CN103387733A - 用于阻燃材料的高分子、高分子混掺物、与包含它们的阻燃材料 - Google Patents
用于阻燃材料的高分子、高分子混掺物、与包含它们的阻燃材料 Download PDFInfo
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- CN103387733A CN103387733A CN201210229265XA CN201210229265A CN103387733A CN 103387733 A CN103387733 A CN 103387733A CN 201210229265X A CN201210229265X A CN 201210229265XA CN 201210229265 A CN201210229265 A CN 201210229265A CN 103387733 A CN103387733 A CN 103387733A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 10
- 229920002959 polymer blend Polymers 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 48
- 239000011574 phosphorus Substances 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 44
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- -1 Hydrogen Chemical class 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 150000002829 nitrogen Chemical class 0.000 claims description 16
- 150000003017 phosphorus Chemical class 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
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- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 239000000047 product Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 4
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- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- JQRBBVRBGGXTLZ-UHFFFAOYSA-N 2-methoxyethanol Chemical compound COCCO.COCCO JQRBBVRBGGXTLZ-UHFFFAOYSA-N 0.000 description 1
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- YKIPUOUMDPLJAZ-UHFFFAOYSA-N C=Cc1ccc(COC(CC2)=CC=C2C2=NC(N)=NC(N)N2)cc1 Chemical compound C=Cc1ccc(COC(CC2)=CC=C2C2=NC(N)=NC(N)N2)cc1 YKIPUOUMDPLJAZ-UHFFFAOYSA-N 0.000 description 1
- 101000609219 Homo sapiens Polyadenylate-binding protein 4 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 102100039424 Polyadenylate-binding protein 4 Human genes 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DORQGZNYICOAAZ-UHFFFAOYSA-N azane cyanamide Chemical compound N.NC#N DORQGZNYICOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
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- C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
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- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
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- C08F12/26—Nitrogen
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Abstract
