CN1497001A - 接枝烯烃共聚物、其制备方法及其用途 - Google Patents
接枝烯烃共聚物、其制备方法及其用途 Download PDFInfo
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- CN1497001A CN1497001A CNA2003101138858A CN200310113885A CN1497001A CN 1497001 A CN1497001 A CN 1497001A CN A2003101138858 A CNA2003101138858 A CN A2003101138858A CN 200310113885 A CN200310113885 A CN 200310113885A CN 1497001 A CN1497001 A CN 1497001A
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- olefin copolymer
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- atom
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- 238000002360 preparation method Methods 0.000 title description 41
- 229920001577 copolymer Polymers 0.000 title description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 103
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 16
- 125000004185 ester group Chemical group 0.000 claims abstract description 15
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 12
- 125000005647 linker group Chemical group 0.000 claims abstract description 12
- 125000005372 silanol group Chemical group 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 50
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- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000004568 cement Substances 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 150000008064 anhydrides Chemical group 0.000 claims description 13
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- 239000002562 thickening agent Substances 0.000 claims description 7
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 25
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 125000004018 acid anhydride group Chemical group 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 150000007942 carboxylates Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 238000006243 chemical reaction Methods 0.000 description 41
- -1 alkyl borane Chemical compound 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000126 substance Substances 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
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- 239000002585 base Substances 0.000 description 17
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- 238000012360 testing method Methods 0.000 description 17
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000010926 purge Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
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- 238000012986 modification Methods 0.000 description 11
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- 239000002904 solvent Substances 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
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- 238000001914 filtration Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
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- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 6
- 244000061458 Solanum melongena Species 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000002900 organolithium compounds Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical group CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 241000428199 Mustelinae Species 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 150000001408 amides Chemical class 0.000 description 3
