CN101405334B - 无机-有机纳米复合材料 - Google Patents
无机-有机纳米复合材料 Download PDFInfo
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- CN101405334B CN101405334B CN2007800101119A CN200780010111A CN101405334B CN 101405334 B CN101405334 B CN 101405334B CN 2007800101119 A CN2007800101119 A CN 2007800101119A CN 200780010111 A CN200780010111 A CN 200780010111A CN 101405334 B CN101405334 B CN 101405334B
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- CN
- China
- Prior art keywords
- inorganic
- organopolysiloxane
- organic nanocomposite
- organic
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 43
- -1 caulks Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 44
- 239000004927 clay Substances 0.000 claims description 42
- 229910052570 clay Inorganic materials 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052900 illite Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002449 FKM Polymers 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001470 polyketone Polymers 0.000 claims description 4
- 229920006216 polyvinyl aromatic Polymers 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 241000353097 Molva molva Species 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920001291 polyvinyl halide Polymers 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 229910021647 smectite Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910000273 nontronite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910000276 sauconite Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 2
- 229920001971 elastomer Polymers 0.000 claims 2
- 239000000806 elastomer Substances 0.000 claims 2
- 229920003002 synthetic resin Polymers 0.000 claims 2
- 239000000057 synthetic resin Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000002902 organometallic compounds Chemical group 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000565 sealant Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 22
- 150000001721 carbon Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012802 nanoclay Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229940085991 phosphate ion Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000138 intercalating agent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 101150040772 CALY gene Proteins 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
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- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- WSFMFXQNYPNYGG-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC WSFMFXQNYPNYGG-UHFFFAOYSA-M 0.000 description 1
