CN117567704A - Block copolymer, preparation method thereof, brominated block copolymer and application thereof - Google Patents
Block copolymer, preparation method thereof, brominated block copolymer and application thereof Download PDFInfo
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- CN117567704A CN117567704A CN202210946260.2A CN202210946260A CN117567704A CN 117567704 A CN117567704 A CN 117567704A CN 202210946260 A CN202210946260 A CN 202210946260A CN 117567704 A CN117567704 A CN 117567704A
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- block copolymer
- hpir
- block
- hvbr
- monomer
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 155
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 69
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 34
- -1 ether compound Chemical class 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229920002223 polystyrene Polymers 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000005065 High vinyl polybutadiene Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940077388 benzenesulfonate Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 230000004580 weight loss Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229920006318 anionic polymer Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 2
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229940041616 menthol Drugs 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 abstract description 24
- 230000031709 bromination Effects 0.000 abstract description 18
- 239000005062 Polybutadiene Substances 0.000 abstract description 10
- 229920002857 polybutadiene Polymers 0.000 abstract description 10
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 abstract description 9
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 9
- 239000012774 insulation material Substances 0.000 abstract description 6
- 229920006327 polystyrene foam Polymers 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 9
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the field of synthesis and preparation of high polymer materials, and discloses a block copolymer, a preparation method thereof, a brominated block copolymer and application thereof. The block copolymer has PS 1 ‑HPIR 1 ‑HVBR‑HPIR 2 ‑PS 2 The block structure shown; at least 80 mole percent of propylene-based structural units based on the total moles of HPIR; at least 80 mole percent vinyl building blocks based on total moles of HVBR; the content of the styrene block is 20-40wt%; the molecular weight distribution of the block polymer is 1 to 1.2. The blockThe copolymer contains a polyisoprene block with high propenyl content and a polybutadiene block with high vinyl content, can effectively improve the bromination selectivity and bromination efficiency, and the prepared brominated block copolymer has high thermal decomposition temperature and high glass transition temperature, and is suitable for being used as a flame retardant of polystyrene foam external wall heat insulation materials.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of high polymer materials, in particular to a block copolymer, a preparation method thereof, a brominated block copolymer and application thereof.
Background
Hexabromocyclododecane (HBCD) is the most main flame retardant for foaming polystyrene (EPS) and extrusion polystyrene (XPS) of external wall heat insulation materials, but HBCD has poor thermal stability, starts to decompose at 150 ℃ to generate hydrogen bromide, and generates severe dehydrobromination reaction at 190 ℃ to cause damage to eyes, skin and respiratory systems, and has a potential long-term hazard to human environment despite excellent flame retardant effect. With the increasing use of HBCD, the problems of durability and long-distance migration of HBCD in environmental media such as air, water, soil sediment and sludge are increasingly pronounced, and bioaccumulation and bioamplification in fish, birds and mammals are also increasingly serious. In order to enhance the management of chemicals and reduce the hazards caused by chemicals, especially toxic and hazardous chemicals, the Stockholm convention sets forth regulations concerning the persistent organic contaminant HBCD to exit the flame retardant market for a limited period of time, which HBCD will exit the global exterior wall insulation flame retardant market.
Following the development rules of flame retardants and combining the production process of polystyrene thermal insulation foam, polymeric additive products will become sustainable flame retardant solutions in polystyrene foam production applications. The polymeric additive has a higher molecular weight and increases migration, extraction and evaporation resistance, thereby reducing the risk of release of the flame retardant from the polymer into the environment. High molecular weight polymers are difficult to pass through biological membranes, so the polymers are not easily absorbed by the intact digestive tract, reducing bioavailability, potential exposure, and adverse health effects. Among all the polymeric additives, the brominated products of thermoplastic elastomers obtained by polymerizing styrene and conjugated dienes are the most efficient sustainable solutions in polymeric flame retardants due to their high molecular weight and good flame retardant effect.
The conventional styrene and conjugated diene block polymer in the market mainly comprises SBS and SIS, but the lateral group content of conjugated diene is low, so that the double bonds capable of participating in bromination reaction are fewer, the thermal decomposition temperature of the prepared styrene and conjugated diene block polymer brominated product is low, and the use requirement of the external wall heat insulation flame retardant can not be met.
Disclosure of Invention
The invention aims to solve the problems that the prior art has low bromination efficiency of a block copolymer, the prepared brominated product has low bromine content and the thermal decomposition temperature cannot meet the flame retardant requirement of an external wall heat insulation material, and provides a block copolymer and a preparation method thereof, and the brominated block copolymer.
In order to achieve the above object, a first aspect of the present invention provides a block copolymer characterized in that the block copolymer has PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block structure shown;
wherein PS 1 And PS (polystyrene) 2 Each independently is a styrene block, HPIR 1 And HPIR 2 Each independently is a high propylene-based polyisoprene block and HVBR is a high vinyl polybutadiene block;
at least 80 mole percent of propylene-based structural units, based on the total moles of HPIR in the block copolymer; at least 80 mole percent of vinyl structural units based on the total moles of HVBR in the block copolymer;
the content of the styrene block is 20-40wt% based on the total weight of the block copolymer;
the molecular weight distribution of the block copolymer is 1-1.2.
The second aspect of the present invention provides a method for producing a block copolymer, characterized by comprising the steps of:
(1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure regulator and an initiator, carrying out a first anionic polymerization reaction on the styrene monomer 1 to obtain a polymer containing PS 1 A polymer solution of the structure;
(2) To said PS-containing 1 Adding isoprene monomer 1 into the polymer solution of (2) to carry out second anionic solution polymerization to obtain PS-containing polymer 1 -HPIR 1 Copolymer solution of structure;
(3) To said PS-containing 1 -HPIR 1 Adding butadiene monomer into the copolymer solution with the structure, and carrying out a third anionic polymerization reaction to obtain PS 1 -HPIR 1 -copolymer solutions of HVBR structure;
(4) To said PS-containing 1 -HPIR 1 Adding isoprene monomer 2 into copolymer solution with HVBR structure, and performing fourth anionic polymerization reaction to obtain PS 1 -HPIR 1 -HVBR-HPIR 2 Copolymer solution of structure;
(5) To said PS-containing 1 -HPIR 1 -HVBR-HPIR 2 Adding a styrene monomer 2 into the copolymer solution with the structure, and carrying out a fifth anionic polymer to obtain PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Copolymer solution of structure, for the PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Drying the copolymer solution with the structure to obtain the block copolymer;
the composite structure regulator comprises a component A, a component B and a component C, wherein the component A is a polar ether compound and/or a polar amine compound, and the component B is a polar ether compound and/or a polar amine compound; the component C is at least one selected from sodium alkoxide, potassium alkoxide, sodium alkyl benzene sulfonate and potassium alkyl benzene sulfonate;
the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction and the fifth anionic polymerization reaction are respectively and independently 0-50 ℃;
the amount of the styrene monomer is 20 to 40wt% based on the total weight of the styrene monomer, the isoprene monomer and the butadiene monomer.