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000004034 viscosity adjusting agent Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
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- 229910000085 borane Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 125000001246 bromo group Chemical group Br* 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 2
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- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- HOROZASJKPUNET-UHFFFAOYSA-N 1-chlorodec-5-yne Chemical compound CCCCC#CCCCCCl HOROZASJKPUNET-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FLYIRERUSAMCDQ-UHFFFAOYSA-N 2-azaniumyl-2-(2-methylphenyl)acetate Chemical compound CC1=CC=CC=C1C(N)C(O)=O FLYIRERUSAMCDQ-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AWQOXJOAQMCOED-UHFFFAOYSA-N 8-Nonenoic acid Natural products OC(=O)CCCCCCC=C AWQOXJOAQMCOED-UHFFFAOYSA-N 0.000 description 1
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
一种在多种应用中显示优异性能的接枝烯烃共聚物,它包括下面式(1)表示的组成嵌段(A)和下面式(2)表示的组成嵌段(B):如上式其中,式(1)中,R1表示氢原子和C1-18的直链或支链脂肪烃基;式(2)中,R2表示C1-18的直链或支链脂族或芳族烃基;F表示杂原子或含杂原子的连接基团;Z表示含有至少一个选自氧原子、氮原子、卤原子和芳基的聚合物片段,其分子量分布为1.0-3.0;W表示选自醇羟基、酚羟基、羧酸基、羧酸酯基、酸酐基、氨基、环氧基、甲硅烷氧基和巯基的基团;n是1-3的整数,m是0,1或2,前提是当n为2或3时,Z彼此可以相同或不同,当m为2时,W彼此可以相同或不同;W可以与R2的相同或不同原子键合形成环状结构。
Description
技术领域
本发明涉及接枝烯烃共聚物及其制备方法,本发明尤其涉及其接枝部分是通过自由基聚合反应或阴离子聚合反应形成的接枝烯烃共聚物、其制备方法及其用途。
背景技术
一般来说,聚烯烃的特征在于具有优异的模压加工性、耐热性、机械性能、耐化学性、卫生稳定性和防水透汽性,并具有优异的模制品外观,因此被广泛地用于挤压成型制品、中空成型制品、和注射成型制品。
然而,聚烯烃分子中一般不含有极性基团,因此与诸如尼龙和EVOH的极性树脂的相容性以及与极性树脂和金属的粘合力差,使之难以作为与这些材料的混合物或层压体使用。
为了解决这些问题,已经广泛采用一种通过在聚烯烃上接枝含极性基团的单体来提高聚烯烃与极性树脂的亲和力的方法。然而该方法中,聚烯烃与接枝反应一起进行分子间交联,或者分子链分裂,因此所得到的接枝聚合物难以与极性树脂的粘度相匹配,或者有时候它们之间的相容性差。此外,通过分子间交联或分子链分裂形成的凝胶化物质能够破坏其成型制品的外观。
JP-A2-51511和JP-A3-177403描述了一种通过使用钛基或钒基催化剂共聚α-烯烃和含极性基团单体的方法。根据该方法,上述分子间交联和分子链分裂难以发生,但是所得共聚物的分子结构是多相的,也就是说,分子量分布宽,或者转化率高,因此它们与极性物质之间的界面处的极性基团的取向不足,有时造成与极性物质的粘合力和相容性不足。
本申请人提交的JP-A2002-145947和JP-A2002-155109公开了一种新型接枝的、含极性基团的烯烃共聚物,其制备方法,含有它的热塑性树脂组合物,及其应用以解决大多数问题。根据其公开内容,该接枝的含极性基团的烯烃共聚物的接枝部分是通过诸如阴离子聚合、开环聚合和缩聚反应的任何扩链反应制成并加上去的。
然而,存在一个限制可用于扩链反应的起始单体的问题。具体地说,缩聚反应不但要严格限制可用的起始单体,而且一般还经受苛刻的反应条件,因此有时引起聚合物恶化。从这个角度看,还需要进一步改善接枝烯烃共聚物。
T.C.Chung等在US5286800和US5401805中报道了通过在聚烯烃的主链或侧链的末端上加成诸如9-BBN的烷基硼烷,然后在氧气存在下将所得聚合物与甲基丙烯酸甲酯(MMA)等进行自由基聚合,制备含极性基团的烯烃共聚物的方法。然而,该方法中所用的烷基硼烷一般昂贵,并且不适于工业化生产。此外,T.C.Chung等人的报道描述了多相条件下仅仅在室温至60℃之间的MMA聚合温度下的聚合实施例,但没有描述在有利于更高反应速率的高温下的聚合实施例。注意到,在T.C.Chung等人的方法中,自由基聚合引发的端基应当采用氧气产生,因此由于残留氧气的影响抑制了自由基聚合反应,或者合适的活性物种由于氧化成硼酸盐或硼化物(boronate)而没有形成(Macromolecules,
26,3467(1996)),因此使得难以控制自由基聚合部分的结构。
本发明要解决上述问题。也就是说,本发明的目的是提供一种接枝部位特别含有多种极性官能团的接枝烯烃共聚物、其有效的制备方法及其应用,所述共聚物与金属或极性树脂的粘合力或相容性优异。
发明内容
本发明的接枝烯烃共聚物(P)包括式(1)表示的组成嵌段(A)和式(2)表示的组成嵌段(B):
其中,式(1)中,R1表示氢原子和C1-18的直链或支链脂肪烃基;式(2)中,R2表示C1-18的直链或支链脂族或芳族烃基;F表示杂原子或含杂原子的连接基团;Z表示含有至少一个选自氧原子、氮原子、卤原子和芳基的聚合物片段,其分子量分布为1.0-3.0;W表示选自醇羟基、酚羟基、羧酸基、羧酸酯基、酸酐基、氨基、环氧基、甲硅烷氧基和巯基的基团;n是1-3的整数,m是0,1或2,前提是当n为2或3时,Z彼此可以相同或不同,当m为2时,W彼此可以相同或不同;W可以与R2的相同或不同原子键合形成环状结构。
本发明接枝烯烃共聚物(P)的优选方式中,式(2)中F表示的连接基团含有至少一个选自羰基和芳基的基团。
本发明的接枝烯烃共聚物(P)通过下面的制备方法(M-1)或(M-2)有效地制成。当接枝烯烃共聚物(P)中的杂原子或含杂原子的连接基团(F)是仅含有醚基的基团之外的基团时,优选使用制备方法(M-1),而当连接基团(F)是仅含有醚连接的基团时,优选使用制备方法(M-2)。