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
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- 239000006072 paste Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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Abstract
本发明涉及改进的纳米复合材料组合物及其制备和使用方法。本发明还涉及这些无机-有机纳米复合材料在组合物，例如涂料、密封剂、填隙剂、粘合剂中的用途，和作为含固体聚合物的组合物用添加剂的用途。
Description
发明领域
本发明一般地涉及改进的纳米复合材料组合物及其制备和使用方法。更具体地，本发明涉及无机-有机纳米复合材料及其制备方法。本发明还涉及这些无机-有机纳米复合材料组合物在例如涂料、密封剂、填隙剂(caulk)、粘合剂和塑料中的用途。
发明背景
无机-有机纳米复合材料可显示出优于其单独组分的机械性能。为了优化这些材料的性能，通常希望在纳米长度尺度上在有机基体内分散无机组分。可打碎成纳米级构造单元(building block)的粘土和其他层状无机材料可用于制备无机-有机纳米复合材料。
添加粘土材料到聚合物中是本领域已知的，然而，掺入粘土到聚合物内不可能提供聚合物的物理性能，尤其机械性能的所需改进。这可能由于例如在粘土和聚合物的界面处或在材料内粘土和聚合物的边界处缺少亲和力之故。通过使粘土材料均匀地分散在整个聚合物当中，粘土和聚合物之间的亲和力可改进所得纳米复合材料的物理性能。若均匀地分散的话，粘土相对较大的表面积可在粘土和聚合物之间提供更多的界面，和随后可通过在这些界面处降低聚合物链的活动性来改进物理性能。相反，在粘土和聚合物之间缺少亲和力时，由于具有集中的粘土团(pocket)，而不是均匀地分散在整个聚合物当中，因此可负面影响组合物的强度和均匀度。粘土和聚合物之间的亲和力与下述事实有关：粘土在本性上通常是亲水的，而聚合物通常是疏水的。
粘土矿典型地由微粒状并具有扁平状晶态(platy habit)的水合硅酸铝构成。典型的粘土矿的晶体结构是由与AlO(OH)2八面体层相连的SiO4四面体层的组合构成的多层结构。粘土矿基于其成分层和阳离子的组合而变化。通常地发生粘土矿的阳离子的同晶型取代，例如Al3+或Fe3+取代四面体网络内的Si4+离子，或者Al3+、Mg2+或Fe2+取代八面体网络内的其他阳离子，以及可赋予粘土结构净的负电荷。在粘土坑道(galley)内天然存在的元素，例如水分子或钠或钾离子因这一净的负电荷被吸收到粘土层的表面上。
为了促进粘土和聚合物在界面处更大的亲和性并提供粘土在聚合物内的均匀分散，可改性粘土的层间表面化学性质，使得硅酸盐层不那么亲水。
烷基铵离子，例如鎓盐常用于制备纳米复合材料的粘土分散体。典型的烷基铵离子的基本化学式为CH3-(CH2)n-NH3 +，其中n为1-18。认为烷基铵离子还容易与在粘土小片(platelet)内存在的天然存在的阳离子发生交换，从而产生插层状态(intercalated state)。此外，认为烷基铵离子可增加粘土层之间的空间且还可降低粘土的表面能，从而允许具有不同极性的有机物质插在粘土层之间。
仍需要具有改进的性能的纳米复合材料。此处公开的发明提供成本可行和有效的方法生产新型无机-有机纳米复合材料组合物，它特别地适合于在密封剂中使用，其中所需的柔软度、可加工性和弹性特征是重要的性能标准。
发明概述
根据本发明，提供无机-有机纳米复合材料，它包括至少一种无机组分和至少一种有机组分，所述无机组分是层状无机纳米颗粒，和所述有机组分是季铵有机基聚硅氧烷。
本发明的新型的无机-有机纳米复合材料可用作填料用于宽泛的各种含聚合物树脂的组合物中，具体地作为这种组合物的填料，预计用于如密封剂、涂料和粘合剂的用途。
发明详述
根据本发明，提供一种无机-有机纳米复合材料，它包括至少一种无机组分和至少一种有机组分，所述无机组分是层状无机纳米颗粒，和所述有机组分是季铵有机基聚硅氧烷。当描述本发明时，下述术语具有下述含义，除非另有说明。
定义
本文使用的术语＂剥落＂描述这样一个过程，其中纳米粘土小片的小包在聚合物基体中彼此分离。在剥落过程中，在各小包最外区的小片裂开，暴露更多的小片用于分离。
本文使用的术语＂坑道(galley)＂描述粘土小片的平行的层之间的空间。坑道空间根据占据空间的分子或聚合物的性质而变。各纳米粘土小片之间的层间空间同样根据占据空间的分子的类型而变。
本文使用的术语＂插层剂(intercalant)＂包括能进入粘土坑道并与其表面结合的任何无机或有机化合物。
本文使用的术语＂插入物(intercalate)＂是指粘土-化学复合物，其中由于表面改性过程增加粘土坑道空间。在适当的温度和剪切条件下，插入物能在树脂基体中剥落。
本文使用的术语＂插层反应(intercalation)＂是指形成插入物的过程。
本文使用的表述＂无机纳米颗粒＂描述其中一个或更多个尺寸(例如长度、宽度或厚度)在纳米大小范围且能进行离子交换的层状无机材料，例如粘土。
本文使用的表述＂改性粘土＂是指经能与存在于粘土的层间表面的阳离子进行离子交换反应的任何无机或有机化合物处理的粘土材料，例如纳米粘土。
本文使用的术语＂纳米粘土＂描述具有独特形态的粘土材料，其中一个方向的尺寸为纳米范围。纳米粘土可和与构成粘土颗粒的各层之间的表面离子结合的插层剂形成化学复合物。插层剂和粘土颗粒的这种缔合导致材料可与许多不同种类的基质树脂(host resin)相容，从而使粘土填料分散其中。
