TWI491628B - An injectable foamed styrene monomer-diene copolymer and preparation method and use thereof - Google Patents
An injectable foamed styrene monomer-diene copolymer and preparation method and use thereof Download PDFInfo
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- TWI491628B TWI491628B TW098124039A TW98124039A TWI491628B TW I491628 B TWI491628 B TW I491628B TW 098124039 A TW098124039 A TW 098124039A TW 98124039 A TW98124039 A TW 98124039A TW I491628 B TWI491628 B TW I491628B
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 101
- 229920001577 copolymer Polymers 0.000 title claims description 89
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims description 106
- 238000006116 polymerization reaction Methods 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 150000001993 dienes Chemical class 0.000 claims description 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- -1 alkyl lithium Chemical compound 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 52
- 229920000642 polymer Polymers 0.000 description 52
- 239000004793 Polystyrene Substances 0.000 description 48
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 38
- 229920002223 polystyrene Polymers 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000463 material Substances 0.000 description 29
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 description 20
- 238000005187 foaming Methods 0.000 description 19
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 17
- 238000002329 infrared spectrum Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 11
- 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 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005859 coupling reaction Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 238000010382 chemical cross-linking Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OTGGHZUEAWMAAK-UHFFFAOYSA-N (1,1-dimethoxy-1-phenyldecan-2-yl)benzene Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)C1=CC=CC=C1)CCCCCCCC OTGGHZUEAWMAAK-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- KEPBYTKEUAZWQU-UHFFFAOYSA-N ClC(C(C)(C)Cl)CCCCCCCC Chemical compound ClC(C(C)(C)Cl)CCCCCCCC KEPBYTKEUAZWQU-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明涉及一種可注射發泡的苯乙烯屬單體-二烯烴共聚物、其製備方法和用途。更具體而言，本發明涉及一種包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物及其製備方法和用途。The present invention relates to an injectable foamable styrenic monomer-diene copolymer, a process for its preparation and use. More particularly, the present invention relates to a styrenic monomer-diene copolymer comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer, and a process for the preparation and use thereof.
眾所周知，苯乙烯/丁二烯嵌段共聚物(SBS)是最早工業化的苯乙烯屬單體基熱塑性彈性體。SBS可用於例如製備鞋底、黏合劑和日用彈性體，和改性瀝青和塑膠。SBS最大的應用領域是鞋底，鞋底用SBS占了世界SBS消費量的50%以上。It is well known that styrene/butadiene block copolymer (SBS) is the first industrialized styrenic monomer-based thermoplastic elastomer. SBS can be used, for example, to make soles, adhesives, and household elastomers, as well as modified asphalts and plastics. The largest application area of SBS is the sole, and SBS for soles accounts for more than 50% of the world's SBS consumption.
傳統的SBS是呈相分離的嵌段共聚物，其熔體的剪切黏度對溫度和剪切速率十分不敏感。SBS在加工過程中苯乙烯的物理纏結會導致其熔體黏度不均(PB鏈段黏度低，PB與PS相介面黏度高)，使得AC發泡劑分散不均勻，引起泡孔不均。因此SBS發泡後製品的撕裂強度、拉伸強度、耐磨性等不能滿足鞋底的要求。為了提高SBS發泡製品的拉伸強度、撕裂強度、耐化學溶劑、耐磨等性能，一個方法是在發泡過程中加入交聯劑，但是這存在兩個難以克服的困難：一是交聯劑的加入問題，一般交聯劑的分解溫度在140℃以下，而SBS的塑化溫度在170℃以上；二是傳統SBS的聚丁二烯相的雙鍵密度高，在交聯劑作用下會出現“膠燒”(一種極迅速的鏈式放熱反應)現象，生產難於進行或存在安全隱患或產品合格率低。由於不能實現SBS的化學交聯發泡，更不能進行注射發泡，SBS製成的鞋底的密度高、耐磨性差，因此近年來逐步被其他材料如EVA、聚氨酯(PU)等所替代。Conventional SBS is a phase-separated block copolymer whose shear viscosity is very insensitive to temperature and shear rate. The physical entanglement of styrene in SBS during processing will result in uneven melt viscosity (low viscosity of PB segment and high viscosity of PB and PS interface), which makes the AC foaming agent disperse unevenly and cause cell unevenness. Therefore, the tear strength, tensile strength, abrasion resistance, etc. of the SBS foamed product cannot meet the requirements of the sole. In order to improve the tensile strength, tear strength, chemical solvent resistance, wear resistance and the like of the SBS foamed product, one method is to add a crosslinking agent during the foaming process, but there are two difficulties that are difficult to overcome: The problem of the addition of the crosslinking agent, the decomposition temperature of the general crosslinking agent is below 140 ° C, and the plasticizing temperature of SBS is above 170 ° C; the second is that the polybutadiene phase of the conventional SBS has a high double bond density and acts as a crosslinking agent. There will be a phenomenon of "gel burning" (a very rapid chain exothermic reaction), which is difficult to produce or has safety hazards or low product yield. Since the chemical cross-linking foaming of SBS cannot be achieved, and injection foaming is not possible, the sole made of SBS has high density and poor wear resistance, and thus has been gradually replaced by other materials such as EVA, polyurethane (PU) and the like in recent years.
無規苯乙烯屬單體-二烯烴共聚物及其製備也被公開在眾多的科技文獻和專利中。中國專利申請CN 101113188A公開了一種共軛二烯/乙烯基芳烴無規共聚物的連續製備方法。所述乙烯基芳烴可以為苯乙烯，所述共軛二烯可以為1,3-丁二烯，該共聚物的分子量為200,000至800,000,多分散性指數Mw /Mn =1.6-2.5。該共聚物設計用於汽車輪胎胎面。該共聚物的較大分子量使得其熔體黏度過大，從而無法進行發泡，更不能被注塑加工。Random styrenic monomer-diene copolymers and their preparation are also disclosed in numerous scientific literature and patents. Chinese patent application CN 101113188A discloses a continuous preparation process of a conjugated diene/vinyl aromatic random copolymer. The vinyl aromatic hydrocarbon may be styrene, and the conjugated diene may be 1,3-butadiene having a molecular weight of 200,000 to 800,000 and a polydispersity index M w /M n =1.6-2.5. The copolymer is designed for use in automotive tire treads. The larger molecular weight of the copolymer makes the melt viscosity too large to be foamed, and it cannot be injection molded.
美國專利USP 4,367,325公開了一種苯乙烯/丁二烯無規共聚物及其生產方法。該苯乙烯/丁二烯無規共聚物的苯乙烯單體含量為3-30%，丁二烯單體的1,2-聚合結構含量為70-90%。這種共聚物用於生產汽車輪胎，具有低的滾動阻力和高的抗濕滑能力。該共聚物熔體黏度高，不能被注塑加工。A styrene/butadiene random copolymer and a process for its production are disclosed in U.S. Patent No. 4,367,325. The styrene/butadiene random copolymer has a styrene monomer content of 3 to 30%, and the butadiene monomer has a 1,2-polymerization content of 70 to 90%. This copolymer is used in the production of automotive tires with low rolling resistance and high resistance to slip. The copolymer has a high melt viscosity and cannot be injection molded.
另外，常規的苯乙烯/丁二烯無規共聚物在化學交聯後不可再生加工。In addition, conventional styrene/butadiene random copolymers are not regeneratively processed after chemical crosslinking.
目前使用的EVA發泡製品的拉伸強度、撕裂強度、壓縮永久變形、耐磨、止滑性能等更多呈現塑膠特性，不能完全滿足制鞋行業的要求。聚氨酯作為鞋底原料也存在缺點，例如生產成本高、聚氨酯單體的毒害性大、發泡工藝複雜、抗濕滑性能差，易龜裂、斷跟等，也不能進行注射發泡。The tensile strength, tear strength, compression set, wear resistance, and slip resistance of the currently used EVA foamed products are more plastic characteristics and cannot fully meet the requirements of the footwear industry. Polyurethanes also have disadvantages as sole materials, such as high production cost, high toxicity of polyurethane monomers, complicated foaming process, poor wet skid resistance, easy cracking, broken heels, etc., and injection foaming.
因此，希望提供例如可用於鞋底應用的新型可注射發泡的苯乙烯屬單體-二烯烴共聚物。Accordingly, it is desirable to provide novel injectable foamed styrenic monomer-diene copolymers that can be used, for example, in shoe sole applications.