制备方法(M-1)是一种顺序进行下述步骤1、2和3的制备方法。
(步骤1)合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G)。
(步骤2)在官能团(G)上接上能够引发自由基聚合的基团的步骤。
(步骤3)在接枝烯烃共聚物(P)中式(2)表示的组成嵌段(B)上,通过自由基聚合基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
制备方法(M-2)是一种顺序进行下述步骤1′、2′和3′的制备方法。
(步骤1′)合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G)。
(步骤2′)将官能团(G)转化为能够引发阴离子聚合的基团的步骤。
(步骤3′)在接枝烯烃共聚物(P)中式(2)表示的组成嵌段(B)上,通过阴离子聚合(不包括开环阴离子聚合)基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
本发明的热塑性树脂组合物含有上述接枝烯烃共聚物(P),并被用于多种用途中。
此外,本发明涉及含有上述接枝烯烃共聚物(P)的薄膜、片材、粘合树脂、相容性试剂、树脂改性剂、润滑油改性剂、水泥改性剂、建筑材料/市政工程材料、用于电器和电子部件的电绝缘材料、磁记录材料、汽车内外材料、汽油箱、填料分散剂或分散剂、水乳浊液、涂料基质、医药和卫生材料和杂物。
此外,本发明涉及含有上述热塑性树脂组合物的片材、粘合树脂、相容性试剂、树脂改性剂、润滑油改性剂、水泥改性剂、建筑材料/市政工程材料、用于电器和电子部件的电绝缘材料、磁记录材料、汽车内外材料、汽油箱、填料分散剂或分散剂、水乳浊液、涂料基质、医药和卫生材料和杂物。
具体实施方式
下面,将更加详细地描述本发明的接枝烯烃共聚物、其制备方法及其应用。本发明中术语“接枝”表示,侧链不但键合到主链的(ω-n)位置(n是1或大于1的正整数),而且还键合到主链的末端(ω位置)。
接枝烯烃基聚物(P)
本发明的接枝烯烃共聚物(P)包括式(1)表示的组成嵌段(A)和式(2)表示的组成嵌段(B):
式(1)中,R1表示氢原子或C1-18的直链或支链脂肪烃基。C1-18的直链或支链脂肪烃基包括,例如甲基、乙基、正丙基、异丙基、2-甲基丙基、正丁基、异丁基、仲丁基、叔丁基、1,1-二甲基丙基、2,2-二甲基丙基、戊基、新戊基、正己基、1-乙基-1-甲基丙基、1,1-二乙基丙基、2-乙基己基、辛基、癸基和十二烷基。这些基团中优选含有1-10个碳原子的基团,特别是1-6个碳原子的基团。
下面,描述式(2)中符号R2、F、Z、W、m和n的含义及其优选实施例。
式(2)中,R2表示C1-18的直链或支链脂族或芳族烃基,包括为R1所列举的基团。这些基团中优选含有1-10个碳原子的基团,特别是1-6个碳原子的基团。
式(2)中,F表示连接下述聚合物片段(Z)和基团R2的杂原子或含杂原子的连接基团。杂原子包括,例如氧原子、氮原子、硫原子、硅原子和磷原子,其中优选氧原子。含杂原子基团包括,例如酯基、酰胺基、酮基、醚基、氨基甲酸乙酯基团、氰基、磺酰基、和硫代酸酯基,其中优选酯基和醚基,特别优选酯基。
式(2)中,W表示选自醇羟基、酚羟基、羧酸基、羧酸酯基、酸酐基、氨基、环氧基、硅烷醇基和巯基的基团,其中优选羧酸基和醇羟基。
式(2)中,n是1-3的整数,m是0、1或2,前提是当n为2或3时,Z彼此可以相同或不同,当m为2时,W彼此可以相同或不同,W可以与R2的相同或不同原子键合形成环状结构。
式(2)表示的组成嵌段(B)包括,例如下面式(3)-(5)表示的组成嵌段:
上面式(3)表示的骨架对应于式(2)的骨架,其中R2是亚甲基,m为0,n为1,连接基团(F)是-O-CO-C(Me)2-。
上面式(4)表示的骨架对应于式(2)的骨架,其中m为1,n为1,W表示羧酸基(-CO2H),R2表示连接到-CO2H上的亚乙基,F表示由亚乙基延伸的含酯的基团(-(CO)O-CH2-CH(Ph)-)。
上面式(5)表示的骨架对应于式(2)的骨架,其中R2是亚甲基,m是0,n是1,连接基团(F)是-O-。
下面,用化学结构表示式(2)表示的组成嵌段(B)的优选实施例。
这些式中,x是0-15的整数。
式(2)中,Z是含有至少一个选自氧原子、氮原子、卤原子和芳基的聚合物片段,特别是由基本上含有碳碳双键化合物(R)的单体组成的聚合物,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团,如下所述。
对于聚合物片段Z的分子量没有特别限制,其重均分子量(Mw)一般为100-100,000,优选500-50,000。本发明的接枝烯烃共聚物(P)中,聚合物片段(Z)的分子量分布(Mw/Mn),当该接枝烯烃共聚物(P)被用于多种应用时,从有效地显示侧链片段的物理性能的角度看是特别重要的。一般来说,聚合物片段(Z)的分子量分布(Mw/Mn)为1.0-3.0,优选1.0-2.5,更优选1.0-1.8,仍然更优选1.0-1.5。当聚合物片段Z是通过自由基反应接上的,由引发自由基反应的官能团(P)产生的残基或由加入来终止聚合的化合物产生的残基可以连接到聚合物片段(Z)的末端。此外,当Z是含有酯连接基或酰胺连接基的单体时,连接基可以部分或完全皂化或水解来提高赋予Z的物理性能。此外,还可以加入多种金属化合物来提高Z片段的极性、导电性、机械物理性能、和耐磨性。
本发明的接枝烯烃共聚物中,式(1)表示的组成嵌段(A)与式(2)表示的组成嵌段(B)的摩尔比,即((A)∶(B))一般为99.95∶0.05至10∶90,优选99.90∶0.10至30∶70。
下面,更详细地描述本发明的接枝烯烃共聚物的制备方法。
本发明的接枝烯烃共聚物(P)可通过下述制备方法(M-1)或(M-2)有效地制成。
当接枝烯烃共聚物(P)中的杂原子或含杂原 子的连接基团(F)是含有羰基和/或芳基的基团时,优选使用制备方法 (M-1),而当连接基团(F)是含有醚基的基团时,优选使用制备 方法(M-2)。
下面,将更加详细地描述制备方法(M-1)和(M-2)。
制备方法(M-1)
本发明的接枝烯烃共聚物(P)是通过顺序进行下述步骤1、2和3制成的。
(步骤1)合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G)。
(步骤2)在官能团(G)上接上能够引发自由基聚合的基团的步骤。
(步骤3)在接枝烯烃共聚物(P)中式(1)表示的组成嵌段(B)上,通过自由基聚合基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
下面,将更加详细地描述本发明制备方法的每个步骤。
步骤1是合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G)。含极性基团的烯烃共聚物(Q)可以通过例如JP-A 2002-155109,JP-A 2000-29031,JP-A 8-109218和JP-A2002-167412中公开的公知方法来制成。具体地说,含极性基团的烯烃共聚物(Q)可以通过使用已知的Ziegler-Natta催化剂或金属茂催化剂共聚下述成分来制成,所述成分是含有3-20个碳原子的α-烯烃,例如乙烯、丙烯、1-丁烯、4-甲基-1-戊烯和1-己烯;其线性烃部分是线性的不饱和醇,例如烯丙醇、4-戊烯-1-醇和5-己烯-1-醇;链烯基羧酸,例如5-己烯酸、6-庚烯酸、7-辛烯酸、8-壬烯酸和9-癸烯酸;链烯基羧酸酯例如3-丁烯酸甲酯、5-己烯酸甲酯和6-庚烯酸甲酯;链烯基氨例如烯丙基胺、5-己烯胺、和6-庚烯胺;(2,7-辛二烯基)琥珀酸酐、五丙烯基琥珀酸酐和含链烯基酸酐例如其中上述链烯基羧酸基中的羧酸基被羧酸酐基代替的化合物。