In a third aspect, the present invention provides a block copolymer produced by the above-described production method.
In a fourth aspect, the present invention provides a brominated block copolymer, characterized in that the brominated block copolymer is prepared by brominating the above block copolymer.
The fifth aspect of the invention provides an application of the brominated block copolymer in an external wall heat preservation flame retardant.
Through the technical scheme, the block copolymer and the preparation method thereof, the brominated block copolymer and the application thereof provided by the invention have the following beneficial effects:
the block copolymer provided by the invention comprises a polyisoprene block with high propenyl content and a polybutadiene block with high vinyl content, can effectively improve the bromination selectivity and bromination efficiency, and ensures that the prepared brominated block copolymer has high thermal decomposition temperature and high glass transition temperature.
Specifically, in the block copolymer provided by the invention, the polyisoprene block contains at least 80 mol% of propenyl structural units, the polybutadiene block contains at least 80 mol% of vinyl structural units, the block copolymer has a narrow molecular weight distribution, the content of the styrene block in the block copolymer is 20-40wt%, more than 95% of double bonds in the block copolymer can be brominated and added, and the prepared brominated block copolymer has high thermal decomposition temperature and high glass transition temperature, so that the brominated block copolymer is particularly suitable for being used as a flame retardant for external wall heat insulation materials such as polystyrene foam and the like.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a block copolymer characterized in that the block copolymer has PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block structure shown;
wherein PS 1 And PS (polystyrene) 2 Each independently is a styrene block, HPIR 1 And HPIR 2 Each independently is a high propylene-based polyisoprene block and HVBR is a high vinyl polybutadiene block;
at least 80 mole percent of propylene-based structural units, based on the total moles of HPIR in the block copolymer; at least 80 mole percent of vinyl structural units based on the total moles of HVBR in the block copolymer;
the content of the styrene block is 20-40wt% based on the total weight of the block copolymer;
The molecular weight distribution of the block copolymer is 1-1.2.
Generally, for butadiene building blocks, the vinyl structure bromination efficiency is highest, and the cis bromination efficiency is lowest for the trans-second; for isoprene building blocks, the bromination efficiency of the propenyl structure is higher than that of the 1, 4-structure. In order to produce a brominated block copolymer having a higher bromine content with the same number of double bonds, it is necessary to increase the pendant content of butadiene and isoprene.
In the invention, the block copolymer provided by the invention has the specific block structure, and the block copolymer comprises a polyisoprene block with high propenyl content and a polybutadiene block with high vinyl content, so that the block copolymer comprises higher side group content, the bromination selectivity and bromination efficiency can be effectively improved, and the prepared brominated block copolymer has high thermal decomposition temperature and high glass transition temperature.
Specifically, in the block copolymer provided by the invention, the polyisoprene block contains at least 80 mol% of propenyl structural units, the polybutadiene block contains at least 80 mol% of vinyl structural units, the block copolymer has a narrow molecular weight distribution, the content of the styrene block in the block copolymer is 20-40wt%, more than 95% of double bonds in the block copolymer can be brominated and added, and the prepared brominated block copolymer has high thermal decomposition temperature and high glass transition temperature, and is particularly used as a flame retardant for external wall heat insulation materials such as polystyrene foam and the like.
In the present invention, the high propylene-based polyisoprene block (HPIR 1 And HPIR 2 ) Content of propylene-based structural units (Ia%), content of vinyl structural units (Bv%) in high vinyl polybutadiene block (HVBR), and high propylene-based polyisoprene block (HPIR) in block copolymer 1 +HPIR 2 ) The content (Ip%) of (c) was measured by a nuclear magnetic resonance hydrogen spectrometry method.
Further, it contains at least 82 mol% of propylene-based structural units, preferably at least 84 mol% of propylene-based structural units, and more preferably at least 86 mol% of propylene-based structural units, based on the total moles of HPIR in the block copolymer.
Further, it contains at least 82 mole% of vinyl structural units, preferably at least 84 mole% of vinyl structural units, and more preferably at least 86 mole% of vinyl structural units, based on the total moles of HVBR in the block copolymer.
Further, the styrene block (PS) 1 +PS 2 ) The content (St%) is 22-35wt%.
According to the invention, PS 1 And PS (polystyrene) 2 The weight ratio of (3/7) to (7/3).
In the present invention, PS 1 And PS (polystyrene) 2 Independently represents styrene blocks, PS 1 And PS (polystyrene) 2 Identical to Or different.
In the present invention, the content of styrene block and PS in the block copolymer are controlled 1 And PS (polystyrene) 2 The weight ratio of (2) is in the range described above to ensure PS 1 And PS (polystyrene) 2 Segment length, in particular PS 1 And PS (polystyrene) 2 The number average molecular weights of (2) are each independently at least 8000, if PS 1 And PS (polystyrene) 2 The number average molecular weight of (2) is too low to be effective in forming a phase-separated structure; PS (PS) 1 And PS (polystyrene) 2 The number average molecular weights of (2) are each independently at most not more than 20000, otherwise the processability of the block polymer is too poor to be industrially stable.
In the present invention, the content (St%) of styrene block in the block copolymer is determined by nuclear magnetic resonance hydrogen spectrometry, PS 1 And PS (polystyrene) 2 The weight ratio of (2) is calculated according to the feeding amount of the styrene monomer.
Further, PS 1 And PS (polystyrene) 2 The weight ratio of (2) is 4/6-6/4.
According to the invention, the high propylene-based polyisoprene block is present in an amount of 30 to 50wt%, based on the total weight of the block polymer.
According to the invention, HPIR 1 And HPIR 2 The weight ratio of (2) is 4/6-6/4.
In the invention, the content of the high propenyl polyisoprene block and HPIR in the block polymer are controlled 1 And HPIR 2 The weight ratio of (c) is within the above range to ensure that there are enough double bonds in the block copolymer that addition reactions can occur to increase the bromine content in the final brominated block copolymer, thereby ensuring that the brominated product has higher thermal stability and glass transition temperature.
In the present invention, the high propylene-based polyisoprene block (HPIR) 1 +HPIR 2 ) Content (Ip%) of (B) was measured by nuclear magnetic resonance hydrogen spectrometry, HPIR 1 And HPIR 2 The weight ratio of (2) is calculated according to the monomer feed.
Further, the high propylene-based polyisoprene block is present in an amount of 35 to 45wt%, based on the total weight of the block polymer.