本發明人通過分子結構設計和勤勉的研究發現，具有適宜的分子量和苯乙烯屬單體含量的、包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物具有良好的可注射發泡性能。這是由於該共聚物在熱加工下具有較低的熔體黏度，使得可以方便地進行注塑加工，而且使得化學發泡劑容易產生微小和均勻的氣泡。在化學發泡過程中均勻分佈的聚二烯烴微嵌段提供了數量適當的化學交聯點。在交聯劑作用下通過這些交聯點所形成的共聚物分子網路和聚苯乙烯屬單體微嵌段形成的物理交聯共同作用可以穩定化學發泡劑產生的微小氣泡。本發明人還發現，由於聚二烯烴微嵌段均勻分佈在聚苯乙烯屬單體微嵌段中，本發明的苯乙烯屬單體-二烯烴共聚物從根本土避免了由於聚丁二烯聚集導致的快速鏈式交聯放熱反應，在交聯過程中不會產生SBS所遇到的“膠燒”現象。這種共聚物結構設計不僅保證採用該共聚物生產的發泡材料具有足夠的類似橡膠材料的彈性，而且聚苯乙烯屬單體微嵌段形成的物理交聯使得該材料仍保留常規SBS的可再生加工性能，因此本發明的苯乙烯屬單體-二烯烴共聚物具有環保特性。本發明的苯乙烯屬單體-二烯烴共聚物可用於鞋底生產，並且所述共聚物可以採用現有的注塑發泡生產裝置低成本地進行生產。在此基礎上完成了本發明。The present inventors have found through molecular structure design and diligent research that styrene containing a micro-block of a polystyrene monomer and a micro-block of a polydiene monomer having a suitable molecular weight and a styrene monomer content. The monomer-diene copolymer has good injectable foaming properties. This is because the copolymer has a lower melt viscosity under thermal processing, which makes it easy to carry out injection molding, and makes the chemical foaming agent easy to generate minute and uniform bubbles. The polydiene microblocks uniformly distributed during the chemical foaming process provide an appropriate number of chemical crosslinking points. The physical crosslinks formed by the molecular network of the copolymer formed by these crosslinking points and the polystyrene monomer microblocks under the action of the crosslinking agent can stabilize the microbubbles generated by the chemical blowing agent. The present inventors have also found that since the polydiene microblocks are uniformly distributed in the polystyrene monomer microblock, the styrenic monomer-diene copolymer of the present invention avoids polybutadiene from the fundamental soil. The rapid chain cross-linking exothermic reaction caused by aggregation does not produce the "gel burning" phenomenon encountered by SBS during the crosslinking process. The structure design of the copolymer not only ensures that the foamed material produced by the copolymer has sufficient elasticity similar to that of the rubber material, and the physical cross-linking of the polystyrene monomer microblock makes the material retain the conventional SBS. The regenerative processability, and therefore the styrenic monomer-diene copolymer of the present invention has environmentally friendly properties. The styrenic monomer-diene copolymer of the present invention can be used for sole production, and the copolymer can be produced at low cost using an existing injection molding foam production apparatus. The present invention has been completed on this basis.
本發明的一個目的是提供一種包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物。It is an object of the present invention to provide a styrenic monomer-diene copolymer comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer.
本發明的另一個目的是提供本發明的包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物的製備方法。Another object of the present invention is to provide a process for producing a styrene monomer-diene copolymer comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer of the present invention.
本發明的另一個目的是提供本發明的包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物的用途。Another object of the present invention is to provide the use of the styrenic monomer-diene copolymer of the microblock of the present invention comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer.
本發明的再一個目的是提供使用本發明的苯乙烯屬單體-二烯烴共聚物生產的發泡製品。It is still another object of the present invention to provide a foamed article produced using the styrenic monomer-diene copolymer of the present invention.
在第一方面，本發明提供了一種包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物。In a first aspect, the present invention provides a styrenic monomer-diene copolymer comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer.
本發明中使用的術語“聚苯乙烯屬單體的微嵌段”是指聚合度為2-100，優選3-70的聚苯乙烯屬單體的鏈段。本發明中使用的術語“聚二烯烴單體的微嵌段”是指聚合度為2-400，優選3-330的聚二烯烴的鏈段。The term "microblock of polystyrene monomer" as used in the present invention means a segment of a polystyrene monomer having a degree of polymerization of from 2 to 100, preferably from 3 to 70. The term "microblock of polydiene monomer" as used in the present invention means a segment of a polydiene having a degree of polymerization of from 2 to 400, preferably from 3 to 330.
按照一個實施方案，本發明的所述包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物中，苯乙烯屬單體的含量為10-80重量%，1,2-聚合結構的二烯烴單元占總二烯烴單元的比例小於30%，並且該共聚物的數均分子量(Mn)在25,000-500,000的範圍內。According to one embodiment, the styrene monomer-diene copolymer of the microblock comprising a polystyrene monomer and a microblock of a polydiene monomer, styrenic monomer The content is from 10 to 80% by weight, the ratio of the diene unit of the 1,2-polymer structure to the total diene unit is less than 30%, and the number average molecular weight (Mn) of the copolymer is in the range of from 25,000 to 500,000.
按照一個實施方案，本發明的所述包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物具有線形結構，其可以用下式(I)表示：According to one embodiment, the styrene monomer-diene copolymer of the microblock comprising a polystyrene monomer and a microblock of a polydiene monomer of the present invention has a linear structure, which can be used Formula (I) means:
PSX1 (PSX2 PBY )n PSX3 (I)PS X1 (PS X2 PB Y ) n PS X3 (I)
其中，PS表示苯乙烯屬單體的聚合物鏈段，PB表示二烯烴單體的聚合物鏈段，X1、X2、X3和Y表示各自的聚合物鏈段的聚合度，並且X1為0-150的整數，每次出現的X2獨立地為1-150，優選1-100，更優選1-70的整數，每次出現的Y獨立地為1-500，優選1-400，更優選1-330的整數，X3是0-150的整數，和n是5-3000，優選10-3000的整數，前提是至少30mol%，優選至少50mol%，更優選至少70mol%，還更優選至少90mol%，還更優選至少95mol%，還更優選至少98mol%，還更優選至少99mol%的苯乙烯屬單體單元在聚合度為2至100，優選3-70的聚苯乙烯屬單體鏈段中，和至少30mol%，優選至少50mol%，更優選至少70mol%，還更優選至少90mol%，還更優選至少95mol%，還更優選至少98mol%，還更優選至少99mol%的二烯烴單體單元在聚合度為2-400，優選3-330的聚二烯烴鏈段中。Wherein PS represents a polymer segment of a styrenic monomer, PB represents a polymer segment of a diolefin monomer, and X1, X2, X3 and Y represent the degree of polymerization of the respective polymer segments, and X1 is 0- An integer of 150, each occurrence of X2 is independently from 1 to 150, preferably from 1 to 100, more preferably from 1 to 70, and each occurrence of Y is independently from 1 to 500, preferably from 1 to 400, more preferably from 1 to 1. An integer of 330, X3 is an integer from 0 to 150, and n is an integer from 5 to 3000, preferably from 10 to 3000, provided that at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%, still more preferably at least 90 mol%, Still more preferably at least 95 mol%, still more preferably at least 98 mol%, still more preferably at least 99 mol% of the styrenic monomer units are in the polystyrenic monomeric segment having a degree of polymerization of from 2 to 100, preferably from 3 to 70, And at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%, still more preferably at least 90 mol%, still more preferably at least 95 mol%, still more preferably at least 98 mol%, still more preferably at least 99 mol% of the diene monomer units are The degree of polymerization is in the range of from 2 to 400, preferably from 3 to 330, in the polydiene segment.
按照另一個實施方案，本發明的所述包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物具有多臂星形結構，其可以用下式(II)表示：According to another embodiment, the styrene monomer-diene copolymer of the microblock comprising a polystyrene monomer and a microblock of a polydiene monomer of the present invention has a multi-arm star structure, It can be expressed by the following formula (II):
[PSX1 (PSX2 PBY )n ]m R (II)[PS X1 (PS X2 PB Y ) n ] m R (II)
其中，PS、PB、X1、X2、Y和n如上面式(I)中所給出的含義，R為星型結構的偶合劑“核”，m為3-10的整數，前提是至少30mol%，優選至少50mol%，更優選至少70mol%，還更優選至少90mol%，還更優選至少95mol%，還更優選至少98mol%，還更優選至少99mol%的苯乙烯屬單體單元在聚合度為2至100，優選3-70的聚苯乙烯屬單體鏈段中，和至少30mol%，優選至少50mol%，更優選至少70mol%，還更優選至少90mol%，還更優選至少95mol%，還更優選至少98mol%，還更優選至少99mol%的二烯烴單體單元在聚合度為2-400，優選3-330的聚二烯烴鏈段中。Wherein, PS, PB, X1, X2, Y and n have the meanings given in the above formula (I), R is a coupling agent "nucleus" of a star structure, m is an integer of 3-10, provided that at least 30 mol %, preferably at least 50 mol%, more preferably at least 70 mol%, still more preferably at least 90 mol%, still more preferably at least 95 mol%, still more preferably at least 98 mol%, still more preferably at least 99 mol% of the degree of polymerization of the styrenic monomer units It is from 2 to 100, preferably from 3 to 70, of the polystyrene monomer segment, and at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%, still more preferably at least 90 mol%, still more preferably at least 95 mol%, Still more preferably, at least 98 mol%, still more preferably at least 99 mol% of the diene monomer units are in the polydiene segment having a degree of polymerization of from 2 to 400, preferably from 3 to 330.
按照另一個實施方案，本發明的所述包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物是線形結構的分子和具有3-10臂的星形結構的分子的組合。According to another embodiment, the styrene monomer-diene copolymer of the microblock comprising a polystyrene monomer and a microblock of a polydiene monomer of the present invention is a linear structure of molecules and has A combination of molecules of a star structure of 3-10 arms.
按照一個優選的實施方案，多個PSX2 PBY 鏈段構成組成逐漸變化的苯乙烯屬單體-二烯烴遞變嵌段，並且(PSX2 PBY )n 鏈段由多個這樣的遞變嵌段構成。According to a preferred embodiment, the plurality of PS X2 PB Y segments constitute a gradual change in the composition of the styrenic monomer-diene tapered block, and the (PS X2 PB Y ) n segment is subjected to a plurality of such changes. Block composition.