在压出机中,通过在熔融聚烯烃上接枝极性基团得到含极性基团的烯烃共聚物的方法是已知的,通过接枝烯键式不饱和羧酸及其衍生物得到的聚烯烃(特别是马来酸酐接枝的聚烯烃)已经被工业化。含极性基团的烯烃共聚物典型地是在高剪切应力下,通过马来酸酐与熔融烯烃聚合物之间的反应得到的。
这样,就能够制成带有官能团(G)例如醇羟基、伯胺基、仲胺基、羧酸基、酯基、硅烷醇基、酸酐基、和环氧基的含极性基团的烯烃共聚物(Q)。该含极性基团的烯烃共聚物(Q)的重均分子量(Mw)一般为500-500,000,优选2,000-200,000。
步骤2是通过步骤1中得到的含极性基团的烯烃共聚物(Q)与含有能够引发自由基聚合的基团的化合物之间的反应,在官能团(G)上接上能够引发自由基聚合的基团的步骤。带有能够引发自由基聚合的基团(S)的化合物所需要的性能应当满足下面两个条件:
1)它应当具有能够化学键合到官能团(G)上的官能团(R);和
2)它应当具有引发自由基聚合的官能团(S)。
满足条件1)的官能团(R)包括,但不限于醇羟基、酚羟基、氨基、羧酸基、酯基、卤代烷基、酸酐基、羧酸卤基团等。
满足条件2)的官能团包括,例如Trend Polym.Sci.,
4,456(1996)中公开的其上带有通过热分裂产生自由基的硝基氧(nitroxide)的基团,或者Macromolecules,28,1721(1995)和Science,
272,866(1996)中公开的带有末端卤原子并且在加入金属例如RuCl或CuCl时产生自由基的基团。
能够引发自由基聚合的基团(S)包括,诸如2,2,6,6-四甲基哌啶-1-氧基(TEMPO),4-羟基-2,2,6,6-四甲基哌啶-1-氧基,2,2,5,5-四甲基-1-吡咯烷氧基,3-氨基-2,2,5,5-四甲基-1-吡咯烷-氧-基,3-羧基-溴基,2,2,5,5-四甲基-1-吡咯烷氧基,二叔丁基硝酰基,溴基,氯基等。这些化合物中,优选2,2,6,6-四甲基哌啶-1-氧基(TEMPO)和溴基。
在含有极性基团的烯烃共聚物(Q)与带有能够引发自由基聚合的基团(S)的化合物之间反应时,该反应是将能够引发自由基聚合的基团(S)接到含极性基团的烯烃共聚物(Q)的官能团(G)上,一般使用无水有机溶剂,但是该反应优选0-120℃下在与聚烯烃高度相容的烃基有机溶剂中进行,例如甲苯、苯、己烷、庚烷等。该反应可以是均相的或多相的,优选均相的。当反应难以进行时,诸如硫酸、甲酸或对甲苯磺酸的Brensted酸或诸如氯化铝的路易斯酸可以用作催化剂。当反应中产生水时,为了使反应能够有效进行,可以通过加入无水硫酸镁或分子筛或利用Dienstag回流来除去水。带有能够引发自由基聚合的基团(S)的化合物与官能团(G)的比例(当量比)(G)∶(S)一般为1∶0.1至1∶100,优选1∶1至1∶30。通过该反应得到的,带有能够引发自由基聚合的基团的含极性基团烯烃共聚物,可以用甲醇或丙酮沉淀,然后过滤来分离。如果需要,带有能够引发自由基聚合的基团(S)的未反应化合物可以简单的通过用溶剂洗涤来除去,在该溶剂中该带有能够引发自由基聚合的基团(S)的化合物是溶解的。
步骤3是通过自由基聚合基本上含有碳碳双键化合物(R)的单体,在步骤(2)制成的产物上接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
自由基聚合反应中使用的含有至少一种选自氧原子、氮原子、卤原子和芳基的含碳碳双键化合物(R)包括,例如丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸羟基乙酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸氨基乙酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸正十二烷基酯、甲基丙烯酸苄酯、甲基丙烯酸环己酯、甲基丙烯酸冰片酯、丙烯腈、甲基丙烯腈、丁基乙烯基醚、偏氯乙烯、氯乙烯、醋酸乙烯酯、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸2-羟乙酯、富马酸二甲酯、富马酸二乙酯、富马酸二异丙酯、富马酸二叔丁酯、富马酸二环己酯、2-丙烯酸4-羟丁酯、4-氯代苯乙烯、4-三氟苯乙烯、4-甲氧基羰基苯乙烯、丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、2,5-降冰片烯-2,3-二羧酸、苯乙烯和4-甲基苯乙烯。步骤3的自由基聚合中,如果需要,单体(R)在至少一种烯烃(R′)存在下进行自由基聚合,所述烯烃(R′)选自乙烯和3个或更多个碳原子的α-烯烃。以R′/(R+R′)比例计,任选使用的至少一种选自乙烯和含3个或更多个碳原子的α-烯烃的用量一般为0-50mol%,优选0-30mol%。
如果需要,根据本发明的自由基聚合是在催化剂存在下进行的。催化剂包括,例如CuBr、CuCl、RuCl、RuCl2、FeCl、FeCl2等。当使用催化剂时,催化剂的用量相对于能够引发自由基聚合的基团(S)为0.01-10当量,优选0.1-2当量。可以加入配位脂肪胺或芳族胺来增加催化剂在反应体系中的溶解性,或者加入烷氧基铝作为反应促进剂。如果需要,还可以加入自由基链转移剂。
下面,将更加详细地描述聚合反应的条件。
具体地说,反应中所用的溶剂包括脂肪烃例如丙烷、丁烷、戊烷、己烷、庚烷、辛烷、癸烷、十二烷和石油;脂环烃例如环戊烷、环己烷和甲基环戊烷;芳烃例如苯、甲苯、二甲苯和均三苯;卤化烃例如氯乙烯和氯代苯,及其组合。其中,特别优选使用脂肪烃。为了抑制副反应,所用溶剂中含有的氧优选被除去。
该反应在惰性气氛中,在0-200℃,优选室温至150℃,更优选60℃-130℃的温度下进行。该反应可以是均相的或多相的,优选是均相的。加入的可自由基聚合单体的量是根据所需的接枝烯烃共聚物的分子量来控制的,能够引发自由基聚合的基团(S)与可自由基聚合单体的比例,即(S)∶(单体中碳碳双键的量)的当量比一般为1∶2至1∶1000,优选1∶5至1∶500。反应用甲醇或异丁醇终止后,聚合物是通过将反应溶液倒入例如大量甲醇中沉淀的,然后通过过滤分离并干燥,由此能够分离所需要的接枝烯烃共聚物(P)。如果需要,将所得接枝烯烃共聚物(P)在Soxhlet萃取设备中,用诸如丙酮或THF的极性溶剂处理,来除去作为副产物形成的均自由基聚合物。
制备方法(M-2)
制备方法(M-2)是一种顺序进行下述步骤1′,2′和3′的制备方法。
(步骤1′)合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G)。
(步骤2′)将官能团(G)转变为能够引发阴离子聚合的基团的步骤。
(步骤3′)在接枝烯烃共聚物中式(2)表示的组成嵌段(B)上,通过阴离子聚合(不包括开环阴离子聚合)基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
下面,将描述本发明制备方法的每个步骤。