According to the invention, the high vinyl polybutadiene block is present in an amount of 20 to 40 wt.%, based on the total weight of the block copolymer.
In the invention, when the content of the high vinyl polybutadiene block in the block copolymer is controlled to meet the range, enough double bonds capable of undergoing addition reaction can be ensured in the block copolymer, so that the bromine content in the final brominated block polymer is increased, and the brominated product is ensured to have higher thermal stability and glass transition temperature.
Further, the high vinyl polybutadiene block is present in an amount of 25 to 35 wt.%, based on the total weight of the block copolymer.
According to the invention, the number average molecular weight of the block copolymer is 50000-200000, preferably 80000-150000.
In the invention, the number average molecular weight of the block copolymer is controlled firstly to provide more double bonds capable of bromination reaction, secondly to ensure a good phase separation structure and thirdly to ensure the processability of the block copolymer. When the number average molecular weight of the block copolymer is less than 50000, the number of double bonds on a single molecular chain which can undergo bromination reaction is small, which is unfavorable for preparing a brominated block copolymer with good thermal stability. When the number average molecular weight of the block copolymer is more than 200000, the processability of the block copolymer is too poor, which is not advantageous for industrial stable production.
According to the invention, the molecular weight distribution of the block copolymer is from 1 to 1.2, preferably from 1.01 to 1.15, more preferably from 1.02 to 1.1.
In the present invention, PS prior to bromination is required in order to prepare a brominated block copolymer with better thermal stability 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block copolymer has narrower molecular weight distribution, PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The low molecular weight component of the block copolymer can have a detrimental effect on the properties of the brominated product, and it is desirable to control the content of the low molecular weight component as much as possible.
The second aspect of the present invention provides a method for producing a block copolymer, characterized by comprising the steps of:
(1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure regulator and an initiator, carrying out a first anionic polymerization reaction on the styrene monomer 1 to obtain a polymer containing PS 1 A polymer solution of the structure;
(2) To said PS-containing 1 Adding isoprene monomer 1 into the polymer solution of (2) to carry out second anionic solution polymerization to obtain PS-containing polymer 1 -HPIR 1 Copolymer solution of structure;
(3) To said PS-containing 1 -HPIR 1 Adding butadiene monomer into the copolymer solution with the structure, and carrying out a third anionic polymerization reaction to obtain the PS-containing polymer 1 -HPIR 1 -copolymer solutions of HVBR structure;
(4) To said PS-containing 1 -HPIR 1 Adding isoprene monomer 2 into copolymer solution with HVBR structure, and performing fourth anionic polymerization reaction to obtain PS-containing polymer 1 -HPIR 1 -HVBR-HPIR 2 Copolymer solution of structure;
(5) To said PS-containing 1 -HPIR 1 -HVBR-HPIR 2 Adding a styrene monomer 2 into the copolymer solution with the structure, and carrying out a fifth anionic polymer to obtain a PS-containing polymer 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Copolymer solution of structure, for the PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Drying the copolymer solution with the structure to obtain the block copolymer;
the composite structure regulator comprises a component A, a component B and a component C, wherein the component A is a polar ether compound and/or a polar amine compound, and the component B is a polar ether compound and/or a polar amine compound; the component C is at least one selected from sodium alkoxide, potassium alkoxide, sodium alkyl benzene sulfonate and potassium alkyl benzene sulfonate;
the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction and the fifth anionic polymerization reaction are respectively and independently 0-50 ℃;
the amount of the styrene monomer is 20 to 40wt% based on the total weight of the styrene monomer, the isoprene monomer and the butadiene monomer.
In the present invention, styrene, butadiene and isoprene are subjected to anionic polymerization in the presence of a complex modifier comprising specific components, and the polymerization temperature of the anionic polymerization and the amount of styrene monomer are controlled, whereby a block copolymer having a specific structure according to the first aspect of the present invention, in particular, a block copolymer comprising a high propylene-based polyisoprene block and a high vinyl-based polybutadiene block, can be produced, whereby the block copolymer comprises a higher side group content, can effectively improve the selectivity and efficiency of bromination, and enables the production of a brominated block copolymer having a high thermal decomposition temperature and a high glass transition temperature.
Specifically, in the block copolymer provided by the invention, the polyisoprene block contains at least 80 mol% of propenyl structural units, the polybutadiene block contains at least 80 mol% of vinyl structural units, the content of the styrene block in the block copolymer is 20-40wt%, more than 95% of double bonds in the block copolymer can be subjected to bromination addition, and the block copolymer has a narrow molecular weight distribution, so that the prepared brominated block copolymer has a high thermal decomposition temperature and a high glass transition temperature, and is particularly suitable for being used as a flame retardant of polystyrene foam external wall heat insulation materials.
In the invention, when the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction and the fifth anionic polymerization reaction are controlled to be 0-50 ℃ respectively, the microstructure of the block copolymer can be controlled, so that the prepared block copolymer has the special block structure disclosed by the first aspect of the invention. Specifically, the polymerization temperature is too low, the polymerization reaction rate is slow, the mass production of the tissue is not facilitated, and the energy consumption of unit product is high; the polymerization temperature is too high, and the control capability of the composite structure regulator on the microstructure of the block copolymer is reduced, which is unfavorable for preparing the block copolymer with high side group content.
Further, the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0 to 40 ℃.
In the present invention, the time of the first anionic polymerization is 5 to 15 minutes, preferably 8 to 12 minutes.
In one embodiment of the present invention, step (1) includes: mixing nonpolar hydrocarbon solvent, composite structure regulator and styrene monomer 1 at lower temperature to obtain a mixture, adding initiator into the mixture, and performing the first anionic polymerization to obtain a polymer containing PS 1 A structured polymer solution.
In the present invention, the time of the second anionic polymerization is 15 to 30 minutes, preferably 18 to 25 minutes.
In the present invention, the time of the third anionic polymerization is 15 to 25 minutes, preferably 18 to 22 minutes.
In the present invention, the time of the fourth anionic polymerization is 15 to 30 minutes, preferably 18 to 25 minutes.
In the present invention, the time of the fifth anionic polymerization is 5 to 15 minutes, preferably 8 to 12 minutes.
According to the invention, the component A has a structure represented by formula I;
Wherein Q1, Q2 and Q3 are each independently N or O, N1 is an integer from 2 to 6, m is 0 or 1, r is 0 or 1, N2 is an integer from 0 to 4, and Q1 and Q2 are each independently 1 or 2.
In the invention, the component A with the specific structure is selected, the structure control capability of anionic polymerization of butadiene and isoprene is strong, and the block copolymer with high side group content can be prepared.