在本發明的苯乙烯屬單體-二烯烴共聚物中，苯乙烯屬單體單元的含量在10-80重量%的範圍內，或者在20-80重量%的範圍內，或者在30-75重量%的範圍內，或者在30-60重量%的範圍內，或者在35-60重量%的範圍內，或者在35-50重量%的範圍內，或者在40-48重量%的範圍內，或者在50-70重量%的範圍內。所述苯乙烯屬單體的實例包括但不限於苯乙烯、甲基苯乙烯、乙基苯乙烯、丁基苯乙烯、叔丁基苯乙烯、二甲基苯乙烯、氯代苯乙烯、溴代苯乙烯、甲氧基苯乙烯、乙醯氧基苯乙烯、α-甲基苯乙烯和它們的組合，優選苯乙烯、對甲基苯乙烯和對叔丁基苯乙烯。In the styrenic monomer-diene copolymer of the present invention, the content of the styrene monomer unit is in the range of 10 to 80% by weight, or in the range of 20 to 80% by weight, or 30 to 75. In the range of % by weight, or in the range of 30-60% by weight, or in the range of 35-60% by weight, or in the range of 35-50% by weight, or in the range of 40-48% by weight, Or in the range of 50-70% by weight. Examples of the styrenic monomer include, but are not limited to, styrene, methyl styrene, ethyl styrene, butyl styrene, t-butyl styrene, dimethyl styrene, chlorostyrene, brominated Styrene, methoxystyrene, ethoxylated styrene, alpha-methylstyrene, and combinations thereof are preferably styrene, p-methylstyrene and p-tert-butylstyrene.
本發明的共聚物還包含二烯烴單體單元。所述二烯烴單體的實例包括但不限於1,3-丁二烯、2-甲基-1,3-丁二烯、1,3-己二烯、2,3-二甲基-1,3-丁二烯和它們的組合，優選1,3-丁二烯和2-甲基-1,3-丁二烯。在本發明的共聚物中，1,2-聚合結構的二烯烴單元占總二烯烴單元的比例可以為<30mol%，優選<25mol%，更優選<20mol%，還優選在5-20mol%的範圍內，更優選在10-20mol%的範圍內。The copolymer of the present invention further comprises a diene monomer unit. Examples of the diene monomer include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-hexadiene, 2,3-dimethyl-1 3-butadiene and combinations thereof, preferably 1,3-butadiene and 2-methyl-1,3-butadiene. In the copolymer of the present invention, the ratio of the diene unit of the 1,2-polymerization structure to the total diene unit may be <30 mol%, preferably <25 mol%, more preferably <20 mol%, still more preferably 5-20 mol%. Within the range, it is more preferably in the range of 10 to 20 mol%.
本發明的苯乙烯屬單體-二烯烴共聚物的數均分子量(Mn )在25,000-500,000的範圍內，優選在25,000-300,000的範圍內，更優選在25,000-250,000的範圍內，更優選在30,000-180,000的範圍內。本發明的苯乙烯屬單體-二烯烴共聚物的分子量分佈Mw /Mn 可以為1.01至1.40，優選1.01至1.30，優選1.01至1.20，更優選1.01至1.15，還更優選1.01-1.10。Styrene-based monomer of the present invention - the number-average molecular weight diene copolymer (M n) in the range of 25,000-500,000, preferably in the range of 25,000-300,000, more preferably in the range of 25,000-250,000, more preferably In the range of 30,000-180,000. The molecular weight distribution M w /M n of the styrenic monomer-diene copolymer of the present invention may be from 1.01 to 1.40, preferably from 1.01 to 1.30, preferably from 1.01 to 1.20, more preferably from 1.01 to 1.15, still more preferably from 1.01 to 1.10.
在本發明的共聚物中，聚苯乙烯屬單體和聚二烯烴主要以微嵌段的形式存在於聚合物分子鏈中，這樣聚苯乙烯屬單體相與聚二烯烴相的相分離程度非常低，同時單一聚苯乙烯屬單體相的分子量低，因此聚合物的剪切黏度低、塑化溫度低，可以在交聯劑如DCP的分解溫度(140℃)以下與加工助劑混合和注塑。而且，由於聚二烯烴相被高度分散，在交聯過程中不易發生“膠燒”的現象。In the copolymer of the present invention, the polystyrene monomer and the polydiene are mainly present in the molecular chain of the polymer in the form of microblocks, such that the degree of phase separation of the polystyrene monomer phase from the polydiene phase Very low, while the single polystyrene monomer phase has a low molecular weight, so the polymer has low shear viscosity and low plasticizing temperature, and can be mixed with processing aids at a decomposition temperature (140 ° C) below the crosslinking agent such as DCP. And injection molding. Moreover, since the polydiene phase is highly dispersed, the phenomenon of "gel burning" is less likely to occur during the crosslinking process.
在本發明的聚合物中，優選不發生聚苯乙烯屬單體相與聚二烯烴相的完全相分離。In the polymer of the present invention, it is preferred that complete phase separation of the polystyrene monomer phase from the polydiene phase does not occur.
按照一個優選的實施方案，本發明的共聚物基本上由聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段組成。“基本上由聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段組成”是指聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段一起占總共聚物的至少90wt%，優選至少95wt%，更優選至少98wt%，更優選至少99wt%。According to a preferred embodiment, the copolymer of the invention consists essentially of microblocks of polystyrene monomers and microblocks of polydiene monomers. "Substantially composed of a microblock of a polystyrene monomer and a microblock of a polydiene monomer" means that the microblock of the polystyrene monomer and the microblock of the polydiene monomer together At least 90% by weight of the total copolymer, preferably at least 95% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight.
本發明的所述包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物顯示了不同於已知的苯乙烯屬單體-二烯烴嵌段共聚物和苯乙烯屬單體-二烯烴無規共聚物的移動視窗二維相關紅外譜圖。如從附圖中可以看到的，本發明共聚物的移動視窗二維相關紅外譜圖中，在約2842~2848cm-1 的波數範圍內、在約70~150℃的溫度範圍內具有兩個或三個連續的熱致轉變峰，而苯乙烯屬單體-二烯烴嵌段共聚物和苯乙烯屬單體-二烯烴共聚物在以上範圍內都只具有一個或多個離散的熱致轉變峰。The styrenic monomer-diene copolymer of the microblock comprising a polystyrene monomer and a microblock of a polydiene monomer of the present invention exhibits a difference from a known styrenic monomer - A two-dimensional correlation infrared spectrum of a moving window of a diene block copolymer and a styrene monomer-diene random copolymer. As can be seen from the drawing, the two-dimensional correlation infrared spectrum of the moving window of the copolymer of the present invention has two in the range of wave numbers of about 2842 to 2848 cm -1 and in the temperature range of about 70 to 150 ° C. One or three consecutive thermally induced transition peaks, while the styrenic monomer-diene block copolymer and the styrenic monomer-diene copolymer have only one or more discrete thermal reactions in the above range Change the peak.
在第二方面，本發明提供了製備線形結構的包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物的方法，該方法包括：In a second aspect, the present invention provides a method of preparing a linear structure of a microblock comprising a polystyrene monomer and a microblock of a polystyrene monomer, a styrene monomer-diene copolymer, the method include:
1)在聚合釜內加入一定量的溶劑以及活化劑，升溫到50-110℃；1) adding a certain amount of solvent and activator in the polymerization vessel, and heating to 50-110 ° C;
2)將0-45重量%的苯乙烯屬單體加入聚合釜；2) adding 0-45% by weight of styrene monomer to the polymerization vessel;
3)向聚合釜中加入需要量的引發劑，允許反應進行0-30分鐘；3) adding the required amount of initiator to the polymerization vessel, allowing the reaction to proceed for 0-30 minutes;
4)將10-100重量%的苯乙烯屬單體和所有二烯烴單體充分混合後，在5-180分鐘的時間內連續、脈衝式或分批加入聚合釜中，加料過程中控制聚合釜的反應溫度，使得最高反應溫度與引發溫度相差不超過50℃，優選不超過30℃，更優選不超過20℃；4) After thoroughly mixing 10-100% by weight of the styrene monomer and all the diene monomers, the catalyst is continuously, pulsed or batchwise added to the polymerization vessel over a period of 5-180 minutes, and the polymerization kettle is controlled during the feeding process. The reaction temperature such that the maximum reaction temperature differs from the initiation temperature by no more than 50 ° C, preferably not more than 30 ° C, more preferably not more than 20 ° C;
5)將剩餘的0-45重量%的苯乙烯屬單體加入聚合釜，反應2-30分鐘；5) adding the remaining 0-45% by weight of the styrene monomer to the polymerization vessel, and reacting for 2-30 minutes;
6)反應完成後終止反應，並回收產生的共聚物。6) The reaction was terminated after completion of the reaction, and the resulting copolymer was recovered.
可用於本發明方法的溶劑可以是通常用於溶聚丁苯橡膠生產中的任何溶劑。其實例包括但不限於環己烷、正己烷、苯、甲苯、二甲苯和己烷，以及它們的組合。在本發明方法中，溶劑的用量可以使得單體的濃度為5-30%(重量)，基於反應混合物的總重量計。The solvent which can be used in the process of the invention can be any solvent commonly used in the production of solution styrene butadiene rubber. Examples thereof include, but are not limited to, cyclohexane, n-hexane, benzene, toluene, xylene, and hexane, and combinations thereof. In the process of the present invention, the solvent may be used in an amount such that the concentration of the monomer is from 5 to 30% by weight based on the total weight of the reaction mixture.