步骤1′是合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G),该制备方法包括与上述制备方法(M-1)相同的方法。制备方法(M-2)中,优选使用含有羟基作为官能团(G)的含极性基团的烯烃共聚物(Q′)。
步骤2′是将官能团(G)转变为能够引发阴离子聚合的基团的步骤。具体地说,通过借助碳原子键合到共聚物(Q′)的主链和/或侧链的末端的羟基与有机锂化合物的反应,将含有极性基团的烯烃共聚物(Q′)转变为末端带有锂的烯烃共聚物。末端上带有羟基的含极性基团的烯烃共聚物(Q′)与有机锂化合物之间的反应一般是在溶剂中进行的。
有机锂化合物包括烷基锂例如丁基锂、丙基锂、乙基锂和甲基锂,以及烷氧基锂例如丁氧基锂、丙氧基锂、乙氧基锂和甲氧基锂。本发明中,更优选使用烷基锂。
具体地说,该反应中所用的溶剂包括脂肪烃例如丙烷、丁烷、戊烷、己烷、庚烷、辛烷、癸烷、十二烷和石油;脂环烃例如环戊烷、环己烷和甲基环戊烷;芳烃例如苯、甲苯、和二甲苯;卤化烃例如氯乙烯和氯代苯,及其组合。其中,特别优选使用脂肪烃。
在末端上带有羟基的烯烃与有机锂化合物之间的反应中,相对于1当量含极性基团烯烃共聚物(Q′)末端上的羟基,有机锂化合物的用量为0.1-100当量,优选0.2-10当量。反应温度一般为-100至100℃,优选0-80℃,反应时间一般为0.1-48小时,优选0.5-12小时。
步骤1′中,有机磷化合物还可以代替有机锂化合物使用。有机磷化合物的优选实例包括卤化物,更优选如下物质的卤化物:三(二甲基氨基)[三(二甲基氨基)亚膦基氨基]鏻,三(二乙基氨基)[三(二乙基氨基)亚膦基氨基]鏻,双(二甲基氨基)双[三(二甲基氨基)亚膦基氨基]鏻,(二甲基氨基)三[三(二甲基氨基)亚膦基氨基]鏻,四[三(二甲基氨基)亚膦基氨基]鏻,四[三(吗啉代)亚膦基氨基]鏻,和四[三(哌啶子基)亚膦基氨基]鏻。
有机磷化合物优选易于产生阳离子的化合物,更优选易于产生亚膦基氨基鏻阳离子的化合物。
步骤3′中使用的含有至少一个选自氧原子、氮原子、卤原子和芳基的含碳碳双键的化合物(R)可以与上面制备方法(M-1)中描述的化合物相同,特别优选使用(甲基)丙烯酸酯或芳族乙烯基化合物。步骤3′的阴离子聚合中,如果需要,单体(R)在至少一种烯烃(R′)存在下进行阴离子聚合,所述烯烃(R′)选自乙烯和含3个或更多个碳原子的α-烯烃。以R′/(R+R′)比例计,任选使用的至少一种选自乙烯和含3个或更多个碳原子的α-烯烃的用量一般为0-50mol%,优选0-30mol%。
步骤3′中的阴离子聚合是通过将溶剂与锂封端的或含有磷的聚烯烃和(甲基)丙烯酸酯或芳族乙烯基化合物进行混合来进行的,或者是通过将锂封端的或含有磷的聚烯烃与液体(甲基)丙烯酸酯或芳族乙烯基化合物进行混合来进行的。
作为步骤3′中使用的溶剂,可以使用例如,脂肪烃例如己烷和庚烷;脂环烃例如环戊烷和环己烷;芳烃例如苯和甲苯;醚溶剂例如二乙醚、二噁烷、四氢呋喃(THF)、monogrime和digrime。这些溶剂可以单独使用,或者以两种或多种的混合物的形式使用。具体地说,优选使用芳烃和醚溶剂。
对于聚合反应,可以加入化合物例如三苯膦、α,α′-二吡啶基、六甲基磷酰胺(HMPA)、四氯化钛、烷基锂和烷氧基锂,来促进阴离子聚合活性种的形成。
阴离子聚合一般在-100至100℃下进行,优选在-80℃至80℃下进行,更优选-70℃至70℃下进行,时间为1分钟至500小时,优选10分钟至300小时,更优选15分钟至150小时。该聚合中,Li封端的聚烯烃的浓度为0.001-100mol/L,优选0.005-50mol/L,更优选0.01-10mol/L,仍然更优选0.1-5mol/L。(甲基)丙烯酸酯或芳族乙烯基化合物的浓度一般为0.001-500mol/L,优选0.005-300mol/L,更优选0.01-150mol/L。
本发明的接枝烯烃共聚物可以用于多种用途中,例如下述用途。
(1)薄膜和片材:含有本发明接枝烯烃共聚物的膜和片材在柔韧性、透明性、粘度、防雾性、耐热性和剥离能力方面是优异的。
(2)含有至少一层由具有聚烯烃骨架的接枝聚合物组成的层压体,例如农用膜、包装膜、收缩膜、保护膜、分离血浆组分的膜、分离膜例如选择透过水的蒸发膜,和选择分离膜例如离子交换膜,电池分液器和光分辨膜。
(3)微胶囊、PTP包装、化学木浆、医药分送体系。
(4)作为改性树脂的改性剂的接枝烯烃共聚物产生改性效果,例如耐冲击性、流动性、涂敷性能、结晶性、粘合力和透明性。
作为橡胶改性剂的接枝烯烃共聚物产生诸如耐候性、耐热性、粘合力和耐油性的改性效果。所述橡胶包括交联橡胶例如天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)、苯乙烯-丁二烯橡胶(SBR)、氯丁二烯橡胶(CR)、丙烯腈-丁二烯橡胶(NBR)、丁基橡胶(IIR)、乙烯-丙烯橡胶(EPM,EPDM)、氯磺化聚乙烯(CSM)、丙烯酸橡胶(ACM,ANM等)、表氯醇橡胶(CO,ECO等)、硅氧烷橡胶(Q)、氟橡胶(FKM等)等;和热塑性橡胶例如那些基于苯乙烯、烯烃、聚氨酯、酯、酰胺和氯乙烯的橡胶。
接枝烯烃共聚物可以用作润滑油的改性剂,所述润滑油例如汽油机油、柴油机油、用于船只的机油、齿轮油、机械油、金属加工油、马达油、机械油、锭子油、和润滑油例如绝缘油、或粘度调节剂,和冰点抑制剂。用作蜡改性剂的接枝烯烃共聚物具有诸如粘合力、流动性和强度的改性效果。该蜡包括诸如褐煤蜡、泥煤蜡、地蜡/不定形蜡和石油蜡的矿蜡;诸如聚乙烯、Fischer-Tropsch蜡、化学改性烃蜡和取代酰胺蜡的合成蜡,植物蜡和动物蜡。
作为水泥改性剂的接枝烯烃共聚物具有诸如流动性和强度的改性效果。水泥包括空气凝固水泥例如石灰、石膏和氧化镁水泥,水硬水泥例如罗马水泥、天然水泥、卜特兰水泥、氧化铝水泥和高硫酸盐炉渣水泥,和特征水泥例如耐酸水泥、耐火水泥、水玻璃水泥、和牙科粘固粉。
(5)接枝烯烃共聚物被用作粘度调节剂,模压加工性改进剂,墨例如凸版印刷油墨、石印油墨、胶版印刷油墨、和凹版印刷油墨,油漆,纤维素衍生物油漆,合成树脂油漆,水基烤漆,粉末水基油漆,用于油墨/涂料的粘度调节剂例如日本漆,和模压加工性改性剂。
(6)建筑材料/市政工程的建筑材料,例如建筑材料/市政工程的树脂和建筑材料/市政工程的模制品例如地板材料、地板砖、地板片材、隔音片材、隔热板、防震材料、装饰板、脚底板、沥青改性剂、垫圈/密封材料、屋顶片材、防水片材等。
(7)汽车内外材料和汽油箱;含有本发明接枝烯烃共聚物的汽车内外材料和汽油箱具有优异的硬度、耐冲击性、耐油性和耐热性。
(8)用于电器和电子部件的电绝缘材料;处理电子部件的工具;电器和电子部件例如磁记录介质,磁记录介质中的粘合剂;电路中的密封材料,家庭器具材料,用于容器例如微波炉容器的装配部件,微波炉用膜,高分子电解质基材料,导电合金基材料,连接器,插座,电阻器,继电器盒开关盘管线轴,冷凝器,头发剪切器盒,拾光器,光连接器,振动器,多种接线端子板,变压器,插头,印刷电路板,调谐器,扬声器,麦克风,头戴式耳机,小电机,磁头基体,动力模块,外罩,半导体,液晶部件,FDD托架,FDD底盘,HDD部件,电动机刷子支架,抛物面天线,和与计算机有关的部件;VTR部件,TV部件,电熨斗,吹风机,电饭锅部件,微波炉部件,音响部件,音响设备部件例如声盘/激光影碟(注册商标)/光盘,光部件,冰箱部件,空调部件,打字机部件,家庭和办公室电器产品部件例如文字处理器部件、与办公室计算机有关的部件,与电话有关的部件,与传真机有关的部件,与复印机有关的部件,电磁屏蔽材料,扬声器球体材料,用于扬声器的振动元件,等。