Further, the component a is selected from at least one of diethylene glycol dimethyl ether (2G) (Q1, Q2 and Q3 are O, Q1 and Q2 are 1, m is 1, r is 0, N1 and N2 are 2), tetramethyl ethylenediamine (Q1 and Q3 are N, Q1 and Q2 are 2, m is 0, r is 0, N1 is 2, N2 is 0), pentamethyl divinyl triamine (Q1, Q2 and Q3 are N, Q1 and Q2 are 2, m is 1, r is 1, N1 and N2 are 2) and bis-dimethylaminoethyl ether (BDMAEE) (Q1 and Q3 are N, Q2 are O, Q1 and Q2 are 2, m is 1, r is 0, N1 and N2 are 2); preferably diethylene glycol dimethyl ether and/or bis dimethylaminoethyl ether.
According to the invention, the component B has a structure represented by formula II;
wherein R is 1 And R is 2 Each independently is H or CH 3 ，R 3 Alkoxy of 2 to 6 carbon atoms,
In the invention, the component B with the specific structure is selected, the temperature sensitivity is low, the polymerization rate adjusting capability is strong, the anionic polymerization rate can be obviously improved, and the side reaction degree of the component A is reduced.
Further, the component B is selected from the group consisting of ditetrahydrofuran propane (DTHFP) (R 1 And R is 2 Is CH 3 ，R 3 Is that) Tetrahydrofurfuryl ethyl ether (ETE) (R) 1 And R is 2 Is H, R 3 Is ethoxy) and N, N-dimethyltetrahydrofurfuryl amine (R) 1 And R is 2 Is H, R 3 Is->) At least one of them.
According to the invention, the component C is selected from sodium alkoxide and/or sodium alkylbenzenesulfonate, preferably at least one selected from Sodium Terpinealkoxide (STP), sodium menthol and Sodium Dodecylbenzenesulfonate (SDBS), more preferably sodium terpinealkoxide.
In the invention, the component C with the specific type is selected to have a synergistic effect with the component A, so that the temperature sensitivity of the component A can be obviously reduced, and the control capability of the component A on the anionic polymerization microstructure of butadiene and styrene is improved.
According to the invention, the component A is used in an amount of 0.2 to 0.8mol relative to 1mol of initiator.
In the invention, the component A is mainly used for controlling the content of the side group of the conjugated diene block (polybutadiene and/or polyisoprene) in the block copolymer, when the content of the side group of the block copolymer is too small, the content of the side group of the block copolymer can not meet the requirement, and the content of the component A is too large, so that the side reaction degree is increased, and the molecular weight distribution of the product is widened.
Further, the component A is used in an amount of 0.3 to 0.6mol with respect to 1mol of the initiator.
According to the invention, the component B is used in an amount of 0.5 to 3mol relative to 1mol of initiator.
In the invention, the component B is mainly used for adjusting the polymerization rate of the anionic polymerization reaction, in order to reduce the side reaction caused by the component A, the anionic polymerization rate needs to be improved, the consumption of the component B is too small, the improvement of the polymerization rate is not obvious, the consumption of the component B is too large, the polymerization rate is not easy to control, and the control capability of the component A on the content of the conjugated diene side group in the block copolymer can be influenced.
Further, the component B is used in an amount of 0.8 to 2mol with respect to 1mol of the initiator.
According to the invention, component C is used in an amount of 0.03 to 0.1mol relative to 1mol of initiator.
In the invention, the component C is mainly used for improving the control capability of the component A on the microstructure of the conjugated diene in the block copolymer and reducing the temperature sensitivity and the side reaction degree of the component A. The use of component C in an amount too small to fully exert the above-mentioned effects, and the use of component C in an amount too large may result in an increase in the degree of side reactions and a broadening of the molecular weight distribution.
Further, the component C is used in an amount of 0.04 to 0.08mol with respect to 1mol of the initiator.
In the present invention, the type of the nonpolar hydrocarbon solvent is not particularly limited, and nonpolar hydrocarbon solvents of conventional types in the art, such as cyclohexane, may be used. The amount of the nonpolar hydrocarbon solvent is not particularly limited as long as the compound structure regulator and the like can be sufficiently dissolved.
In the present invention, the kind of the initiator is not particularly limited, and an anionic polymerization initiator commonly used in the art, such as n-butyllithium, may be used. The amount of initiator may also be in accordance with the amounts customary in the art, for example, from 0.5 to 2mmol, based on 100g of polymerized monomer (styrene, butadiene and isoprene).
According to the invention, the styrene monomer is used in an amount of 20 to 40% by weight, preferably 22 to 35% by weight, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer.
According to the invention, the weight ratio of the styrene monomer 1 to the styrene monomer 2 is 3/7 to 7/3, preferably 4/6 to 6/4.
According to the invention, the isoprene monomer is used in an amount of 30 to 50 wt.%, preferably 35 to 45 wt.%, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer.
According to the present invention, the weight ratio of the isoprene monomer 1 to the isoprene monomer 2 is 4/6 to 6/4.
According to the invention, the monomers of butadiene are used in amounts of from 20 to 40% by weight, preferably from 25 to 35% by weight, based on the total weight of styrene monomers, isoprene monomers and butadiene monomers.
According to the invention, the block copolymer with a phase separation structure can be obtained by controlling the feeding sequence of the polymerization monomers of styrene, butadiene and isoprene and the feeding amount of each step, so that the brominated block copolymer obtained by bromination has higher thermal stability.
According to the invention, the preparation method further comprises the following steps: for the PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymer solution of the structure undergoes a termination reaction.In general, the terminating agent for anionic polymerization may be an acid, an alcohol, water or the like, but the acid and the alcohol adversely affect bromination reaction, and the terminating agent in the terminating reaction of the present invention is preferably deionized water.
In the present invention, the preparation method is performed in the presence of nitrogen.
In a third aspect, the present invention provides a block copolymer produced by the above-described production method.
In a fourth aspect, the present invention provides a brominated block copolymer, characterized in that the brominated block copolymer is prepared by brominating the above block copolymer.
In the present invention, when the block copolymer provided in the first or third aspect of the present invention is subjected to bromination, the bromination reaction is carried out only in HPIR 1 、HPIR 2 And HVBR block, PS 1 And PS (polystyrene) 2 The blocks do not participate in the bromination reaction, HPIR 1 、HPIR 2 And more than 95% of the double bonds in the HVBR block are brominated, the number of unreacted double bonds in the block copolymer determining the bromine content of the brominated block copolymer, preferably the brominated block copolymer has a bromine content of 60 to 68 weight percent, preferably 61 to 67 weight percent, more preferably 62 to 66 weight percent.
According to the invention, the brominated block copolymer has a number average molecular weight of 50000 to 200000, preferably 80000 to 150000.