可用於本發明方法中的引發劑包括通常用於陰離子聚合的各種烷基鋰，例如正丁基鋰和仲丁基鋰。所述引發劑的用量可以根據需要的產物分子量進行選擇，這在本領域技術人員的知識範圍內。Initiators useful in the process of the invention include various alkyl lithiums commonly used in anionic polymerization, such as n-butyllithium and sec-butyllithium. The amount of the initiator to be used may be selected depending on the desired molecular weight of the product, which is within the knowledge of those skilled in the art.
可用於本發明方法中的活化劑的實例是四氫呋喃，其可以以在聚合溶劑中的含量為50-1200mg/kg，優選80-500mg/kg，更優選100-300mg/kg，還更優選120-220mg/kg，最優選約150-200mg/kg的量使用。An example of an activator which can be used in the process of the present invention is tetrahydrofuran, which may be contained in the polymerization solvent in an amount of 50 to 1200 mg/kg, preferably 80 to 500 mg/kg, more preferably 100 to 300 mg/kg, still more preferably 120- It is used in an amount of 220 mg/kg, most preferably about 150-200 mg/kg.
本發明的方法中還任選使用微觀結構調節劑。其實例包括路易士鹼類化合物，例如四甲基乙二胺、乙二醇二乙醚等，其可以以在聚合溶劑中的含量為1-50mg/kg的量使用。Microstructural modifiers are also optionally employed in the process of the invention. Examples thereof include a Lewis base compound such as tetramethylethylenediamine, ethylene glycol diethyl ether or the like, which can be used in an amount of from 1 to 50 mg/kg in a polymerization solvent.
在本發明的方法中，苯乙烯屬單體佔總單體量的10-80重量%，或者20-80重量%，或者30-75重量%，或者30-60重量%，或者35-60重量%，或者35-50重量%，或者40-48重量%，或者50-70重量%，餘量為二烯烴單體。In the process of the invention, the styrenic monomer comprises from 10 to 80% by weight of the total monomer, or from 20 to 80% by weight, or from 30 to 75% by weight, or from 30 to 60% by weight, or from 35 to 60% by weight. %, or 35-50% by weight, or 40-48% by weight, or 50-70% by weight, the balance being a diene monomer.
在本發明方法的步驟3)中，所述單體混合物可以在5-180分鐘，優選10-120分鐘，更優選15-90分鐘，最優選20-60分鐘的時間內添加到聚合釜中。在步驟3)和任選的步驟4)的單體添加結束後，任選允許反應進一步進行5-120分鐘，優選10-60分鐘。In step 3) of the process of the invention, the monomer mixture can be added to the polymerization vessel over a period of from 5 to 180 minutes, preferably from 10 to 120 minutes, more preferably from 15 to 90 minutes, and most preferably from 20 to 60 minutes. After the end of the monomer addition of step 3) and optional step 4), the reaction is optionally allowed to proceed for a further 5 to 120 minutes, preferably 10 to 60 minutes.
在聚合過程中，反應溫度控制在50-110℃的範圍內，優選在60-100℃的範圍內，更優選在70-90℃的範圍內。In the polymerization, the reaction temperature is controlled in the range of 50 to 110 ° C, preferably in the range of 60 to 100 ° C, more preferably in the range of 70 to 90 ° C.
在聚合結束後，添加終止劑來終止反應。可用於本發明的終止劑可以是本領域通常採用的任何終止劑，例如水、醇和其他含質子氫的化合物。After the end of the polymerization, a terminator was added to terminate the reaction. The terminator useful in the present invention can be any terminator commonly employed in the art, such as water, alcohols, and other proton-containing hydrogen-containing compounds.
最後，可以通過本領域技術人員熟知的技術回收所生產的共聚物。例如，可以向反應混合物中加入一定量的常規的抗氧劑，然後對產物進行凝聚和乾燥，以得到成品共聚物。Finally, the copolymer produced can be recovered by techniques well known to those skilled in the art. For example, an amount of a conventional antioxidant can be added to the reaction mixture, and then the product is coagulated and dried to obtain a finished copolymer.
本發明的星型結構的共聚物可以通過包括如下步驟的方法製備：The star-structured copolymer of the present invention can be prepared by a process comprising the following steps:
1)在聚合釜內加入一定量的溶劑以及活化劑，升溫到50-110℃；1) adding a certain amount of solvent and activator in the polymerization vessel, and heating to 50-110 ° C;
2)將0-45重量%的苯乙烯屬單體加入聚合釜；2) adding 0-45% by weight of styrene monomer to the polymerization vessel;
3)向聚合釜中加入需要量的引發劑，允許反應進行0-30分鐘；3) adding the required amount of initiator to the polymerization vessel, allowing the reaction to proceed for 0-30 minutes;
4)將55-100重量%的苯乙烯屬單體和90-100重量%的二烯烴單體充分混合後，在5-180分鐘的時間內連續、脈衝式或分批加入聚合釜中，加料過程中控制聚合釜的反應溫度，使得最高反應溫度與引發溫度相差不超過50℃，優選不超過30℃，更優選不超過20℃；4) After thoroughly mixing 55-100% by weight of the styrene monomer and 90-100% by weight of the diene monomer, continuously, pulsed or batchwise added to the polymerization vessel in a period of 5-180 minutes, feeding Controlling the reaction temperature of the polymerization vessel such that the maximum reaction temperature differs from the initiation temperature by no more than 50 ° C, preferably no more than 30 ° C, more preferably no more than 20 ° C;
5)任選地，將剩餘的0-10重量%的二烯烴單體加入聚合釜，允許反應進行5-30分鐘；5) Optionally, the remaining 0-10% by weight of the diene monomer is added to the polymerization vessel, allowing the reaction to proceed for 5-30 minutes;
6)向反應混合物中添加需要量的偶聯劑，並允許反應進行5-60分鐘；6) adding the required amount of coupling agent to the reaction mixture, and allowing the reaction to proceed for 5 to 60 minutes;
7)反應完成後終止反應，並回收產生的共聚物。7) The reaction was terminated after completion of the reaction, and the resulting copolymer was recovered.
除偶聯反應步驟6)以外，上述方法使用的原料和工藝條件如上面對製備線形結構的本發明共聚物的方法所述。In addition to the coupling reaction step 6), the materials and process conditions used in the above method are as described above for the method of preparing the linear copolymer of the present invention.
為了製備本發明的星型結構的共聚物，應控制合成工藝條件，使得用於偶聯反應的活性鏈端為聚二烯烴鏈段或含有較高二烯烴單元含量的聚苯乙烯屬單體-二烯烴共聚物鏈段，以提高偶合度和偶合效率。In order to prepare the copolymer of the star structure of the present invention, the synthesis process conditions should be controlled such that the active chain end for the coupling reaction is a polydiene segment or a polystyrene monomer containing a higher diene unit content - two Olefin copolymer segments to increase coupling and coupling efficiency.
所述偶聯步驟6)中，可以使用本領域技術人員熟知的各種偶聯劑和工藝條件。例如，偶聯劑可以為四氯化矽、二乙烯苯、二氯二甲基矽烷、四乙氧基矽烷、二苯基二甲氧基矽烷，偶聯劑與活性鏈端的當量比可以在寬範圍內變化，並且偶聯反應可以在50-110的溫度下進行例如5-60分鐘。In the coupling step 6), various coupling agents and process conditions well known to those skilled in the art can be used. For example, the coupling agent may be ruthenium tetrachloride, divinyl benzene, dichloro dimethyl decane, tetraethoxy decane, diphenyl dimethoxy decane, and the equivalent ratio of the coupling agent to the active chain end may be wide. The range is varied, and the coupling reaction can be carried out at a temperature of 50 to 110, for example, for 5 to 60 minutes.
採用上述方法，可以通過選擇偶聯劑的量來獲得基本上由星型結構的共聚物組成的產物(偶聯劑與活性鏈端的當量比為約1：1或更大)和由星型結構的共聚物以及線形結構的共聚物組成的產物(偶聯劑與活性鏈端的當量比小於1：1，例如小於0.95：1)。By using the above method, a product consisting essentially of a star-structured copolymer (equivalent ratio of coupling agent to active chain end of about 1:1 or greater) and a star structure can be obtained by selecting the amount of coupling agent. The product of the copolymer and the copolymer of the linear structure (the equivalent ratio of the coupling agent to the active chain end is less than 1:1, such as less than 0.95:1).
在一個實施方案中，可以首先分別製備得到線形結構的共聚物和基本上星型結構的共聚物，然後根據需要按比例混合二者，來獲得線形結構的共聚物和基本上星型結構的共聚物的組合物。In one embodiment, a copolymer of a linear structure and a copolymer of a substantially star structure may be separately prepared first, and then both may be mixed in proportion as needed to obtain a copolymer of a linear structure and a copolymer of a substantially star structure. Composition of matter.
儘管不希望局限於特定的理論，但下面描述的機理可能有助於理解本發明的包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物如何形成。While not wishing to be bound by a particular theory, the mechanism described below may be helpful in understanding the styrenic monomers of the microblocks of the present invention comprising microblocks of polystyrene monomers and microblocks of polydiene monomers - How is the diene copolymer formed.
例如在苯乙烯-丁二烯共聚物的製備中，據信在聚合過程中存在以下6種不同的反應：For example, in the preparation of styrene-butadiene copolymers, it is believed that there are six different reactions during the polymerization:
其中Bu表示丁二烯單體或其聚合形式，St表示苯乙烯單體或其聚合形式，LiR表示烷基鋰引發劑。Wherein Bu represents a butadiene monomer or a polymerization form thereof, St represents a styrene monomer or a polymerization form thereof, and LiR represents an alkyl lithium initiator.