(9)水乳浊液:含有本发明接枝烯烃共聚物的水乳浊液提高了耐磨性、金属粘合力、润滑性能和防锈性能,因此具有作为水基油墨耐磨剂、用于水基油漆的润滑剂、防结块剂、水基油墨防滑剂、乳液改性剂、用于铝的涂料和用于钢板的防锈涂料的优异性能。此外,它可以作为热封性优异的用于聚烯烃的粘合剂。
(10)涂料基质:含有本发明接枝烯烃共聚物的溶剂分散体在溶剂中具有优异的分散稳定性,在将金属或极性树脂粘合到聚烯烃上时具有高的粘合力。
(11)医药制品例如医药和卫生无纺织物,无纺织物的层压体,驻极体,医药管,医药容器,血液输液袋,预填充的注射器,假牙材料,皮下注射器,医药材料,人工器官,人工肌肉,过滤膜,食品卫生/健康制品,甑袋,保鲜膜等。
(12)杂物台垫,切割垫,标尺,钢笔体/把手/帽,剪刀和切割器的把手,磁性片材,钢笔盒,纸夹,粘合剂,标签纸,胶带,书写材料例如白板,日用杂物例如衣服,窗帘,被单,地毯,门口垫子,浴室垫子,存储桶,胶管,袋子,花盆,空调器中的过滤器或通风扇,餐具,托盘,杯子,午餐盒,咖啡虹吸管的漏斗,玻璃杯框,容器,储物箱,挂钩,绳子和洗涤网;体育用品例如鞋子,护眼罩,溜冰鞋,球拍,球,帐篷,游泳护眼罩,橡胶脚掌,钓鱼杆,冷却器箱子,休闲板和体育网状物;玩具例如块和卡;容器例如汽油箱,鼓形容器,和用于洗涤剂和洗发剂的瓶子;显示器例如招牌,路标塔和塑料链。
(13)填料改性剂:本发明的接枝烯烃共聚物可以优选用作用于填料分散能力的改进剂以及制备提高了分散能力的填料的添加剂。
(14)相容性试剂:本发明的接枝烯烃共聚物可以用作相容性试剂。当采用本发明的具有聚烯烃骨架的接枝聚合物时,具有极性基团的聚烯烃和热塑性树脂可以以任意比例混合。本发明的具有聚烯烃骨架的接枝聚合物具有聚烯烃片段和功能片段,由此能够使得原本上相互不相容的组分彼此相容,并且与不使用具有聚烯烃骨架的接枝聚合物相比,明显提高了断裂伸长。
实施例
下面,将参考实施例对本发明进行更详细的描述,但是本发明并不限于这些实施例。
实施例1
[2-溴丁酰基改性的含极性基团的烯烃共聚物的制备]
将根据Chem.Lett.,2001,710-711所述方法制成的12g乙烯/10-十一烯-1-醇共聚物(Mw=47200,Mw/Mn=1.98,共聚单体含量3.6mol%)加入到1L氮气吹扫的两颈茄子型烧瓶中,然后向其中加入500ml干甲苯、32ml三乙胺和12.9ml 2-溴异丁酰溴,并将混合物在80℃加热,并在加热下搅拌2小时。将反应溶液倒入2L甲醇中,并将沉淀的聚合物用玻璃过滤器过滤。将玻璃过滤器中的聚合物用100ml甲醇洗涤3次,用100ml 1N盐酸洗涤一次,并用100ml甲醇洗涤两次。将聚合物在50℃、10托的减压条件下干燥10小时。1H-NMR的结果,得到了用2-溴异丁酸基团改性的含有99%末端OH基的含极性烯烃共聚物(2-溴异丁酸基团改性的PE)。
[接枝烯烃共聚物(PE-g-PMMA-1)的制备以及其侧链分子量的确定]
向氮气吹扫的100ml Schrenk烧瓶中加入215mg(1.50mmol)氯化铜(I)、1.50ml(3.0mmol)2M溶于二甲苯中的N,N,N′,N″,N″-五甲基二乙基三胺、0.80ml(7.5mmol)甲基丙烯酸甲酯和27.7ml邻二甲苯,然后盖上隔膜盖。从该溶液中,通过冰冻泵和解冻方法制备其中溶解的氧气已经除去的均匀溶液(A)。单独地,将上述含有极性基团的烯烃共聚物(2-溴异丁酸基改性的PE)1.50g(含有1.50mmol改性基团)加入到另一个用氮气吹扫的100ml Schrenk烧瓶中,然后盖上隔膜盖。将上述溶液(A)转移到该Schrenk烧瓶中,加热到120℃并反应5小时。将反应混合物冷却到室温,将该反应通过加入大约5ml甲醇终止,然后将反应溶液倒入500ml甲醇中并搅拌一整夜。将沉淀的聚合物用玻璃过滤器通过过滤分离,将聚合物在80℃、15托的减压条件下干燥10小时。1H-NMR测试表明,得到了含有9.1wt%甲基丙烯酸甲酯聚合物的含极性基团的接枝烯烃共聚物(PE-g-PMMA-1)。将1.0g所得到的PE-g-PMMA放入200ml茄子型烧瓶中,然后向其中加入100mlTHF,向其中加入3ml 5mol/L的氢氧化钠水溶液,并将悬浮液在50℃下搅拌一整夜。将反应溶液冷却到室温,并将由于水解裂开的不可溶聚乙烯主链通过用玻璃过滤器过滤除去,然后将有机相在减压下蒸馏,并将所得侧链用GPC分析。结果,侧链PMMA(或其水解产物)的Mw为980,Mw/Mn为1.45。
实施例2
[接枝烯烃共聚物(PE-g-PMMA-2)的制备]
向氮气吹扫的100ml Schrenk烧瓶中加入215mg(1.50mmol)氯化铜(I)、1.50ml(3.0mmol)2M溶于二甲苯中的N,N,N′,N″,N″-五甲基二乙基三胺、9.62ml(89.9mmol)甲基丙烯酸甲酯和18.9ml邻二甲苯,然后盖上隔膜盖。从该溶液中,通过冰冻泵和解冻方法制备其中溶解的氧气已经除去的均匀溶液(A)。单独地,将在实施例1中制备的含有极性基团的烯烃共聚物(2-溴异丁酸基改性的PE)1.50g(含有1.50mmol改性基团)加入到另一个用氮气吹扫的100ml Schrenk烧瓶中,然后将该烧瓶盖上隔膜盖。将上述溶液(A)转移到该Schrenk烧瓶中,加热到120℃并反应5小时。将反应混合物冷却到室温,将该反应通过加入大约5ml甲醇终止,然后将反应溶液倒入500ml甲醇中并搅拌一整夜。将沉淀的聚合物用玻璃过滤器通过过滤分离,并在80℃、15托的减压条件下干燥10小时。1H-NMR测试表明,得到了含有79.1wt%甲基丙烯酸甲酯聚合物的含极性基团的接枝烯烃共聚物(PE-g-PMMA-2)。将1.0g所得到的PE-g-PMMA放入200ml茄子型烧瓶中,然后向其中加入100ml THF,向其中加入3ml 5mol/L的氢氧化钠水溶液,并将悬浮液在50℃下搅拌一整夜。将反应溶液冷却到室温,并将由于水解裂开的不可溶聚乙烯主链通过用玻璃过滤器过滤除去,然后将有机相在减压下蒸馏,并将所得侧链用GPC分析。结果,侧链PMMA(或其水解产物)的分子量和分子量分布分别为Mw=18100,Mw/Mn为1.34。
实施例3
[接枝烯烃共聚物(PE-g-(MA-co-BA))的制备]
向氮气吹扫的100ml Schrenk烧瓶中加入215mg(1.50mmol)氯化铜(I)、1.50ml(3.0mmol)2M溶于二甲苯中的N,N,N′,N″,N″-五甲基二乙基三胺、2.5ml(32.2mmol)丙烯酸甲酯、4.0ml(27.9mmol)丙烯酸丁酯和26.5ml邻二甲苯,然后盖上隔膜盖。从该溶液中,通过冰冻泵和解冻方法制备其中溶解的氧气已经除去的均匀溶液(A)。单独地,将在实施例1中制备的含有极性基团的烯烃共聚物(2-溴异丁酸基改性的PE)1.50g(含有1.50mmol改性基团)加入到另一个用氮气吹扫的100ml Schrenk烧瓶中,然后盖上隔膜盖。将上述溶液(A)转移到该Schrenk烧瓶中,加热到110℃并反应3小时。将反应混合物冷却到室温,将该反应通过加入大约5ml甲醇终止,然后将反应溶液倒入500ml甲醇中并搅拌一整夜。将沉淀的聚合物用玻璃过滤器通过过滤分离,然后在80℃、15托的减压条件下干燥10小时。1H-NMR测试表明,得到了含有48wt%丙烯酸甲酯—丙烯酸丁酯共聚物的接枝烯烃共聚物(PE-g-(MA-co-BA))。