In the present invention, during bromination of the isoprene block and butadiene block polymers in the block copolymer, a portion of the molecular chains will break, and the number average molecular weight of the final brominated block copolymer is substantially equivalent to the number average molecular weight of the block copolymer prior to bromination.
According to the invention, the brominated block copolymer has a molecular weight distribution of from 1 to 1.2, preferably from 1.01 to 1.15, more preferably from 1.02 to 1.1. In the present invention, the molecular weight distribution of the brominated block copolymer is substantially the same as the molecular weight distribution of the block copolymer prior to bromination.
According to the present invention, the brominated block copolymer has a 5wt% thermal weight loss temperature of 260℃or higher, preferably 260 to 268℃and more preferably 261 to 267 ℃.
According to the present invention, the brominated block copolymer has a glass transition temperature of 120℃or higher, preferably 121 to 133℃and more preferably 123 to 131 ℃.
The fourth aspect of the invention provides an application of the brominated block copolymer in an external wall heat preservation flame retardant.
The present invention will be described in detail by examples.
The vinyl structure unit content, propenyl structure unit content, styrene structure unit content, butadiene structure unit content, isoprene structure unit content of the block polymer of styrene and conjugated diene and bromine content of the brominated block polymer adopt Bruker AVANCE400 type superconductive nuclear magnetic resonance spectrometer 1 H-NMR) test, sample tube diameter 5mm, solvent deuterated chloroform CDCl 3 The sample concentration was 15% (W/V), the test temperature was ambient, the number of scans was 16, and the sample was scaled with a tetramethylsilane chemical shift of 0 ppm.
The molecular weights of the styrene and conjugated diene block polymers and the distribution thereof were measured using an HLC-8320 type gel permeation chromatograph of Tosoh corporation, japan, wherein the test conditions include: the chromatographic column is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure THF, the calibration standard sample is polystyrene, the mass concentration of the sample is 1mg/mL, the sample injection amount is 10 mu L, the flow rate is 0.35mL/min, and the test temperature is 40 ℃.
The glass transition temperature of the brominated block polymer is measured by a TA-2980DSC differential scanning calorimeter according to a method specified in GB/T29611-2013 raw rubber glass transition temperature, and the temperature rising rate is 20 ℃/min.
The weight loss of 5wt% of the brominated block polymer was determined using a TA-2980DSC differential scanning calorimeter, with the following specific procedures: firstly heating to 100 ℃, keeping the temperature constant for 5min, and then heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere.
The experimental setup and process are as follows.
PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block polymer: the experiments were carried out in a 5L polymerization reactor with solvent, butadiene, isoprene andadding styrene monomer from a polymerization pipeline, adding an initiator and a structure regulator from the top of a polymerization kettle by adopting an injector, performing condensation treatment by adopting water vapor after polymerization, and drying by adopting a plasticator to obtain PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block polymers.
Brominated block polymer: the preparation method comprises the steps of carrying out the process in a 10L stainless steel reaction kettle coated with a polytetrafluoroethylene lining, redissolving the obtained basic block copolymer in chloroform, dropwise adding a chloroform solution containing liquid bromine under high-speed stirring, keeping the temperature of a reaction system constant by utilizing a constant-temperature water bath in the dropwise adding process, and continuing stirring after the dropwise adding is finished to fully carry out the reaction. Then adding aqueous solution prepared by deionized water, sodium hydroxide and sodium sulfite, and fully stirring. And (3) standing and settling the reaction mixture, separating and removing water phase and solid residues, repeatedly washing the obtained solution of the brominated block copolymer with deionized water until the pH value is neutral, adding calcium stearate, epoxidized soybean oil and an antioxidant, finally removing the solvent and drying to obtain the brominated block copolymer of the required product.
The pressures described in this experiment are all gauge pressures.
Antioxidant 1076 and antioxidant 1010 were purchased from enoKai reagent company;
cyclohexane is purchased from national medicine reagent company, the purity is more than 99.9, the molecular weight sieve is soaked for 15 days, and the water content is lower than 5ppm;
trichloromethane, industrial grade, is derived from the petrifaction of Yanshan;
styrene, polymeric grade, source is crape;
butadiene, polymer grade, source is the petrifaction of swallow mountain;
n-butyllithium (Li) was purchased from the reagent Calif. of carbofuran, 100ml, 1.6 mol.L -1 Cyclohexane solution, diluted to 0.4 mol.L -1 A cyclohexane solution;
diethylene glycol dimethyl ether (2G) was purchased from enokava reagent company with a purity of > 99wt%;
didimethylaminoethyl ether (BDMAEE) was purchased from Inokie reagent company in a purity of > 98wt%;
ditetrahydrofurfuryl propane (DTHFP) is purchased from the reagent company carbofuran, the purity is more than 98wt%;
tetrahydrofurfuryl ethyl ether (ETE) is purchased from the company carbofuran reagent with a purity of > 98wt%;
sodium Terpineol (STP) was purchased from Qingshi Hua Feng reagent company as a 1.0mol/L hexane solution;
sodium Dodecyl Benzene Sulfonate (SDBS) was purchased from the carbofuran reagent company in a purity of > 98wt%;
liquid bromine (Br) can be obtained from Qingqia Hua Feng reagent company, and the purity is more than 99%;
calcium stearate (Ca) can be obtained from qingkai Hua Feng reagent company, technical grade;
Epoxidized soybean Oil (OA)) can be obtained from qingkai Hua Feng reagent company, technical grade;
sodium hydroxide (Na) was available from qingkai Hua Feng reagent company, technical grade.
Example 1
This example is for the purpose of illustrating PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block polymers and methods of making the same.
S1, adding cyclohexane solvent (2300 g), a composite structure regulator and styrene monomer 1 (the types and the amounts are shown in a table 1, the amounts listed in the table are all measured by pure compounds, the same applies below) into a 5L reactor under the protection of nitrogen, controlling the initiation reaction temperature within the range of 0-50 ℃ (the polymerization temperature and the pressure are shown in a table 2, the same applies below), adding n-butyllithium with a preset amount into the 5L reactor, controlling the polymerization reaction temperature within the range of 0-50 ℃, and obtaining the catalyst containing PS after 10min 1 Copolymer solution of structure;
s2 to PS-containing 1 Adding isoprene monomer 1 into copolymer solution with structure, controlling polymerization reaction temperature to be 0-50 ℃ and 30min to obtain PS-containing polymer 1 -HPIR 1 Copolymer solution of structure;
s3, to PS-containing 1 -HPIR 1 Adding butadiene monomer into copolymer solution with structure, controlling polymerization reaction temperature to 0-50 ℃ for 30min to obtain PS-containing polymer 1 -HPIR 1 -copolymer solutions of HVBR structure;
s4, to PS-containing 1 -HPIR 1 Copolymers of HVBR structureControlling the polymerization temperature of the solution isoprene monomer 2 to be 0-50 ℃ for 20min to obtain the PS-containing polymer 1 -HPIR 1 -HVBR-HPIR 2 Copolymer solution of structure;
s5, to PS-containing 1 -HPIR 1 -HVBR-HPIR 2 Adding styrene monomer 2 into the copolymer solution with the structure, controlling the polymerization reaction temperature to be 0-50 ℃ and obtaining the PS-containing polymer after 10min 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Copolymer solution of structure;
s6, to PS-containing 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Adding enough deionized water into the copolymer solution with the structure to carry out termination reaction, adding 1g of 1076 antioxidant after termination, and then condensing and drying to obtain PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block copolymer P1 was subjected to analytical tests, and the analytical results are shown in Table 3.