本发明提供一种用于阻燃材料的高分子,其为磷系单体聚合而成的聚合物、氮系单体聚合而成的聚合物、或者磷系单体与氮系单体共聚而成的聚合物;其中磷系单体的结构如下:R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;其中氮系单体的结构如下:R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。本发明还提供一种用于阻燃材料的高分子混掺物。本发明还提供一种包含所述高分子或高分子混掺物的阻燃材料。
Description
技术领域
本发明是关于一种用于阻燃材料的高分子、高分子混掺物、及包含它们的阻燃材料。
背景技术
阻燃剂(Flame retarder)是指添加于可燃性材料(如塑料、橡胶、纤维、纸、木材等)中使其难以燃烧或是火焰不扩展的药剂。近几十年来应用阻燃剂的领域广泛,举凡各种民生化工与电子产品皆可见其应用。常见阻燃剂皆以卤素为主,然而2006年7月1日欧盟颁布了RoHS(有害物质限用)指令规定在3C产业的用途上(如计算机、电视等产品中的基板与塑料外壳等)禁用卤素阻燃剂。开发高性能无卤阻燃剂,以便未来法规趋严时能有所因应并保持竞争力,成为一重要课题。
发明内容
本发明的目的在于提供一种具有高性能的用于阻燃材料的高分子,其与现有技术中常见的阻燃剂相比较,在高温下的外观不会有出油的现象,且均具有250C的热分解温度(Td)。
本发明的另一目的在于提供一种包含上述高分子的、用于阻燃材料的高分子混掺物。
本发明的再一目的在于提供一种包含上述高分子或高分子混掺物的阻燃材料。
本发明一实施方式提供一种用于阻燃材料的高分子,其为磷系单体聚合而成的聚合物、氮系单体聚合而成的聚合物、或磷系单体与氮系单体共聚而成的聚合物;其中磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;其中氮系单体的结构如下:R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
本发明一实施方式提供一种用于阻燃材料的高分子混掺物,是磷系单体聚合而成的聚合物、氮系单体聚合而成的聚合物、与该磷系单体与该氮系单体共聚而成的聚合物中至少二者的混掺物,其中该磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;
其中该氮系单体的结构如下:
R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
本发明一实施方式提供一种阻燃材料,包括:无卤阻燃剂,其为磷系单体聚合而成的聚合物、氮系单体聚合而成的聚合物、磷系单体与氮系单体共聚而成的聚合物、或上述至少二者的混掺物;其中磷系单体的结构如下:R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;其中氮系单体的结构如下:R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;以及热固性树脂,其中无卤阻燃剂与热固性树脂的重量比约介于1:1至1:200之间。
本发明一实施方式提供一种阻燃材料,包括:无卤阻燃剂,其为磷系单体聚合而成的聚合物、氮系单体聚合而成的聚合物、磷系单体与氮系单体共聚而成的聚合物、或上述至少二者的混掺物;其中磷系单体的结构如下:R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;其中氮系单体的结构如下:R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;以及热塑性树脂,其中无卤阻燃剂与热塑性树脂的重量比约介于1:1至1:200之间。
本发明的优点在于:与现有技术中常见的阻燃剂,例如DOPO、三聚氰胺、或聚磷酸铵相比,本发明的阻燃材料因包含了本发明的高分子或高分子混掺物而在高温下的外观不会有出油的现象,且均具有250C的热分解温度(Td)。
具体实施方式
本发明一实施方式中,取磷系单体如式1聚合形成的高分子作为无卤阻燃剂。
在式1中,R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
本发明一实施方式中,取氮系单体如式2聚合形成的高分子作为无卤阻燃剂。
在式2中,R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
在本发明一实施方式中,取氮系单体与磷系单体共聚形成的高分子作为无卤阻燃剂。在此实施例中,氮系单体与磷系单体的摩尔比约介于1:1至1:10之间。上述聚合物的阻燃效果,优于氮系单体的聚合物与磷系单体的聚合物。若聚合物中氮系单体的摩尔比例过低,则聚合物的阻燃效果将与磷系单体的聚合物类似。若聚合物中磷系单体的摩尔比例过低,则聚合物的阻燃效果将与氮系单体的聚合物类似。
本发明一实施方式中,混合氮系单体的聚合物与磷系单体的聚合物,以作为无卤阻燃剂;其中氮系单体的聚合物与磷系单体的聚合物的重量比约为1:1~1:5。
在本发明一实施方式中,混合氮系单体的聚合物、磷系单体的聚合物、与氮系单体与磷系单体的聚合物中至少两者,以作为无卤阻燃剂。
上述的聚合物的重量平均分子量约介于1,000至1,000,000之间或约介于5,000至15,000之间。若聚合物的重量平均分子量过高,则缺乏加工性。若聚合物的重量平均分子量过低,则缺乏阻燃性与耐热性。
在本发明一实施方式中,上述的磷系单体的结构如式3所示:
上述的无卤阻燃剂可进一步与热塑性树脂或热固性树脂混合,以形成阻燃材料。热塑性树脂可为聚酰胺、聚烯烃(如C2~C6的聚烯烃)、或苯乙烯-乙烯-丁二烯-苯乙烯共聚物。热固性树脂可为环氧树脂。当阻燃材料包含热固性树脂与无卤阻燃剂时,无卤阻燃剂与该热固性树脂的重量比约介于1:1至1:200之间或约介于1:1至1:10。当阻燃材料包含热塑性树脂与无卤阻燃剂时,无卤阻燃剂与该热塑性树脂的重量比约介于1:1至1:200之间或约介于1:1至1:10。若无卤阻燃剂的比例过高,则固含量过多而无法加工。若无卤阻燃剂的比例过低,则无法使阻燃材料具有足够的阻燃效果。值得注意的是,上述无卤阻燃剂与热固性树脂(或热塑性树脂)彼此混合,两者之间并未产生交联或具有共价键结。
在本发明一实施方式中,上述的阻燃材料可进一步含有其它添加剂,比如加工助剂、颜料、其它市售阻燃剂、或其它常见添加剂。
为了让本发明的上述和其它目的、特征、和优点能更明显易懂,下文特举数实施例,作详细说明如下:
【实施例】
合成例1
将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(100.0克,0.46摩尔(AldrichCo.))置于2公升圆底瓶内,加入600毫升的乙醇中搅拌溶解,再加入300毫升的双氧水溶液,加热回流反应12小时,运用薄层色层分析法,点片追踪确定反应完全。冷却至室温,利用真空旋转浓缩机移除溶剂,用异丙醇和水(3比1体积比)再结晶,过滤取固体;将过滤物放入真空干燥箱干燥,得到白色固体,产率为95%。上述反应如式5,而产物的氢谱如下:1H NMR(400MHz,DMSO-d6,ppm):4.41(s,1H),7.23-7.31(m,2H),7.41-7.56(m,2H),7.72-7.83(m,2H),8.11-8.15(m,2H)。
(式5)
取式5的产物(50.0克,0.22摩尔)置于500毫升双颈瓶内,在氮气系统下先加入300毫升的无水四氢呋喃混合搅拌溶解,随后加入甲基丙烯酸缩水甘油酯(39.8克,0.28摩尔(Adrich Co.))搅拌均匀,再打入液状催化剂N,N-二甲基苄胺(0.87克,6.5毫摩尔),加热至70°C后反应一天。运用薄层色层分析法,点片追踪确定反应完全。冷却至室温,利用真空旋转浓缩机移除溶剂,以正己烷洗涤,用真空抽器干燥,得到半透明粘稠液体,产率85%。上述反应如式6,而产物的氢谱如下:1H NMR(400MHz,CDCl3,ppm):1.90(s,3H),1.96(s,1H),3.45-3.50(m,2H),4.10-4.19(m,3H),5.55(s,1H),6.07(s,1H),7.23-7.30(m,2H),7.40-7.53(m,2H),7.74-8.00(m,4H)。
(式6)
取式6的产物(50.0克,0.13摩尔)和催化剂2,2'-二氰基-2,2'-偶氮丙烷(1.2克,6.7毫摩尔)置于1公升圆底瓶内,在氮气系统下,加入500毫升的无水四氢呋喃混合搅拌溶解,加热至65°C后反应一天。将反应后的混合物冷却至室温,再倒入到乙醚中并析出大量白色固体。将乙醚悬浮液过滤后,取滤饼放入真空干燥箱干燥,得到白色固体,产率为80%。上述反应如式7,而产物重量平均分子量为8,600,其氢谱如下:1H NMR(400MHz,DMSO-d6,ppm):0.67(br,5H),3.80-3.97(br,m,4H),5.28-5.40(br,m,1H),7.21-7.34(br,m,3H),7.49(br,1H),7.69(br,1H),7.85(br,1H),8.19(br,2H)。
合成例2
将4-羟基苯甲腈(50.0克,0.42摩尔(Adrich Co.))、碳酸钾(116.0克,0.84摩尔)和碘化钾(5.0克,30毫摩尔)置于1公升圆底瓶内,加入600毫升的丙酮(acetone)混合搅拌,然后慢慢滴入4-氯甲基苯乙烯(78.3克,0.51摩尔(AdrichCo.))加热回流48小时,运用薄层色层分析法,点片追踪确定反应完全。冷却至室温,过滤并用丙酮洗涤取滤液,真空旋转浓缩移除溶剂,再利用真空旋转浓缩机移除溶剂,最后以正己烷再结晶,过滤取固体。将过滤物放入真空干燥箱干燥,得到白色固体,产率为93%。上述反应如式8,而产物的氢谱如下:1H NMR(400MHz,CDCl3,ppm):5.10(s,2H),5.28(d,J=14.5Hz,1H),5.77(d,J=23.4Hz,1H),6.73(dd,J1=14.5Hz,J2=23.4Hz,3H),7.02(d,J=9.1Hz,2H),7.37(d,J=10.9Hz,2H),7.44(d,J=10.9Hz,2H),7.59(d,J=9.1Hz,2H)。
(式8)
将式8的产物(40.0克,0.17摩尔)和氢氧化钾(38.1克,0.68摩尔)置于500毫升圆底瓶内,加入160毫升的乙二醇甲醚(2-methoxy-ethanol)混合搅拌,然后慢慢加入氰基胍(dicyandiamine,78.3克,0.51摩尔)加热至90°C后反应8小时,运用薄层色层分析法,点片追踪确定反应完全。冷却至室温,倒入到冰水中,此时大量白色固体析出,过滤并用水洗涤取固体,在用异丙醇和水(5比1体积比)再结晶,过滤取固体;将过滤物放入真空干燥箱干燥,得到白色固体,产率为88%。上述反应如式9,而产物的氢谱如下:1H NMR(400MHz,DMSO-d6,ppm):5.14(s,2H),5.26(d,J=10.9Hz,1H),5.84(d,J=17.7Hz,1H),6.66(s,4H),6.73(dd,J1=10.9Hz,J2=17.7Hz,1H),7.07(d,J=8.8Hz,2H),7.43(d,J=8.1Hz,2H),7.49(d,J=8.1Hz,2H),8.19(d,J=8.8Hz,2H).