所述6種反應的反應速率常數存在如下關係：The reaction rate constants of the six reactions have the following relationships:
K1＞K2＞K5＞K3＞K6＞K4K1>K2>K5>K3>K6>K4
當單體以脈衝方式加料時，在聚合反應開始階段，單體混合物中的苯乙烯和丁二烯單體與烷基鋰引發劑如丁基鋰反應，形成活性引發劑BuLi和StLi。因為丁二烯的沸點低，因此在加料的瞬間丁二烯大部分被氣化，參與引發反應的絕大部分是苯乙烯，因此在起始反應中形成的StLi是主要的。StLi優先與混合單體中的苯乙烯反應，從而主要形成聚苯乙烯嵌段。當苯乙烯單體在聚合體系中的濃度降低到足夠低時，丁二烯單體將參與反應，形成苯乙烯-丁二烯的交替共聚物嵌段，並且隨著苯乙烯單體濃度的進一步降低，將主要形成聚丁二烯嵌段。在下一次的脈衝加料後，上述過程重複進行。由此形成包含聚苯乙烯屬單體的微嵌段和聚二烯烴單體的微嵌段的苯乙烯屬單體-二烯烴共聚物。When the monomer is fed in a pulsed manner, the styrene and butadiene monomers in the monomer mixture are reacted with an alkyllithium initiator such as butyllithium at the beginning of the polymerization to form the active initiators BuLi and StLi. Since butadiene has a low boiling point, most of the butadiene is vaporized at the moment of feeding, and most of the reactions involved in the initiation of the reaction are styrene, so the StLi formed in the initial reaction is dominant. StLi preferentially reacts with the styrene in the mixed monomer to thereby form a polystyrene block. When the concentration of the styrene monomer in the polymerization system is reduced sufficiently low, the butadiene monomer will participate in the reaction to form an alternating copolymer block of styrene-butadiene, and with the further concentration of styrene monomer Lower, will mainly form a polybutadiene block. The above process is repeated after the next pulse feed. Thus, a styrene monomer-diene copolymer comprising a microblock of a polystyrene monomer and a microblock of a polydiene monomer is formed.
在本發明方法中，如果採用脈衝加料或分批加料方式，則控制單體混合物的加料時間，使得單體在聚合中消耗的速度與單體添加的速度相當或更大；如果採用連續加料方式，則控制單體混合物的加料時間，使得單體在聚合中消耗的速度與單體添加的速度相當或略大。這樣會形成包含很多聚苯乙烯微嵌段和聚丁二烯微嵌段的聚合物，(PSX2 PBY )n 。多個PSX2 PBY 鏈段將構成組成逐漸變化的遞變嵌段，並且所述(PSX2 PBY )n 鏈段將由多個這樣的遞變嵌段構成。In the process of the present invention, if a pulsed feed or batch feed mode is employed, the feed time of the monomer mixture is controlled such that the rate of monomer consumption in the polymerization is comparable to or greater than the rate of monomer addition; if continuous feed is employed The feed time of the monomer mixture is then controlled such that the rate of monomer consumption in the polymerization is comparable to or slightly greater than the rate of monomer addition. This will result in a polymer (PS X2 PB Y ) n comprising a plurality of polystyrene microblocks and polybutadiene microblocks. A plurality of PS X2 PB Y segments will constitute a tapered block of progressive composition, and the (PS X2 PB Y ) n segments will be composed of a plurality of such tapered blocks.
在第三方面，本發明提供了本發明的苯乙烯屬單體-二烯烴共聚物的應用。In a third aspect, the invention provides the use of a styrenic monomer-diene copolymer of the invention.
本發明的苯乙烯屬單體-二烯烴共聚物可以在低於110℃的溫度下與各種添加劑混合後，在170～195℃的模具內進行注射發泡，其發泡工藝與EVA相似，發泡設備可以與EVA完全相同。按照一個實施方案，可以通過如下方法由本發明的共聚物製備發泡製品：將本發明的共聚物與添加劑如硬脂酸、硬脂酸鋅、滑石粉，交聯劑如過氧化二枯基(DCP)，發泡劑如偶氮二甲醯胺(發泡劑AC或AC)在80℃的溫度下於密煉機中捏合5～10分鐘，之後將物料用開放式煉膠機壓成薄片，送入單螺桿擠出機於90℃造粒。將粒料送入單螺桿注塑機中，於90℃注入溫度為170～195℃的模具中，並保溫200～500秒，然後泄壓並打開模具，得到發泡製品。The styrenic monomer-diene copolymer of the present invention can be injected and foamed in a mold at 170 to 195 ° C after being mixed with various additives at a temperature lower than 110 ° C, and the foaming process is similar to that of EVA. The bubble device can be identical to the EVA. According to one embodiment, a foamed article can be prepared from the copolymer of the present invention by copolymerizing the copolymer of the present invention with an additive such as stearic acid, zinc stearate, talc, a crosslinking agent such as dicumyl peroxide ( DCP), a foaming agent such as azomethicin (foaming agent AC or AC) is kneaded in an internal mixer at a temperature of 80 ° C for 5 to 10 minutes, and then the material is pressed into a sheet by an open rubber mixer. It was fed into a single screw extruder and pelletized at 90 °C. The pellets are fed into a single-screw injection molding machine, and are injected into a mold having a temperature of 170 to 195 ° C at 90 ° C for 200 to 500 seconds, and then the pressure is released and the mold is opened to obtain a foamed product.
在第四方面，本發明提供了由本發明的共聚物發泡製備的發泡製品。In a fourth aspect, the invention provides a foamed article prepared by foaming a copolymer of the invention.
本發明的發泡製品中既存在苯乙烯纏結的物理交聯點，又具有化學交聯點，因此發泡製品具有好的拉伸強度、撕裂強度和耐磨性，而且可以被再生加工。同時，本發明的發泡製品具有優異的止滑性能。本發明的發泡製品可以用於製造沙灘鞋和拖鞋，還可以用於製造旅遊鞋、運動鞋中底和皮鞋大底，也可以用於汽車內裝飾材料和各種場合的保溫材料。The foamed article of the invention has both physical cross-linking points of styrene entanglement and chemical cross-linking points, so the foamed article has good tensile strength, tear strength and wear resistance, and can be reprocessed . At the same time, the foamed article of the present invention has excellent slip resistance. The foamed article of the present invention can be used for the manufacture of beach shoes and slippers, and can also be used for the manufacture of sneakers, sports shoe midsole and leather outsole, as well as automotive interior materials and insulation materials for various occasions.
1)該苯乙烯屬單體-二烯烴共聚物可以採用現有的苯乙烯屬單體基熱塑性彈性體生產裝置進行生產，生產設備無需改造。1) The styrenic monomer-diene copolymer can be produced by using an existing styrene monomer-based thermoplastic elastomer production apparatus, and the production equipment does not need to be modified.
2)該苯乙烯屬單體-二烯烴共聚物的發泡材料中，苯乙烯類聚合物的物理纏結可代替化學交聯點，從而顯著地減少化學交聯劑的用量。在對磨耗和耐溫性能要求不高的應用領域，甚至可以在不加化學交聯劑的情況下高發泡，從而為發泡材料的完全再生利用和生產低味或無味的環保發泡材料提供了可能性。2) In the foamed material of the styrene monomer-diene copolymer, physical entanglement of the styrene polymer can replace the chemical crosslinking point, thereby significantly reducing the amount of the chemical crosslinking agent. In applications where wear and temperature resistance are not critical, high foaming can be achieved without chemical cross-linking, providing complete recycling of foamed materials and production of low-odor or odorless environmentally friendly foam materials. The possibility.
3)該苯乙烯屬單體-二烯烴共聚物的發泡材料仍保持橡膠特性，其低溫性能優於EVA發泡材料，人體舒適性更佳。3) The foamed material of the styrene monomer-diene copolymer still retains the rubber property, and its low temperature performance is superior to that of the EVA foaming material, and the human body comfort is better.
4)該苯乙烯屬單體-二烯烴共聚物的發泡材料具有優異的抗濕滑性能。4) The foamed material of the styrene monomer-diene copolymer has excellent wet skid resistance.
5)該苯乙烯屬單體-二烯烴共聚物的發泡材料壓縮永久變形低，彈性回復好，耐磨性、扯斷強度和撕裂強度均強於EVA發泡材料。根據聚合單體含量的不同，該聚合物的發泡材料硬度在很大範圍內可調。5) The foamed material of the styrene monomer-diene copolymer has low compression set and good elastic recovery, and the abrasion resistance, the tear strength and the tear strength are stronger than the EVA foaming material. The foaming material hardness of the polymer is adjustable over a wide range depending on the content of the polymerized monomer.
6)該苯乙烯屬單體-二烯烴共聚物可以採用注射方式在模具內進行發泡，泡孔均勻。6) The styrene monomer-diene copolymer can be foamed in a mold by injection, and the cells are uniform.
7)該苯乙烯屬單體-二烯烴共聚物的發泡產品可以用於製造沙灘鞋和拖鞋，還可以用於製造旅遊鞋、運動鞋中底和皮鞋大底，也可以用於汽車內裝飾材料和各種場合的保溫材料。7) The foamed product of the styrenic monomer-diene copolymer can be used in the manufacture of beach shoes and slippers, and can also be used in the manufacture of sneakers, sports midsole and outsole, as well as in car interiors. Materials and insulation materials for various occasions.