Examples 2 to 13
This example is for the purpose of illustrating PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block polymers and methods of making the same.
According to the method of example 1, except that the parameters shown in tables 1 and 2 were used to prepare block polymers, thereby obtaining PS, respectively 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymers P2-P13 were analyzed and the results are shown in Table 3.
Comparative example 1
According to the method of example 1, except that 2G was not added, specific parameter systems are shown in tables 1 and 2, PS was obtained 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymer DP1 was analyzed and the results are shown in Table 3.
Comparative example 2
According to the method of example 1, except that DTHFP was not added, specific parameters are shown in tables 1 and 2, and the reaction was abnormally slow, to obtain PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block Polymer DP2, analysis results are shown in Table 3, with a styrene residual monomer content of 8.4wt%, butadiene residues The residual monomer content was 6.5wt% and the isoprene residual monomer content was 13.2wt%.
Comparative example 3
According to the method of example 1, except that STP was not added, specific parameters are shown in tables 1 and 2, PS was obtained 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymer DP3 was analyzed and the results are shown in Table 3.
Comparative example 4
According to the method of example 1, except that the initiation temperature was adjusted only, specific parameter systems are shown in tables 1 and 2, PS was obtained 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymer DP4 was analyzed and the results are shown in Table 3.
Comparative example 5
According to the method of example 1, PS was obtained by the following specific parameters, which are shown in tables 1 and 2, except that the amounts of styrene monomers used were varied 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block polymer DP5 was analyzed and the results are shown in Table 3.
TABLE 1
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Table 1 (subsequent)
| Numbering device | Styrene 1/g | Isoprene 1/g | Butadiene/g | Isoprene 2/g | Styrene 2/g |
| Example 1 | 56 | 75 | 112 | 75 | 56 |
| Example 2 | 56 | 75 | 112 | 75 | 56 |
| Example 3 | 56 | 75 | 112 | 75 | 56 |
| Example 4 | 56 | 68 | 126 | 68 | 56 |
| Example 5 | 56 | 83 | 96 | 83 | 56 |
| Example 6 | 48 | 75 | 128 | 75 | 48 |
| Example 7 | 64 | 67 | 112 | 67 | 64 |
| Example 8 | 45 | 75 | 112 | 75 | 67 |
| Example 9 | 56 | 60 | 112 | 90 | 56 |
| Example 10 | 56 | 75 | 112 | 75 | 56 |
| Example 11 | 56 | 75 | 112 | 75 | 56 |
| Example 12 | 56 | 75 | 112 | 75 | 56 |
| Example 13 | 56 | 75 | 112 | 75 | 56 |
| Comparative example 1 | 56 | 75 | 112 | 75 | 56 |
| Comparative example 2 | 56 | 75 | 112 | 75 | 56 |
| Comparative example 3 | 56 | 75 | 112 | 75 | 56 |
| Comparative example 4 | 56 | 75 | 112 | 75 | 56 |
| Comparative example 5 | 33 | 75 | 158 | 75 | 33 |
Table 1 (subsequent)
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TABLE 2
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TABLE 3 Table 3
| Examples of the invention | Mn/10 4 | MWD | Bv/％ | Ia/％ | St/％ | Bd/％ | Ip/％ | PS 1 /PS 2 | HPIR 1 /HPIR 2 |
| P1 | 10.5 | 1.06 | 88.5 | 88.3 | 30.2 | 29.7 | 40.1 | 5/5 | 5/5 |
| P2 | 8.2 | 1.05 | 88.3 | 88.1 | 30.2 | 29.8 | 40.0 | 5/5 | 5/5 |
| P3 | 13.1 | 1.07 | 86.4 | 86.2 | 30.1 | 29.8 | 40.1 | 5/5 | 5/5 |
| P4 | 10.4 | 1.06 | 86.2 | 86.3 | 30.2 | 33.4 | 36.4 | 5/5 | 5/5 |
| P5 | 10.6 | 1.07 | 82.8 | 82.4 | 30.3 | 25.4 | 44.3 | 5/5 | 5/5 |
| P6 | 10.3 | 1.07 | 82.1 | 82.3 | 25.9 | 33.9 | 40.2 | 5/5 | 5/5 |
| P7 | 10.7 | 1.07 | 85.2 | 85.4 | 34.5 | 29.7 | 35.8 | 5/5 | 5/5 |
| P8 | 10.5 | 1.06 | 86.3 | 86.2 | 30.2 | 29.7 | 40.1 | 4/6 | 5/5 |
| P9 | 10.6 | 1.08 | 86.1 | 86.3 | 30.1 | 29.8 | 40.1 | 5/5 | 4/6 |
| P10 | 10.5 | 1.04 | 80.6 | 80.5 | 30.1 | 29.7 | 40.2 | 5/5 | 5/5 |
| P11 | 9.8 | 1.17 | 86.8 | 86.9 | 30.2 | 29.7 | 40.1 | 5/5 | 5/5 |
| P12 | 10.3 | 1.15 | 86.4 | 86.6 | 30.1 | 29.8 | 40.1 | 5/5 | 5/5 |
| P13 | 10.5 | 1.04 | 82.1 | 82.4 | 30.1 | 29.8 | 40.1 | 5/5 | 5/5 |
| DP1 | 10.2 | 1.05 | 77.8 | 77.5 | 30.1 | 29.9 | 40.0 | 5/5 | 5/5 |
| DP2 | 7.7 | 1.38 | 85.3 | 85.2 | 30.1 | 32.6 | 37.3 | 5/5 | 5/5 |
| DP3 | 9.8 | 1.20 | 79.5 | 79.3 | 30.2 | 29.8 | 40.0 | 5/5 | 5/5 |
| DP4 | 10.3 | 1.07 | 77.2 | 77.2 | 30.2 | 29.8 | 40.0 | 5/5 | 5/5 |
| DP5 | 10.4 | 1.06 | 88.3 | 88.2 | 17.8 | 42.1 | 40.1 | 5/5 | 5/5 |
| SBS1301 | 11.4 | 1.04 | 12.4 | 0 | 30.4 | 69.6 | 0 | 5/5 | 5/5 |
| SBS1401 | 8.4 | 1.04 | 12.1 | 0 | 40.6 | 59.4 | 0 | 5/5 | 5/5 |
Note that: bv% is the content of vinyl building blocks in the high vinyl polybutadiene block HVBR; ia% HPIR 1 And HPIR 2 The content of propylene-based structural units; st% styrene Block (PS) in the Block copolymer 1 +PS 2 ) Is contained in the composition; ip% is the content of polyisoprene blocks in the block copolymer; bd% is the content of polybutadiene blocks in the block copolymer.