实施例4
[接枝烯烃共聚物(PE-g-PS)的制备以及其侧链分子量的确定]
向氮气吹扫的100ml Schrenk烧瓶中加入215mg(1.50mmol)氯化铜(I)、1.50ml(3.0mmol)2M溶于二甲苯中的N,N,N′,N″,N″-五甲基二乙基三胺、10.3ml(8.99mmol)苯乙烯和18.2ml邻二甲苯,然后盖上隔膜盖。从该溶液中,通过冰冻泵和解冻方法制备其中溶解的氧气已经除去的均匀溶液(A)。单独地,将在实施例1中制备的含有极性基团的烯烃共聚物(2-溴异丁酸基改性的PE)1.50g(含有1.50mmol改性基团)加入到一个用氮气吹扫的100ml Schrenk烧瓶中,然后盖上隔膜盖。将上述溶液(A)转移到该Schrenk烧瓶中,加热到120℃并反应5小时。将反应混合物冷却到室温,将该反应通过加入大约5ml甲醇终止,然后将反应溶液倒入500ml甲醇中并搅拌一整夜。将沉淀的聚合物用玻璃过滤器通过过滤分离,然后在80℃、15托的减压条件下干燥10小时。1H-NMR测试表明,得到了含有85.6wt%苯乙烯共聚物的含极性基团的接枝烯烃共聚物(PE-g-PS)。
将1.0g所得到的PE-g-PMMA放入200ml茄子型烧瓶中,然后向其中加入100ml THF,向其中加入3ml 5mol/L的氢氧化钠水溶液,并将悬浮液在50℃下搅拌一整夜。将反应溶液冷却到室温,并将由于水解裂开的不可溶聚乙烯主链通过用玻璃过滤器过滤除去,并将滤液用50ml纯水洗涤两次。将有机相在减压下蒸馏,并将所得侧链在减压(80℃,10小时)下干燥。GPC分析的结果是,侧链聚苯乙烯的分子量和分子量分布分别为Mw=9400,Mw/Mn=1.32。
实施例5
[TEMPO改性的乙烯—丁烯共聚物(TEMPO-EBR)的制备]
将10g马来酸酐接枝的乙烯丁烯共聚物(MAH-EBR)(Mw=102000,乙烯∶丁烯(摩尔比)=80∶20,接枝度0.75wt%)放入1L用氮气吹扫的两颈茄子型烧瓶中,然后向其中加入下述的0.21g(0.76mmol)TEMPO改性的化合物X,500ml干甲苯和20mg对甲苯磺酸单水合物,将混合物温度升高到80℃,并将混合物加热下搅拌6小时。将反应溶液倒入2L甲醇中,并将沉淀的聚合物用玻璃过滤器过滤。将玻璃过滤器上的聚合物用100ml甲醇洗涤3次。将聚合物在60℃下、15托的减压条件下干燥10小时。1H-NMR结果表明,得到了含有87%被式(6)表示的化合物酯化了的马来酸酐基的含极性基团的烯烃共聚物(TEMPO-EBR)。
[接枝烯烃共聚物(EBR-g-PS)的制备以及其侧链分子量的测定]
向200ml安装有机械搅拌器并用氮气吹扫的三颈烧瓶中加入上面制成的5.0g含极性基团的烯烃共聚物(含有0.33mmol末端改性基团),然后向其中加入70ml邻二甲苯和6.5ml苯乙烯单体,并将混合物的温度升高到120℃。搅拌12小时后,将反应溶液恢复到室温,然后倒入到1L甲醇中。将沉淀的聚合物用玻璃过滤器通过过滤分离,并将聚合物在80℃下、15托的减压条件下干燥10小时。1H-NMR测试表明,得到了含有42wt%苯乙烯共聚物的接枝烯烃共聚物(EBR-g-PS)。
将1.0g所得到的EBR-g-PS放入200ml茄子型烧瓶中,然后向其中加入100ml THF,3ml 5mol/L的氢氧化钠水溶液,并将悬浮液在50℃下搅拌一整夜。将反应溶液冷却到室温,并将由于水解裂开的EBR主链通过用玻璃过滤器过滤除去,并将滤液用50ml纯水洗涤两次。将有机相在减压下蒸馏,并将所得侧链进一步在减压(80℃,10小时)下干燥。GPC分析的结果是,侧链聚苯乙烯的分子量和分子量分布分别为Mw=4280,Mw/Mn=1.23。
实施例6
[乙烯/10-十一烯-1-醇共聚物的制备]
将10.0mg双(1,3-二甲基环戊二烯基)二氯化锆放入用氮气彻底吹扫的玻璃容器中,并加入甲基铝氧烷在甲苯中的溶液,其加入以铝原子计为17.2mmol,然后在23℃下用超声波照射15分钟。随后,加入适当量的甲苯将总体积调整到50ml,并用作催化剂溶液。
室温下氮气氛中,向内部体积为1L并被氮气充分吹扫的不锈钢反应釜中加入600ml含有21g 10-十一烯-1-醇的环己烷溶液。然后,向其中加入150mmol三异丁基铝,并用乙烯吹扫该体系。体系用乙烯加压并加热以使体系温度为50℃,总压力为0.7Mpa。将12.8ml上面制备的催化剂溶液用加压氮气推入反应釜来引发聚合。随后,聚合在50℃下总压力为0.7Mpa下进行30分钟,同时仅仅供给乙烯。引发聚合30分钟后,将50ml异丙醇(IPA)用加压氮气推入反应釜来终止聚合反应。
释压后,取出聚合物溶液,将每1L水中含有50ml盐酸的水溶液与聚合物溶液按照1∶1的比例在用均化器剧烈搅拌下进行接触,将催化剂残渣转移到水相中。该接触的混合溶液静置后,分离并取出水相,并用水洗涤两次来纯化和分离聚合物液相。
随后,将纯化分离的聚合物溶液用过量3倍的甲醇在剧烈搅拌下接触,沉淀出共聚物,通过过滤收集固体(共聚物)并用甲醇充分洗涤。通过过滤收集固体并在80℃、160mmHg的减压下在氮气流中干燥10小时。
由此得到25.7g乙烯/10-十一烯-1-醇共聚物。NMR分析的结果是,10-十一烯-1-醇含量为2.5mol%。GPC测试的结果是,Mw(重均分子量)为80,000,Mw/Mn(数均分子量)为2.5。从GPC测试和NMR分析的结果看,可以证实,羟基存在于所得聚烯烃的主链和/或侧链的末端。
[接枝烯烃共聚物(PE-g-PMMA)的制备]
将30ml甲苯加入到2.5g上述乙烯/10-十一烯-1-醇共聚物中,向其中加入1ml在己烷中的1.6M的正丁基锂,并将混合物室温下搅拌24小时。反应后,将淤浆冷却到-20℃,将通过过滤分离的聚乙烯冷却到-20℃,同时用甲苯洗涤几次。通过1H-NMR证实,锂被接到所得到的乙烯/10-十一烯-1-醇共聚物的末端。
将30ml苯和30ml甲基丙烯酸甲酯(MMA)加入到2.0g所得到的末端接有锂的乙烯/10-十一烯-1-醇共聚物中,并将该混合物20℃下用磁搅拌器搅拌下反应100小时。加入甲醇终止反应,并将反应混合物用甲烷充分洗涤,然后在45℃减压下干燥。
MAA的转化率为10.5%,所得接枝烯烃共聚物(PE-g-PMMA)中,聚MMA片断的三单元组构规整度为77%。通过13C-NMR证实,所得接枝烯烃共聚物是带有通过醚氧基键合到聚MMA上的聚乙烯的接枝共聚物。
实施例7
[接枝烯烃共聚物(PE-g-PS)的制备]
将实施例6制备的10g Li封端的乙烯/10-十一烯-1-醇共聚物放入密封烧瓶中,并加入5.0g干苯乙烯(St)和50mlTHF来引发反应。将混合物室温下搅拌135小时,然后加入10ml甲醇终止反应。将沉淀的聚合物用丙酮和庚烷在氮气氛下,于Soxhlet萃取装置中萃取并分离24小时,得到作为不可溶组分的接枝烯烃共聚物(PE-g-PS)。
该方式中制成的接枝烯烃共聚物(PE-g-PS),其MFR(230℃)为14g/10min,Mw/Mn为2.5。
实施例8
将实施例6中制成的接枝烯烃共聚物(PE-g-PMMA)在200℃下模压成型和管成型(tube-molded)得到测试样品。将该测试样品按照下述方式测试多种物理性能。结果表示在表1中。
[JIS A硬度(A)]
按照JIS K7215测试。
[拉伸强度]