8)該苯乙烯屬單體-二烯類共聚物的發泡產品生產成本與EVA相當，但各方面性能更優，有重大的市場價值。8) The production cost of the foamed product of the styrene monomer-diene copolymer is equivalent to that of EVA, but the performance is superior in all aspects and has great market value.
給出以下實施例來舉例說明本發明，而不是限制發明的範圍。The following examples are given to illustrate the invention and not to limit the scope of the invention.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加8.9mmol正丁基鋰。在攪拌5分鐘後，將由105g苯乙烯和245g丁二烯組成的混合單體在60分鐘時間內連續加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)的抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到苯乙烯/丁二烯共聚物1。該共聚物的分子量為31,000(Mn )，分子量分佈為1.02，二烯烴中1,2-結構含量為17.5%，邵氏C硬度為65。該聚合物中苯乙烯與丁二烯以無規的方式聚合，核磁譜圖見圖1。該產品可用於高阻尼材料。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 8.9 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 105 g of styrene and 245 g of butadiene was continuously added to the polymerization vessel over a period of 60 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for an additional 20 minutes, and then 5 ml of water was added to terminate the reaction. To the reaction mixture, 0.2% by weight of an antioxidant 1076 and 0.4% by weight of an antioxidant 168 based on the weight of the polymer were added and stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a dry box to obtain a styrene/butadiene copolymer 1. The molecular weight of the copolymer was 31,000 (M n), the molecular weight distribution of 1.02, a diene content of 1,2-structure was 17.5%, a Shore C hardness of 65. In the polymer, styrene and butadiene are polymerized in a random manner, and the nuclear magnetic spectrum is shown in Fig. 1. This product can be used for highly damped materials.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加2.71mmol正丁基鋰。在攪拌5分鐘後，將由175g苯乙烯和175g丁二烯組成的混合單體在20分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行25分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)的抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到苯乙烯/丁二烯共聚物2。該共聚物的分子量為140,000(Mn )，分子量分佈為1.01，二烯烴中1,2-結構含量為15.6%，邵氏C硬度為80。該共聚物的移動視窗二維相關紅外譜圖見附圖2。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 2.71 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 175 g of styrene and 175 g of butadiene was continuously pulsed into the polymerization vessel over 20 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer addition, the reaction was allowed to proceed for an additional 25 minutes, and then 5 ml of water was added to terminate the reaction. To the reaction mixture, 0.2% by weight of an antioxidant 1076 and 0.4% by weight of an antioxidant 168 based on the weight of the polymer were added and stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a drying oven to obtain a styrene/butadiene copolymer 2. The molecular weight of the copolymer is 140,000 (M n), the molecular weight distribution of 1.01, a 1,2-structure content of 15.6% diene, Shore C hardness of 80. The two-dimensional correlation infrared spectrum of the moving window of the copolymer is shown in Fig. 2.
移動視窗二維相關紅外譜的測定方法可以參見“Molecular Chain Movements and Transitions of SEBS above Room Temperature Studied by Moving-Window Two-Dimensional Correlation Infrared Spectroscopy”，Tao Zhou,et al.,Macromolecules，2007，40，9009-9017。For the determination of the two-dimensional infrared spectrum of the moving window, see "Molecular Chain Movements and Transitions of SEBS above Room Temperature Studied by Moving-Window Two-Dimensional Correlation Infrared Spectroscopy", Tao Zhou, et al., Macromolecules, 2007, 40, 9009 -9017.
作為比較，在附圖3，4，5，6，7，8中給出了三嵌段苯乙烯-丁二烯共聚物SBS(S:B=30:70)，全無規苯乙烯-丁二烯共聚物(S:B=30:70)，三嵌段苯乙烯-2-甲基-1,3-丁二烯共聚物SIS(S:I=50:50)，微嵌段苯乙烯-2-甲基-1,3-丁二烯共聚物(SI)n (S:I=50:50)，三嵌段SIBS(S:I:B=50:25:25)和微嵌段(SIB)n (S:I:B=50:25:25)的移動視窗二維相關紅外譜圖。For comparison, the triblock styrene-butadiene copolymer SBS (S: B = 30: 70), fully random styrene-butyl is shown in Figures 3, 4, 5, 6, 7, 8. Diene copolymer (S: B = 30: 70), triblock styrene-2-methyl-1,3-butadiene copolymer SIS (S: I = 50: 50), microblock styrene -2-methyl-1,3-butadiene copolymer (SI) n (S: I = 50: 50), triblock SIBS (S: I: B = 50: 25: 25) and microblocks (SIB) n (S:I:B=50:25:25) Two-dimensional correlation infrared spectrum of the moving window.
從圖3中可以看到，三嵌段SBS的二維相關紅外譜圖較簡單。70℃代表了聚丁二烯嵌段的微結晶的熔融；126℃是聚苯乙烯嵌段的玻璃化轉變；144℃是聚苯乙烯嵌段的黏流溫度。圖4-8由於共聚物分子結構的不同而表現出各自不同的熱致轉變。As can be seen from Figure 3, the two-dimensional correlation infrared spectrum of the triblock SBS is relatively simple. 70 ° C represents the melting of the microcrystals of the polybutadiene block; 126 ° C is the glass transition of the polystyrene block; 144 ° C is the viscous temperature of the polystyrene block. Figures 4-8 show different thermotropic transitions due to differences in the molecular structure of the copolymer.
從圖2中可以看到，本發明聚合物的二維相關紅外譜圖在80℃、101℃和126℃均出現了明顯的熱致轉變。80℃是苯乙烯-丁二烯無規共聚鏈段的玻璃化轉變溫度。101℃是聚苯乙烯短嵌段的玻璃化轉變溫度；126℃是短的聚苯乙烯嵌段的黏流溫度。As can be seen from Figure 2, the two-dimensional correlation infrared spectra of the polymers of the present invention exhibited significant thermotropic transitions at 80 ° C, 101 ° C and 126 ° C. 80 ° C is the glass transition temperature of the styrene-butadiene random copolymerized segment. 101 ° C is the glass transition temperature of the polystyrene short block; 126 ° C is the viscous temperature of the short polystyrene block.
由所述移動視窗二維相關紅外譜圖的結果可知，本實施例得到的聚合物是一種典型的微嵌段結構，微嵌段中還夾雜著苯乙烯-二烯烴無規共聚鏈段。It can be seen from the results of the two-dimensional correlation infrared spectrum of the moving window that the polymer obtained in the present embodiment is a typical micro-block structure, and the micro-block is also interspersed with a random copolymerization segment of styrene-diene.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加2.65mmol正丁基鋰。在攪拌5分鐘後，將由175g苯乙烯和175g丁二烯組成的混合單體在9分鐘時間內連續加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到對比苯乙烯/丁二烯共聚物1。該產品中苯乙烯鏈段與丁二烯鏈段呈完全相分離狀態。該對比共聚物1的分子量為146,000(Mn )，分子量分佈為1.01，二烯烴中1,2-結構含量為13.0%，邵氏C硬度為89度，扯斷拉伸強度為17.8MPa。該聚合物的塑化溫度為135℃。當在聚合物塑化溫度135℃之上加入DCP和AC等加工助劑加工時，在密煉機中發生交聯並產生氣泡；而降低加工溫度至110℃則聚合物與加工助劑的混合不均勻，不能用於發泡材料；採用開放式煉膠機於110℃下加入助劑再在185℃下發泡，產品發生膠燒。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 2.65 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 175 g of styrene and 175 g of butadiene was continuously added to the polymerization vessel over a period of 9 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for an additional 20 minutes, and then 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a dry box to obtain a comparative styrene/butadiene copolymer 1. In this product, the styrene segment is completely phase separated from the butadiene segment. The molecular weight of the copolymer of Comparative 146,000 (M n), the molecular weight distribution of 1.01, diolefins 1,2-structure content of 13.0%, a Shore C hardness of 89 degrees, the ultimate tensile strength of 17.8MPa. The plasticization temperature of the polymer was 135 °C. When adding processing aids such as DCP and AC at a plasticizing temperature of 135 ° C, cross-linking occurs in the internal mixer and bubbles are generated. When the processing temperature is lowered to 110 ° C, the polymer and the processing aid are mixed. It is not uniform and can not be used for foaming materials; it is added into the foaming machine at 110 °C by an open type rubber mixer and then foamed at 185 °C.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加3.9mmol正丁基鋰。在攪拌5分鐘後，將由157.5g苯乙烯和182.9g 2-甲基-1,3-丁二烯組成的混合單體在30分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，再將剩餘的9.6g 2-甲基-1,3-丁二烯加入聚合釜聚合，20分鐘後添加0.875mmol四氯化矽偶聯劑，在偶聯反應進行30分鐘後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到星型苯乙烯/2-甲基-1,3-丁二烯共聚物。單臂分子量為48,600(Mn )，平均臂數為3.70，聚合物分子量為180,000(Mn )，分子量分佈為1.02，邵氏C硬度為52。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 3.9 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 157.5 g of styrene and 182.9 g of 2-methyl-1,3-butadiene was continuously pulsed into the polymerization vessel over 30 minutes, during which the maximum reaction temperature was controlled to be less than 100 ° C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for another 20 minutes, and the remaining 9.6 g of 2-methyl-1,3-butadiene was added to the polymerization vessel for polymerization. After 20 minutes, 0.875 mmol of ruthenium tetrachloride coupling agent was added. After the coupling reaction was carried out for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dewatering machine, and lyophilized in a dry box to obtain a star-shaped styrene/2-methyl-1,3-butadiene copolymer. The single arm has a molecular weight of 48,600 (M n ), an average number of arms of 3.70, a polymer molecular weight of 180,000 (M n ), a molecular weight distribution of 1.02, and a Shore C hardness of 52.