As can be seen from Table 3, the PS prepared according to the present invention 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block copolymer has high vinyl content in the polybutadiene block and propylene content in the polyisoprene block, has narrow molecular weight distribution, and is particularly suitable for being used as a precursor of the external wall heat insulation brominated block polymer.
Application example 1
This application example is intended to illustrate PS prepared according to the present invention 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block copolymer in brominated Block copolymerApplication.
In a 10L stainless steel reaction kettle coated with a polytetrafluoroethylene lining, redissolving the block copolymer P1 in chloroform to obtain a solution with the concentration of 10 weight percent, dropwise adding 4000g of chloroform solution containing 750g of liquid bromine under high-speed stirring, keeping the temperature of a reaction system at 10 ℃ by utilizing a constant-temperature water bath during the dropwise adding process, and continuously stirring for 300 minutes after the dropwise adding is finished to fully carry out the reaction. An aqueous solution prepared from 1500g of deionized water, 160g of sodium hydroxide and 275g of sodium sulfite was then added and stirred well for 20 minutes. The reaction mixture was allowed to stand still for sedimentation, the aqueous phase and solid residues were separated and the resulting brominated block copolymer solution was repeatedly washed with deionized water to neutral pH, 11g of calcium stearate, 11g of epoxidized soybean oil and 1010 1g of antioxidant were added, and finally the solvent was removed and dried to obtain the desired product brominated block copolymer XP1, the analysis results of which are shown in Table 4.
Application examples 2 to 13
Preparation of PS by the same procedure as in application example 1 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The brominated block copolymer XP2-XP13 was prepared with the exception that block copolymers P2-P13 were used in place of block copolymer P1, and the analytical results are shown in Table 4.
Comparative application examples 1 to 5
Preparation of PS by the same procedure as in application example 1 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The brominated block copolymers XDP1-XDP5 of (A) were prepared except that the block copolymers DP1-DP5 were used in place of the block copolymer P1, and the analysis results are shown in Table 4.
Comparative application examples 6 to 7
A brominated block polymer was prepared by the same method as in application example 1, except that commercial SBS brands SBS1301 and SBS1401 were used instead of PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Block polymer P1, brominated block polymers XSBS1301-XSBS1401, SBS1301 and SBS1401 were prepared, the analytical results of which are shown in Table 3, and the analytical test results of XSBS1301-XSBS1401 are shown in Table 4.
TABLE 4 Table 4
| Examples of the invention | Number average molecular weight/ten thousand | Molecular weight distribution | Bromine content/wt% | 5wt% thermal weight loss temperature/°c | Glass transition temperature/DEGC |
| XP1 | 11.6 | 1.08 | 65.9 | 264 | 129 |
| XP2 | 8.9 | 1.07 | 65.8 | 264 | 126 |
| XP3 | 14.4 | 1.08 | 65.3 | 265 | 131 |
| XP4 | 11.5 | 1.07 | 65.1 | 265 | 126 |
| XP5 | 11.4 | 1.08 | 64.2 | 263 | 127 |
| XP6 | 11.2 | 1.08 | 65.8 | 267 | 123 |
| XP7 | 11.6 | 1.09 | 62.9 | 261 | 131 |
| XP8 | 11.7 | 1.08 | 65.0 | 263 | 128 |
| XP9 | 11.5 | 1.09 | 64.9 | 264 | 128 |
| XP10 | 11.4 | 1.07 | 63.1 | 260 | 124 |
| XP11 | 10.7 | 1.18 | 65.2 | 260 | 128 |
| XP12 | 11.1 | 1.16 | 65.1 | 261 | 128 |
| XP13 | 11.4 | 1.06 | 64.0 | 262 | 127 |
| XDP1 | 11 | 1.08 | 61.6 | 256 | 124 |
| XDP2 | 8.5 | 1.47 | 62.3 | 239 | 120 |
| XDP3 | 11.1 | 1.28 | 62.4 | 244 | 124 |
| XDP4 | 11.3 | 1.10 | 60.9 | 251 | 123 |
| XDP5 | 11.4 | 1.08 | 66.7 | 241 | 117 |
| XSBS1301 | 11.2 | 1.07 | 33.9 | 228 | 110 |
| XSBS1401 | 8.8 | 1.08 | 29.8 | 216 | 106 |
As can be seen from Table 4, by employing the PS provided by the present invention 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The segmented copolymer is used as a precursor, can prepare a brominated segmented copolymer with narrow molecular weight distribution, high bromine content, 5wt% of thermal weight loss temperature and high glass transition temperature, and is particularly suitable for being used as an environment-friendly flame retardant for heat insulation of polystyrene foam external walls.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (22)
1. A block copolymer, characterized in that the block copolymer has PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 The block structure shown;
wherein PS 1 And PS (polystyrene) 2 Each independently is a styrene block, HPIR 1 And HPIR 2 Each independently is a high propylene-based polyisoprene block and HVBR is a high vinyl polybutadiene block;
at least 80 mole percent of propylene-based structural units, based on the total moles of HPIR in the block copolymer; at least 80 mole percent of vinyl structural units based on the total moles of HVBR in the block copolymer;
the content of the styrene block is 20-40wt% based on the total weight of the block copolymer;
the molecular weight distribution of the block copolymer is 1-1.2.
2. The block copolymer according to claim 1, wherein at least 82 mole% of the propylene-based structural units, preferably at least 84 mole% of the propylene-based structural units, more preferably at least 86 mole% of the propylene-based structural units are contained based on the total moles of HPIR in the block copolymer;
Preferably, the block copolymer contains at least 82 mole percent vinyl structural units, preferably at least 84 mole percent vinyl structural units, and more preferably at least 86 mole percent vinyl structural units, based on the total moles of HVBR in the block copolymer.
3. The block copolymer according to claim 1 or 2, wherein the styrene block is present in an amount of 22-35 wt.%, based on the total weight of the block copolymer.