取式9的产物化合物(50.0克,0.15摩尔)和催化剂2,2'-二氰基-2,2'-偶氮丙烷(AIBN,1.3克,7.6毫摩尔)置于1公升圆底瓶内,在氮气系统下,加入500毫升的无水二甲基甲酰胺混合搅拌溶解,加热至65°C后反应一天。冷却至室温,倒入到甲醇中大量白色析出,过滤取固体。将过滤物放入真空干燥箱干燥,得到白色固体,产率为75%。上述反应如式10,而产物重量平均分子量为11,500,其氢谱如下:1H NMR(400MHz,DMSO-d6,ppm):1.65(br,2H),4.93(br,2H),6.63(br,6H),6.92(br,m,4H),8.18(br,2H).
合成例3
取前述结构为式6的化合物(25.0克,66毫摩尔)、结构为式9的化合物(21.3克,66毫摩尔)、和催化剂2,2'-二氰基-2,2'-偶氮丙烷(1.1克,6.8毫摩尔)置于1公升圆底瓶内,在氮气系统下,加入460毫升的无水二甲基甲酰胺混合搅拌溶解,加热于65°C下反应一天。冷却至室温,倒入到甲醇和乙醚(4/1体积比)中大量白色析出,过滤取固体。将过滤物放入真空干燥箱干燥,得到白色固体,产率为60%。上述反应如式11,而产物重量平均分子量为12,500,其氢谱如下:1H NMR(400MHz,DMSO-d6,ppm):0.66-1.60(br,m,8H),3.74-3.96(br,m,4H),4.93-5.27(br,m,3H),6.48-7.62(br,m,12H),7.83-7.94(br,m,4H),8.11-8.18(br,4H)。
(式11)
在式11的产物中,m与n的比例为1:1,且式11的产物为无规聚合物。
实施例1
取50重量份的聚丙烯(购自李长荣化工的PT100)、50重量份的苯乙烯-乙烯-丁二烯-苯乙烯共聚物(SEBS,购自台化的3151)、不同重量份的式7的产物、不同重量份的式10的产物、不同重量份的式11的产物、不同重量份的DOPO、不同重量份的三聚氰胺、不同重量份的聚磷酸铵(恒桥APP-1),混合后以热压成型法(190°C,5~10分钟)制成12.5cm×1.3cm×0.3cm的试片,上述试片组成如表1所示。
表1
批次 | 聚丙烯 | SEBS | 式7的产物 | 式10的产物 | 式11的产物 | DOPO | 三聚氰胺 | 聚磷酸铵 |
a | 50 | 50 | 20 | 0 | 0 | 0 | 0 | 0 |
b | 50 | 50 | 0 | 20 | 0 | 0 | 0 | 0 |
c | 50 | 50 | 10 | 10 | 0 | 0 | 0 | 0 |
d | 50 | 50 | 20 | 10 | 0 | 0 | 0 | 0 |
e | 50 | 50 | 0 | 0 | 20 | 0 | 0 | 0 |
f | 50 | 50 | 0 | 0 | 0 | 20 | 0 | 0 |
g | 50 | 50 | 0 | 0 | 0 | 0 | 20 | 0 |
h | 50 | 50 | 0 | 0 | 0 | 0 | 0 | 20 |
接着测量试片的分解温度(Td,热重损失5%的温度)、800°C下的成碳量、氧极限指数(LOI)、UL-94-V、以及加热至190°C后的试片外观、及加热至90°C下两天后的试片外观,如表2所示。
表2
批次 | 热分解温度(℃) | 成碳量(%) | LOI | UL94-V* | 190℃下的外观 | 90℃下两天后的外观 |
a | 258 | 9.1 | 21 | V1 | 未出油 | 未出油 |
b | 343 | 1.6 | 19 | V2 | 未出油 | 未出油 |
c | 275 | 6.3 | 20 | V1 | 未出油 | 未出油 |
d | 268 | 7.7 | 22 | V0 | 未出油 | 未出油 |
e | 290 | 15.6 | 23 | V0 | 未出油 | 未出油 |
f | 220 | 8.8 | 20 | V1 | 出油 | 出油 |