將100重量份該聚合物與4.1重量份AC、0.26重量份DCP、2.25重量份ZnO、0.45重量份硬脂酸鋅、0.25重量份硬脂酸、10重量份滑石粉、1重量份石蠟和3重量份EBS在開放式煉膠機中於110℃混合，然後用單螺桿擠出機在110℃擠出造粒。粒料於110℃注射到185℃的模具內發泡。該發泡產品可以用於製造皮鞋大底。100 parts by weight of the polymer with 4.1 parts by weight of AC, 0.26 parts by weight of DCP, 2.25 parts by weight of ZnO, 0.45 parts by weight of zinc stearate, 0.25 parts by weight of stearic acid, 10 parts by weight of talc, 1 part by weight of paraffin and 3 The parts by weight of EBS were mixed at 110 ° C in an open mill and then extruded and pelletized at 110 ° C using a single screw extruder. The pellets were foamed at 110 ° C and injected into a mold at 185 ° C. The foamed product can be used to make a leather outsole.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加6.2mmol正丁基鋰。在攪拌5分鐘後，將由175g苯乙烯和166.3g丁二烯組成的混合單體在40分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，再向聚合釜內加入8.7g丁二烯，聚合20分鐘後添加11.6mmol二乙烯基苯偶聯劑，在偶聯反應進行30分鐘後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到星型苯乙烯/丁二烯共聚物。該共聚物為6臂星形結構的苯乙烯-丁二烯共聚物，數均分子量為150,000，分子量分佈為1.07，二烯烴中1,2-結構含量為13.2%，邵氏C硬度為55。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 6.2 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 175 g of styrene and 166.3 g of butadiene was continuously pulsed into the polymerization vessel over 40 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer, the reaction was allowed to proceed for another 20 minutes, and then 8.7 g of butadiene was added to the polymerization vessel. After polymerization for 20 minutes, 11.6 mmol of divinylbenzene coupling agent was added, and the coupling reaction was carried out for 30 minutes. 5 ml of water was used to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a dry box to obtain a star-shaped styrene/butadiene copolymer. The copolymer was a 6-arm star-shaped styrene-butadiene copolymer having a number average molecular weight of 150,000, a molecular weight distribution of 1.07, a 1,2-structure content of 13.2% in a diene, and a Shore C hardness of 55.
將100重量份該聚合物與4.1重量份AC、0.26重量份DCP、2.25重量份ZnO、0.45重量份硬脂酸鋅、0.25重量份硬脂酸、10重量份滑石粉、1重量份石蠟和3重量份EBS在開放式煉膠機中於110℃混合，然後用單螺桿擠出機在110℃擠出造粒。粒料於110℃注射到185℃的模具內發泡。該發泡產品可以用於製造旅遊鞋和運動鞋中底。100 parts by weight of the polymer with 4.1 parts by weight of AC, 0.26 parts by weight of DCP, 2.25 parts by weight of ZnO, 0.45 parts by weight of zinc stearate, 0.25 parts by weight of stearic acid, 10 parts by weight of talc, 1 part by weight of paraffin and 3 The parts by weight of EBS were mixed at 110 ° C in an open mill and then extruded and pelletized at 110 ° C using a single screw extruder. The pellets were foamed at 110 ° C and injected into a mold at 185 ° C. The foamed product can be used to make travel shoes and sports midsole.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加2.30mmol正丁基鋰。在攪拌5分鐘後，將由157.5g苯乙烯和192.5g丁二烯組成的混合單體在45分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到苯乙烯/丁二烯共聚物。該共聚物為苯乙烯以微嵌段形式存在的苯乙烯/丁二烯共聚物，聚合物分子量為111,000(Mn )，分子量分佈為1.05，二烯烴中1,2-結構含量為16.0%，邵氏C硬度為75。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 2.30 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 157.5 g of styrene and 192.5 g of butadiene was continuously pulsed into the polymerization vessel over 45 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for an additional 20 minutes, and then 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dewatering machine, and lyophilized in a drying oven to obtain a styrene/butadiene copolymer. The styrene copolymer is present in the form of micro-block styrene / butadiene copolymers, polymer molecular weight 111,000 (M n), the molecular weight distribution of 1.05, a diene content of 1,2-structure was 16.0%, The Shore C hardness is 75.
將該聚合物與DCP、發泡劑、滑石粉、硬脂酸鋅、氧化鋅混合後加入到密煉機中於75℃以下密煉10分鐘，再用單螺桿在110℃以下造粒，粒料於110℃以下注射到180℃模具中進行發泡。該發泡產品可以用作管道外層的保溫材料。The polymer is mixed with DCP, a foaming agent, talc, zinc stearate, and zinc oxide, and then added to an internal mixer and kneaded at 75 ° C for 10 minutes, and then granulated by a single screw at 110 ° C or less. It is expected to be injected into a 180 ° C mold at 110 ° C or lower for foaming. The foamed product can be used as an insulating material for the outer layer of the pipe.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加3.8mmol正丁基鋰。在攪拌5分鐘後，將由175g苯乙烯和166.25g 2-甲基-1,3-丁二烯組成的混合單體在25分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，再向聚合釜內加入8.75g 2-甲基-1,3-丁二烯，聚合20分鐘後添加0.825mmol四氯化矽偶聯劑。在偶聯反應進行30分鐘後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到星型苯乙烯/2-甲基-1,3-丁二烯共聚物。該星型聚合物的單臂分子量為47,000(Mn )，平均臂數為3.72，聚合物分子量為175,000(Mn )，分子量分佈為1.02，邵氏C硬度為65。該聚合物可以採用注塑方式於185℃在模具內進行發泡。該發泡產品可以用於汽車內裝飾材料。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 3.8 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 175 g of styrene and 166.25 g of 2-methyl-1,3-butadiene was continuously pulsed into the polymerization vessel over 25 minutes, during which the maximum reaction temperature was controlled to be less than 100. °C. After the completion of the mixed monomer addition, the reaction was allowed to proceed for an additional 20 minutes, and 8.75 g of 2-methyl-1,3-butadiene was added to the polymerization vessel. After polymerization for 20 minutes, 0.825 mmol of ruthenium tetrachloride coupling agent was added. After the coupling reaction was carried out for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dewatering machine, and lyophilized in a dry box to obtain a star-shaped styrene/2-methyl-1,3-butadiene copolymer. The molecular weight of the single-arm star polymer was 47,000 (M n), the average number of arms was 3.72, the polymer molecular weight 175,000 (M n), the molecular weight distribution of 1.02, a Shore C hardness of 65. The polymer can be foamed in a mold at 185 ° C by injection molding. The foamed product can be used for automotive interior finishing materials.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加1.67mmol正丁基鋰。在攪拌5分鐘後，將由140g叔丁基苯乙烯和210g丁二烯組成的混合單體在55分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到叔丁基苯乙烯以微嵌段形式存在的叔丁基苯乙烯/丁二烯共聚物，聚合物分子量為234,000(Mn )，分子量分佈為1.08，二烯烴中1,2-結構含量為15.5%，邵氏C硬度為68。該聚合物可以採用注塑方式於185℃在模具內進行發泡。該聚合物的發泡產品可以用於製造高反彈材料。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 1.67 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 140 g of t-butylstyrene and 210 g of butadiene was continuously pulsed into the polymerization vessel over 55 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for an additional 20 minutes, and then 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and devolatilized in a dry box to obtain a tert-butylstyrene/butadiene copolymer in the form of a microblock of t-butylstyrene having a molecular weight of 234,000 ( M n ), the molecular weight distribution was 1.08, the 1,2-structure content of the diolefin was 15.5%, and the Shore C hardness was 68. The polymer can be foamed in a mold at 185 ° C by injection molding. The foamed product of the polymer can be used to make high rebound materials.
將實施例2得到的苯乙烯/丁二烯共聚物2按下面表1中所示配方複配，並將混合物料在90℃的密煉機混合，然後用單螺桿造粒。將所述粒料在110℃以下注射到180℃的模具內進行發泡，得到發泡材料。該發泡工藝與普通EVA發泡工藝相似。得到的發泡材料的性能示於表2。發泡材料斷面的掃描電子顯微鏡照片見附圖9。可以看到該苯乙烯/丁二烯共聚物可以得到泡孔均一的發泡材料。本實施例得到的發泡產品可以用於製造沙灘鞋和拖鞋。The styrene/butadiene copolymer 2 obtained in Example 2 was compounded according to the formulation shown in Table 1 below, and the mixture was mixed in an internal mixer at 90 ° C, and then granulated by a single screw. The pellets were injected into a mold of 180 ° C at 110 ° C or lower to foam, thereby obtaining a foamed material. The foaming process is similar to the conventional EVA foaming process. The properties of the obtained foamed material are shown in Table 2. A scanning electron micrograph of the cross section of the foamed material is shown in Fig. 9. It can be seen that the styrene/butadiene copolymer can obtain a foamed material having a uniform cell. The foamed product obtained in this embodiment can be used for the manufacture of beach shoes and slippers.