4. A block copolymer according to any one of claims 1 to 3, wherein PS 1 And PS (polystyrene) 2 The weight ratio of (2) is 3/7-7/3, preferably 4/6-6/4.
5. The block copolymer according to claims 1-4, wherein the high propylene-based polyisoprene block is present in an amount of 30-50wt%, preferably 35-45wt%, based on the total weight of the block polymer;
preferably HPIR 1 And HPIR 2 The weight ratio of (2) is 4/6-6/4.
6. The block copolymer according to claims 1 to 5, wherein the high vinyl polybutadiene block is present in an amount of 20 to 40 wt.%, preferably 25 to 35 wt.%, based on the total weight of the block copolymer.
7. The block copolymer according to claims 1-6, wherein the number average molecular weight of the block copolymer is 50000-200000, preferably 80000-150000;
Preferably, the molecular weight distribution of the block copolymer is from 1.01 to 1.15, more preferably from 1.02 to 1.1.
8. A method of preparing a block copolymer, the method comprising the steps of:
(1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure regulator and an initiator, carrying out a first anionic polymerization reaction on the styrene monomer 1 to obtain a polymer containing PS 1 A polymer solution of the structure;
(2) To said PS-containing 1 Adding isoprene monomer 1 into the polymer solution of (2) to carry out second anionic solution polymerization to obtain PS-containing polymer 1 -HPIR 1 Copolymer solution of structure;
(3) To said PS-containing 1 -HPIR 1 Adding butadiene monomer into the copolymer solution with the structure, and carrying out a third anionic polymerization reaction to obtain the PS-containing polymer 1 -HPIR 1 -copolymer solutions of HVBR structure;
(4) To said PS-containing 1 -HPIR 1 Adding isoprene monomer 2 into copolymer solution with HVBR structure, and performing fourth anionic polymerization reaction to obtain PS-containing polymer 1 -HPIR 1 -HVBR-HPIR 2 Copolymer solution of structure;
(5) To said PS-containing 1 -HPIR 1 -HVBR-HPIR 2 Adding a styrene monomer 2 into the copolymer solution with the structure, and carrying out a fifth anionic polymer to obtain a PS-containing polymer 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Copolymer solution of structure containing PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Drying the copolymer solution with the structure to obtain the block copolymer;
The composite structure regulator comprises a component A, a component B and a component C, wherein the component A is a polar ether compound and/or a polar amine compound, and the component B is a polar ether compound and/or a polar amine compound; the component C is at least one selected from sodium alkoxide, potassium alkoxide, sodium alkyl benzene sulfonate and potassium alkyl benzene sulfonate;
the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction and the fifth anionic polymerization reaction are respectively and independently 0-50 ℃;
the amount of the styrene monomer is 20 to 40wt% based on the total weight of the styrene monomer, the isoprene monomer and the butadiene monomer.
9. The preparation method according to claim 8, wherein the component a has a structure represented by formula I;
wherein Q1, Q2 and Q3 are each independently N or O, N1 is an integer from 2 to 6, m is 0 or 1, r is 0 or 1, N2 is an integer from 0 to 4, and Q1 and Q2 are each independently 1 or 2;
preferably, the component A is at least one selected from diethylene glycol dimethyl ether, tetramethyl ethylene diamine, pentamethyl divinyl triamine and bis-dimethylaminoethyl ether; preferably diethylene glycol dimethyl ether and/or bis dimethylaminoethyl ether.
10. The production method according to claim 8 or 9, wherein the component B has a structure represented by formula II;
wherein R is 1 And R is 2 Each independently is H or CH 3 ，R 3 Alkoxy of 2 to 6 carbon atoms,
Preferably, the component B is at least one selected from the group consisting of ditetrahydrofurfuryl propane, tetrahydrofurfuryl ethyl ether and N, N-dimethyltetrahydrofurfuryl amine.
11. The preparation method according to any one of claims 9 to 10, wherein the component C is selected from sodium alkoxide and/or sodium alkylbenzenesulfonate, preferably at least one selected from sodium terpineate, sodium menthol and sodium dodecylbenzenesulfonate.
12. The preparation process according to any one of claims 9 to 11, wherein the amount of component a is 0.2 to 0.8mol, preferably 0.3 to 0.6mol, the amount of component B is 0.5 to 3mol, preferably 0.8 to 2mol, and the amount of component C is 0.03 to 0.1mol, preferably 0.04 to 0.08mol, relative to 1mol of the initiator.
13. The production method according to any one of claims 9 to 12, wherein the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0 to 40 ℃.
14. The production method according to any one of claims 9 to 13, wherein the styrene monomer is used in an amount of 22 to 35% by weight based on the total weight of the styrene monomer, the isoprene monomer and the butadiene monomer;
preferably, the weight ratio of the styrene monomer 1 to the styrene monomer 2 is 3/7 to 7/3, preferably 4/6 to 6/4.
15. The preparation method according to any one of claims 9 to 14, wherein the isoprene monomer is used in an amount of 30 to 50wt%, preferably 35 to 45wt%, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer;
preferably, the weight ratio of the isoprene monomer 1 to the isoprene monomer 2 is 4/6 to 6/4.
16. The preparation process according to any one of claims 9 to 15, wherein the monomer amount of butadiene is 20 to 40wt%, preferably 25 to 35wt%, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer.
17. The production method according to any one of claims 9 to 16, wherein the production method further comprises: for the PS 1 -HPIR 1 -HVBR-HPIR 2 -PS 2 Carrying out termination reaction on the block polymer solution with the structure;
preferably, the terminating agent in the termination reaction is deionized water.
18. A block copolymer prepared by the method of any one of claims 9-17.
19. A brominated block copolymer prepared by brominating the block copolymer of any one of claims 1-8 and 18.
20. The brominated block copolymer of claim 19, wherein the bromine content is 60 to 68wt%, preferably 61 to 67wt%, more preferably 62 to 66wt%, based on the total weight of the brominated block copolymer.
21. The brominated block copolymer of claim 19 or 20, wherein the number average molecular weight of the brominated block copolymer is 50000-200000, preferably 80000-150000;
preferably, the brominated block copolymer has a molecular weight distribution of 1 to 1.2, preferably 1.01 to 1.15, more preferably 1.02 to 1.1;
preferably, the brominated block copolymer has a 5wt% thermal weight loss temperature of 260 ℃ or greater, preferably from 260 to 268 ℃, more preferably from 261 to 267 ℃;
preferably, the brominated block copolymer has a glass transition temperature of 120℃or higher, preferably 121 to 133℃and more preferably 123 to 131 ℃.
22. Use of the brominated block copolymer of any of claims 19-21 in an exterior wall insulation flame retardant.
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