g | 276 | 0.8 | 19 | V2 | 未出油 | 未出油 |
h | 288 | 26.6 | 23 | V0 | 出油 | 出油 |
在表1中,批次a至e采用合成例1-3的产物作为阻燃剂,而批次f至h采用DOPO、三聚氰胺、或聚磷酸铵作为阻燃剂。由表2的比对可知,本发明的阻燃剂在高温下的外观不会有出油(blooming)的现象,且均具有250°C的热分解温度(Td)。
虽然本发明已以数个较佳实施例揭露如上,然其并非用以限定本发明,任何熟习此技艺者,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (11)
1.一种用于阻燃材料的高分子,其为一磷系单体聚合而成的聚合物、一氮系单体聚合而成的聚合物、或该磷系单体与该氮系单体共聚而成的聚合物;
其中该磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;
其中该氮系单体的结构如下:
R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
4.如权利要求1所述的用于阻燃材料的高分子,其中该磷系单体与该氮系单体共聚而成的聚合物之中,该磷系单体与该氮系单体的摩尔比介于1:1至10:1之间。
5.如权利要求1所述的用于阻燃材料的高分子,其中该磷系单体聚合而成的聚合物、该氮系单体聚合而成的聚合物、或该磷系单体与该氮系单体共聚而成的聚合物的重均分子量介于1,000至1,000,000之间。
6.一种用于阻燃材料的高分子混掺物,其为一磷系单体聚合而成的聚合物、一氮系单体聚合而成的聚合物、与该磷系单体与该氮系单体共聚而成的聚合物中至少二者的混掺物,其中该磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;
其中该氮系单体的结构如下:
R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基。
7.如权利要求6所述的用于阻燃材料的高分子混掺物,其为1重量份的该氮系单体聚合而成的聚合物与1至5重量份的该磷系单体聚合而成的聚合物的混掺物。
8.一种阻燃材料,包括:
一无卤阻燃剂,其为一磷系单体聚合而成的聚合物、一氮系单体聚合而成的聚合物、该磷系单体与该氮系单体共聚而成的聚合物、或上述至少二者的混掺物;
其中该磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;
其中该氮系单体的结构如下:
R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;以及
一热固性树脂,
其中该无卤阻燃剂与该热固性树脂的重量比介于1:1至1:200之间。
9.如权利要求8所述的阻燃材料,其中该热固性树脂为环氧树脂。
10.一种阻燃材料,包括:
一无卤阻燃剂,其为一磷系单体聚合而成的聚合物、一氮系单体聚合而成的聚合物、该磷系单体与该氮系单体共聚而成的聚合物、或上述至少二者的混掺物;
其中该磷系单体的结构如下:
R1是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R2是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;
其中该氮系单体的结构如下:
R3是氢、苯基、C1-12的烷苯基、C1-12的烷基、C1-12的醚基、C1-12的烷醇基、或C1-12的羟基烷基;
R4是苯撑基、C1-12的烷苯撑基、C1-12的烷撑基、C1-12的醚撑基、C1-12的烷醇撑基、或C1-12的羟基烷撑基;以及
一热塑性树脂,
其中该无卤阻燃剂与该热塑性树脂的重量比介于1:1至1:200之间。
11.如权利要求10所述的阻燃材料,其中该热塑性树脂为聚酰胺、聚烯烃、或苯乙烯-乙烯-丁二烯-苯乙烯聚合物。
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