根据JIS K6251,23℃下用JIS哑铃3号,在夹具(span)之间距离为20mm下,以500mm/sec的拉伸速率下进行测试。
[粘合力测试]
根据JIS K6256进行测试。
[TMA(针入度温度:耐热性)]
针入度温度是用直径为1.8mm的压痕器,在2kg/cm2和升温速度为5℃/min的条件下进行测试的。
[表面硬度(肖氏A硬度)]
根据ASTM D676进行测试。
[耐划痕性(Martens硬度)]
Martens硬度:用金刚石针在20g载荷下在冲压测试样品上划出一划痕,测试划痕宽度,将该宽度的倒数作为Martens硬度。
[反复脉冲]
在一1mm导线上形成一内部导电层,并在其周围形成一层测试共聚物的绝缘层(厚度1.5mm)。将所得电缆进行闪电脉冲测试(以5分钟的间隔施加100KV)。
[击穿电压]
根据ASTM D-149,25℃下用1mm的冲压样片进行测试。
对比实施例1
除了使用乙烯/丁烯共聚物(乙烯含量88mol%,密度885kg/m3,Mw 155,000,Mw/Mn 1.87)之外,按照与实施例8相同的方式测试物理性能。结果表示在表1中。
表1
实施例8 | 对比实施例1 | |
样品 | 接枝烯烃共聚物(PE-g-PMMA) | 乙烯/丁烯共聚物 |
TMA(℃) | 106 | 80 |
肖氏硬度 | 75 | 88 |
Martens硬度(1/mm) | 17 | 9 |
反复脉冲(击穿频率) | 9 | 3 |
电介质击穿电压(kV/mm) | 62 | 58 |
显然,实施例8的接枝烯烃共聚物在耐热性、柔韧性、抗划痕性、反复脉冲和电介质击穿电压方面都优于非接枝烯烃共聚物。
Claims (8)
1.一种接枝烯烃共聚物,它包括式(1)表示的组成嵌段(A)和式(2)表示的组成嵌段(B):
其中,式(1)中,R1表示氢原子或C1-18的直链或支链脂肪烃基;式(2)中,R2表示C1-18的直链或支链脂族或芳族烃基;F表示杂原子或含杂原子的连接基团;Z表示含有至少一个选自氧原子、氮原子、卤原子和芳基的聚合物片段,其分子量分布为1.0-3.0;W表示选自醇羟基、酚羟基、羧酸基、羧酸酯基、酸酐基、氨基、环氧基、甲硅烷氧基和巯基的基团;n是1-3的整数,m是0,1或2,前提是当n为2或3时,Z彼此可以相同或不同,当m为2时,W彼此可以相同或不同;W可以与R2的相同或不同原子键合形成环状结构。
2.根据权利要求1所述的接枝烯烃共聚物,其中式(2)中用F表示的连接基团含有至少一个选自羰基和芳基的基团。
3.一种制备权利要求1或2所述的接枝烯烃共聚物的方法,它包括顺序进行下述步骤1、2和3:
步骤1:合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G),
步骤2:将官能团(G)转变为能够引发自由基聚合的基团的步骤,和
步骤3:在接枝烯烃共聚物中式(2)表示的组成嵌段(B)上,通过自由基聚合基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
4.一种制备权利要求1-3中任意一项所述的接枝烯烃共聚物的方法,它包括顺序进行下述步骤1′、2′和3′:
步骤1′:合成含有极性基团的烯烃共聚物(Q)的步骤,所述共聚物含有至少一种选自羟基、羧酸基、酯基、氨基、环氧基、硅烷醇基和酸酐基的官能团(G),
步骤2′:将官能团(G)转变为能够引发阴离子聚合的基团的步骤,和
步骤3′:在含极性基团的接枝烯烃共聚物中式(2)表示的组成嵌段(B)上,通过阴离子聚合(不包括开环阴离子聚合)基本上包括含碳碳双键化合物(R)的单体接上聚合物片段(Z)的步骤,所述化合物(R)含有至少一个选自氧原子、氮原子、卤原子和芳基的基团。
5.一种制备权利要求3或4所述的接枝烯烃共聚物的方法,其中官能团(G)是伯羟基或马来酸酐基。
6.一种含有权利要求1或2所述的接枝烯烃共聚物的热塑性树脂组合物。
7.含有权利要求1或2的接枝烯烃共聚物的薄膜、片材、粘合树脂、相容性试剂、树脂改性剂、润滑油改性剂、水泥改性剂、建筑材料/市政工程材料、用于电器和电子部件的电绝缘材料、磁记录介质、汽车内外材料、汽油箱、填料分散剂或分散剂、水乳浊液、涂料基质、医药和卫生材料和杂物。
8.含有权利要求6所述的热塑性树脂组合物的薄膜、片材、粘合树脂、相容性试剂、树脂改性剂、润滑油改性剂、水泥改性剂、建筑材料/市政工程材料、用于电器和电子部件的电绝缘材料、磁记录介质、汽车内外材料、汽油箱、填料分散剂或分散剂、水乳浊液、涂料基质、医药和卫生材料和杂物。
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2002
- 2002-10-11 JP JP2002298420A patent/JP4208543B2/ja not_active Expired - Lifetime
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- 2003-10-08 CN CNB2003101138858A patent/CN1259353C/zh not_active Expired - Lifetime
- 2003-10-09 US US10/681,181 patent/US7022763B2/en not_active Expired - Lifetime
- 2003-10-10 DE DE60301042T patent/DE60301042T2/de not_active Expired - Lifetime
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Cited By (3)
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CN101223200B (zh) * | 2005-07-12 | 2011-07-06 | 三井化学株式会社 | 聚烯烃系杂化聚合物及其制造方法 |
CN111152532A (zh) * | 2019-12-27 | 2020-05-15 | 东莞市正新包装制品有限公司 | Pe收缩膜 |
CN111152532B (zh) * | 2019-12-27 | 2022-10-04 | 东莞市正新包装制品有限公司 | Pe收缩膜 |
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US20040110903A1 (en) | 2004-06-10 |
KR20040033267A (ko) | 2004-04-21 |
DE60301042T2 (de) | 2006-04-20 |
DE60301042D1 (de) | 2005-08-25 |
KR100576637B1 (ko) | 2006-05-08 |
JP4208543B2 (ja) | 2009-01-14 |
EP1408058B1 (en) | 2005-07-20 |
CN1259353C (zh) | 2006-06-14 |
EP1408058A1 (en) | 2004-04-14 |
US7022763B2 (en) | 2006-04-04 |
JP2004131620A (ja) | 2004-04-30 |
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