將市售EVA按照下面表1中所示配方複配，並採用與實施例8相同的操作，得到發泡材料。得到的發泡材料的性能示於表2。Commercially available EVA was compounded in accordance with the formulation shown in Table 1 below, and the same operation as in Example 8 was carried out to obtain a foamed material. The properties of the obtained foamed material are shown in Table 2.
ZnO：氧化鋅，ZnO: zinc oxide,
Znst：硬脂酸鋅，Znst: zinc stearate,
TA：滑石粉，TA: talcum powder,
EBS：N,N-乙撐雙硬脂醯胺EBS: N, N-ethylene distearylamine
硬度按GB/T10807-2006標準測定Hardness is determined according to GB/T10807-2006 standard
回彈性按GB/T6670-1997標準測定Resilience is determined according to GB/T6670-1997 standard
壓縮永久變形按GB6669-86標準測定Compression set is determined according to GB6669-86 standard
耐磨性按GB11208-89標準測定Wear resistance is determined according to GB11208-89 standard
止滑性按GB/T3903.6-2005標準測定The slip resistance is determined according to GB/T3903.6-2005 standard
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加2.71mmol正丁基鋰。在攪拌5分鐘後，將由192.5g苯乙烯和157.5g丁二烯組成的混合單體在20分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行25分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)的抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到苯乙烯/丁二烯共聚物9。該共聚物的分子量為145,000(Mn )。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 2.71 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 192.5 g of styrene and 157.5 g of butadiene was continuously pulsed into the polymerization vessel over 20 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer addition, the reaction was allowed to proceed for an additional 25 minutes, and then 5 ml of water was added to terminate the reaction. To the reaction mixture, 0.2% by weight of an antioxidant 1076 and 0.4% by weight of an antioxidant 168 based on the weight of the polymer were added and stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a dry box to obtain a styrene/butadiene copolymer 9. The molecular weight of the copolymer is 145,000 (M n).
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加2.10mmol正丁基鋰。在攪拌5分鐘後，將由245g苯乙烯和105g丁二烯組成的混合單體在45分鐘內連續脈衝式加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到苯乙烯/丁二烯共聚物。該共聚物為苯乙烯以微嵌段形式存在的苯乙烯/丁二烯共聚物，聚合物分子量為191000(Mn )。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 2.10 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 245 g of styrene and 105 g of butadiene was continuously pulsed into the polymerization vessel over 45 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer feed, the reaction was allowed to proceed for an additional 20 minutes, and then 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dewatering machine, and lyophilized in a drying oven to obtain a styrene/butadiene copolymer. The styrene copolymer is present in the form of micro-block styrene / butadiene copolymers, the polymer molecular weight was 191000 (M n).
將該聚合物與DCP、發泡劑、滑石粉、硬脂酸鋅、氧化鋅混合後加入到密煉機中於75℃以下密煉10分鐘，再用單螺桿在110℃以下造粒，粒料於110℃以下注射到180℃模具中進行發泡。該發泡產品可以用作管道外層的保溫材料。The polymer is mixed with DCP, a foaming agent, talc, zinc stearate, and zinc oxide, and then added to an internal mixer and kneaded at 75 ° C for 10 minutes, and then granulated by a single screw at 110 ° C or less. It is expected to be injected into a 180 ° C mold at 110 ° C or lower for foaming. The foamed product can be used as an insulating material for the outer layer of the pipe.
向經氮氣淨化的10升聚合釜中加入3.5升環己烷和抽餘油混合物(環己烷和抽餘油的混合比為9:1)，其中以200mg/kg的量含有四氫呋喃。將該混合物升溫至50℃，並添加3.4mmol正丁基鋰。在攪拌5分鐘後，將由227.5g苯乙烯和122.5g異戊二烯組成的混合單體在25分鐘內連續加入到聚合釜中，其間控制最高反應溫度小於100℃。混合單體加料完成後，允許反應再進行20分鐘，然後添加0.825mmol四氯化矽偶聯劑，在偶聯反應進行30分鐘後添加5ml水以終止反應。向反應混合物中加入基於聚合物的重量計0.2%(wt)的抗氧劑1076和0.4%(wt)抗氧劑168，攪拌5分鐘。最後將產物加入到蒸汽和水的混合物中，溶劑被蒸發，而聚合物則以固體的狀態離析出來懸浮在水中。將固體分離出來，用擠壓脫水機擠水、乾燥箱脫揮發分，得到星型苯乙烯/異戊二烯共聚物。該星型聚合物的單臂分子量為118000(Mn )，平均臂數為3.72，聚合物分子量為438900(Mn )。該聚合物可以採用模壓方式於185℃在模具內進行發泡。該發泡產品可以用於汽車內裝飾材料。To a nitrogen-purified 10 liter polymerization vessel, 3.5 liters of a mixture of cyclohexane and a raffinate oil (mixing ratio of cyclohexane and raffinate oil of 9:1) was added, wherein tetrahydrofuran was contained in an amount of 200 mg/kg. The mixture was warmed to 50 ° C and 3.4 mmol of n-butyllithium was added. After stirring for 5 minutes, a mixed monomer consisting of 227.5 g of styrene and 122.5 g of isoprene was continuously added to the polymerization vessel over 25 minutes, during which the maximum reaction temperature was controlled to be less than 100 °C. After the completion of the mixed monomer addition, the reaction was allowed to proceed for an additional 20 minutes, then 0.825 mmol of ruthenium tetrachloride coupling agent was added, and after the coupling reaction was carried out for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2% by weight of the antioxidant 1076 and 0.4% by weight of the antioxidant 168 based on the weight of the polymer were added to the reaction mixture, and the mixture was stirred for 5 minutes. Finally, the product is added to a mixture of steam and water, the solvent is evaporated, and the polymer is isolated as a solid and suspended in water. The solid was separated, squeezed with a squeeze dehydrator, and lyophilized in a dry box to obtain a star styrene/isoprene copolymer. The single-arm star polymer molecular weight is 118000 (M n), the average number of arms of 3.72, molecular weight of polymer 438900 (M n). The polymer can be foamed in a mold at 185 ° C by molding. The foamed product can be used for automotive interior finishing materials.
本申請說明書中提到的專利、專利申請、測試方法通過引用結合在本文。The patents, patent applications, and test methods mentioned in the specification of the present application are incorporated herein by reference.
雖然參考示例性實施方案描述了本發明，但本領域技術人員將理解，在不偏離本發明的精神和範圍的情況下，可以做出各種改變和修改。因此，本發明不限於作為實施本發明的最佳方式公開的特定實施方案，而是包括落入所附申請專利範圍內的所有實施方案。While the invention has been described with respect to the embodiments of the embodiments the embodiments Therefore, the invention is not limited to the specific embodiments disclosed as the best mode for carrying out the invention, but all embodiments falling within the scope of the appended claims.
圖1是實施例1的苯乙烯-丁二烯共聚物的1 H NMR譜圖。1 is a 1 H NMR spectrum of the styrene-butadiene copolymer of Example 1.
圖2是實施例2的苯乙烯-丁二烯共聚物的二維相關紅外譜圖。2 is a two-dimensional correlation infrared spectrum of the styrene-butadiene copolymer of Example 2.
圖3是一種常規三嵌段SBS的二維相關紅外譜圖。Figure 3 is a two-dimensional correlation infrared spectrum of a conventional triblock SBS.
圖4是一種全無規苯乙烯-丁二烯共聚物的二維相關紅外譜圖。Figure 4 is a two-dimensional correlation infrared spectrum of a wholly random styrene-butadiene copolymer.
圖5是一種SIS的二維相關紅外譜圖。Figure 5 is a two-dimensional correlation infrared spectrum of a SIS.
圖6是一種苯乙烯-異戊二烯微嵌段共聚物的二維相關紅外譜圖。Figure 6 is a two-dimensional correlation infrared spectrum of a styrene-isoprene microblock copolymer.
圖7是一種SIBS的二維相關紅外譜圖。Figure 7 is a two-dimensional correlation infrared spectrum of an SIBS.
圖8是一種苯乙烯-異戊二烯-丁二烯微嵌段共聚物的二維相關紅外譜圖。Figure 8 is a two-dimensional correlation infrared spectrum of a styrene-isoprene-butadiene microblock copolymer.
圖9是實施例8得到的發泡材料的掃描電子顯微鏡照片。Fig. 9 is a scanning electron micrograph of the foamed material obtained in Example 8.
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| CN1377905A (en) * | 2002-04-04 | 2002-11-06 | 巴陵石化岳阳石油化工总厂 | Styrene, butadiene block copolymer and its using method |
| CN1524888A (en) * | 2003-09-16 | 2004-09-01 | 中国石化集团巴陵石油化工有限责任公 | Transparent high-impact styrene-butadiene copolymer and preparation method thereof |
| TW200716685A (en) * | 2005-09-22 | 2007-05-01 | Asahi Kasei Chemicals Corp | Conjugated diene polymer and its polymerization method |
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| CN1377905A (en) * | 2002-04-04 | 2002-11-06 | 巴陵石化岳阳石油化工总厂 | Styrene, butadiene block copolymer and its using method |
| CN1524888A (en) * | 2003-09-16 | 2004-09-01 | 中国石化集团巴陵石油化工有限责任公 | Transparent high-impact styrene-butadiene copolymer and preparation method thereof |
| TW200716685A (en) * | 2005-09-22 | 2007-05-01 | Asahi Kasei Chemicals Corp | Conjugated diene polymer and its polymerization method |
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