monovinylarene-conjugated diene and a conjugated diolefin homopolymerization section by the anionic polymerization synthetic; This polymkeric substance single armed molecular weight is not less than 60000, and polymericular weight is not less than 180000, and the arm number is no less than 3; 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%, initiator is once added, polymerization temperature is 60 ℃～160 ℃, monovinylarene and conjugated diolefine hydrocarbon mixture add in two batches, and twice polymerization under high temperature and low temperature, high temperature polymerization forms random section, and low temperature polymerization forms transition.
2. the radial segmented copolymer of functionalized monomorphism according to claim 1 is characterized in that the copolymer structure formula
In, Y is Si.
3. the radial segmented copolymer of functionalized 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 functionalized 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 functionalized 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 functionalized 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 functionalized 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:
In each step, when polyreaction is performed until no free monomer and exists till, polymerization temperature is 60 ℃～160 ℃.
7. the preparation method of the radial segmented copolymer of functionalized monomorphism according to claim 6 is characterized in that polymerization temperature is 65～150 ℃.
8. the preparation method of the radial segmented copolymer of functionalized monomorphism according to claim 6, it is characterized in that at polymerization process II in the step, the mixture that in paradigmatic system, adds a part of monovinylarene and conjugated diene earlier, rapid polymerization at high temperature, random section S of monovinylarene and conjugated diene
1-B
1/ S
2-Me carries out the polyreaction III step then, reduces temperature, once injects remaining mono vinyl arenes monomer S
3With conjugated diene monomer B
2Mix monomer, the control feed rate makes feed rate be higher than speed of reaction, thereby at transition S of the terminal formation of living chain
1-B
1/ S
2(B
2→ S
3)-Me.
9. the preparation method of the radial segmented copolymer of functionalized monomorphism according to claim 8 is characterized in that polymerization temperature is 130 ℃～160 ℃ in polymerization process II goes on foot, and polymerization temperature was 65 ℃～75 ℃ during III went on foot.
10. the preparation method of the radial segmented copolymer of functionalized 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% monovinylarene that at first will account for all total monomer weights adds polymerized unit, add the 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 at twice to paradigmatic system continuously, monovinylarene accounts for 15.7%～47.4% of all total monomer weights in the mixture, conjugated diene accounts for 40.0%～67.9% of all total monomer weights, its method be with said mixture weight 60%～80% 130 ℃～160 ℃ following polymerizations, obtain random section S of monovinylarene and conjugated diene
1-B
1/ S
2-Me; Be cooled to 65 ℃～75 ℃, once inject the residue mix monomer, make feed rate be higher than speed of reaction, form the polymkeric substance S that the living chain end has transition
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, at polymer chain S
1-B
1/ S
2(B
2→ S
3)-B
3-Me carries out coupling with the silicon or the stannane coupling agent that contain functional group at last, forms the radial segmented copolymer of functionalized monomorphism
11. the preparation method of the radial segmented copolymer of functionalized 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, and monovinylarene accounts for 18.5%～42.0Wt% of all total monomer weights in the mixture, and conjugated diene accounts for 44.7%～61.2Wt% of all total monomer weights; It is to account for 2.5%～6.4% of all total monomer weights that conjugated diene adds fashionable add-on separately.
12. the preparation method of the radial segmented copolymer of functionalized 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 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 at twice to paradigmatic system continuously, 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, its method be with said mixture weight 60%～80% 130 ℃～160 ℃ following polymerizations, obtain random section S of monovinylarene and conjugated diene
1-B
1/ S
2-Me; Be cooled to 65 ℃～75 ℃, once inject the residue mix monomer, make feed rate be higher than speed of reaction, form the polymkeric substance S that the living chain end has transition
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, at polymer chain S
1-B
1/ S
2(B
2→ S
3)-B
3-Me carries out coupling with the silicon or the stannane coupling agent that contain functional group at last, forms the radial segmented copolymer of functionalized monomorphism
13. the preparation method of the radial segmented copolymer of monomorphism according to claim 11, 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 25.2%～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.
14. preparation method according to claim 6 or the radial segmented copolymer of 8 or 11 described functionalized 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. the preparation method according to claim 6 or the radial segmented copolymer of 8 or 11 described functionalized monomorphism is characterized in that initiator is n-Butyl Lithium, s-butyl lithium.
16. preparation method according to claim 6 or the radial segmented copolymer of 8 or 11 described functionalized monomorphism, it is characterized in that coupling agent is alkoxyl silicone, the tin compound that contains one or more epoxy group(ing), amino or imido grpup, sulfydryl, its general formula is: X-R
1-Y-(OR
2)
3Wherein X is a functional group of containing epoxy group(ing), amino or imido grpup, sulfydryl, R
1Be alkylidene group or the cycloalkylidene that contains 1～8 carbon atom, R
2For containing the alkyl of 1～4 carbon atom; Y is Siliciumatom or tin atom.
17. the preparation method of the radial segmented copolymer of functionalized 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 segmented copolymer of functionalized 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.
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