本文使用的术语“纳米颗粒”是指粒度通常小于约1000nm，该粒度一般以直径确定。
本文使用的术语“小片”是指层状材料的单个层。
无机-有机纳米复合材料中的无机纳米颗粒可为天然或合成的(例如绿土粘土)且应具有某些离子交换性能，例如绿土粘土、累托石、蛭石、伊利石、云母及其合成的类似物，包括合成粘土、合成的云母-蒙脱土和四硅酸云母。
在第一种实施方案中，所述纳米颗粒的平均最大横向尺寸(宽度)可为约0.01μm至约10μm，在第二种实施方案中，为约0.05μm至约2μm，在第三种实施方案中，为约0.1μm至约1μm。在第一种实施方案中，所述纳米颗粒的平均最大纵向尺寸(厚度)通常可在约0.5nm至约10nm之间变化，在第二种实施方案中，为约1nm至约5nm。
本发明的可用的无机纳米颗粒材料包括天然或合成的页硅酸盐，尤其是绿土粘土，例如蒙脱土、蒙脱土钠、蒙脱土钙、蒙脱土镁、绿脱石、贝得石、铬岭石、合成粘土、锂蒙脱石、皂石、锌蒙脱石、NaSiO13(OH)3.3H2O(magadite)、水羟硅钠石、sobockite、svindordite、富镁蒙脱石、滑石、云母、高岭石、蛭石、多水高岭石、铝酸盐氧化物或水滑石、云母矿物例如伊利石和混合的层状伊利石/绿土矿物例如累托石、tarosovite、三八面体伊利石和伊利石与以上所述的一种或更多种粘土矿物的混合物。充分吸收有机分子以增加相邻页硅酸盐小片之间的层间间距为至少约5埃或至少约10埃(当测量干燥页硅酸盐时)的任何可溶胀的层状材料均可用于制备本发明的无机-有机纳米复合材料。
本发明的改性的无机纳米颗粒通过定量的具有可交换的阳离子(例如Na+、Ca2+、Al3+、Fe2+、Fe3+和Mg2+)的层状无机颗粒与至少一种含铵的有机基聚硅氧烷接触制得。所得到的改性的颗粒为具有插层的有机基聚硅氧烷铵离子的无机-有机纳米复合材料。
含铵的有机基聚硅氧烷必须包括至少一种铵基且可包括两种或更多个铵基。季铵基可位于有机基聚硅氧烷的末端和/或沿着硅氧烷主链。一类可用的含铵的有机基聚硅氧烷具有以下通式：
MaDbD′c
其中＂a＂为2，＂b＂等于或大于1，且＂c＂为0或正数；M为
[R3 zNR4]3-x-yR1 xR2 ySiO1/2
其中＂x＂为0、1或2，且＂y＂为0或1，条件是x+y小于或等于2，＂z＂为2，R1和R2各自独立地为至多60个碳的单价烃基；R3选自H和至多60个碳的单价烃基；R4是至多60个碳的单价烃基；D是
R5R6SiO1/2
其中R5和R6各自独立地为至多60个碳原子的单价烃基；和D′是
R7R8SiO2/2
其中R7和R8各自独立地为具有下述通式的含胺的单价烃基：
[R9 aNR10]
其中＂a＂为2，R9选自H和至多60个碳的单价烃基；R10为至多60个碳的单价烃基。
在本发明的另一实施方案中，含铵的有机基聚硅氧烷是R11R12R13N，其中R11、R12和R13各自独立地为烷氧基硅烷或至多60个碳的单价烃基。烷氧基硅烷的通式为：
[R14O]3-x-yR15 xR16 ySiR17
其中＂x＂为0、1或2，且＂y＂为0或1，条件是x+y小于或等于2；R14是至多30个碳的单价烃基；R15和R16各自独立地选自至多60个碳的单价烃基；R17是至多60个碳的单价烃基。可用于本发明的改性的无机组分的其他化合物为胺化合物或具有结构R18R19R20N的相应的铵离子，其中R18、R19和R20各自独立地为至多30个碳原子的烷基或链烯基，和在另一实施方案中，各自独立为可相同或不同的具有至多20个碳原子的烷基或链烯基。在再一实施方案中，有机分子是长链叔胺，其中R18、R19和R20各自独立地为14个碳-20个碳的烷基或链烯基。
不需要将本发明的层状无机纳米颗粒组合物转化为质子交换形式。通常使用溶剂法和无溶剂法。通过阳离子交换将有机基聚硅氧烷铵离子插至层状无机纳米颗粒材料中。在基于溶剂的方法中，将有机基聚硅氧烷铵组分放置在对聚合或偶合反应惰性的溶剂中。特别合适的溶剂为水或水-乙醇、水-丙酮等水-极性助溶剂体系。除去溶剂后，制得插层的颗粒浓缩物。在无溶剂法中，通常需要高剪切共混机来进行插层反应。所述无机-有机纳米复合材料可为悬浮、凝胶、糊剂或固体形式。
含铵的有机基聚硅氧烷的具体类型为在美国专利5,130,396中所述的那些物质，且可由已知的材料(包括市售可得的那些材料)制备，该专利通过参考并入本申请。
美国专利5,130,396的含铵的有机基聚硅氧烷用以下通式表示：
其中R1和R2相同或不同，且用下式的基团表示：
其中(I)中的氮原子与(II)中的硅原子通过R5基团相连，且R5表示具有1-10个碳原子的亚烷基、具有5-8个原子的环亚烷基或以下通式的单元：
其中n为1-6的数，且表示在氮位置中的亚甲基的数目，且m为0-6的数，与在二氧化硅骨架中的一样，与硅原子相连的氧原子的自由价通过其他式(II)基团的硅原子和/或以下一个或更多个交联连接键的金属原子饱和
其中M为硅、钛或锆原子，R′为具有1-5个碳原子的直链或支链烷基，且这些式(II)基团的硅原子与连接键中的金属原子的比率为1:0，且其中R3等于R1、或R2、或氢、或具有1-20个碳原子的直链或支链烷基、具有5-8个碳原子的环烷基或苄基，且R4等于氢、或具有1-20个碳原子的直链或支链烷基，或由5-8个碳原子构成的氯丙基、环烷基、苄基、烷基、炔丙基、氯乙基、或羟乙基，且X为阴离子，x的化合价等于1-3，且选自卤化物、次氯酸根、硫酸根、硫酸氢根、亚硝酸根、硝酸根、磷酸根、磷酸二氢根、磷酸氢根、碳酸根、碳酸氢根、氢氧根、氯酸根、高氯酸根、铬酸根、重铬酸根、氰化物、氰酸根、硫氰酸根、硫化物、硫化氢、硒化物、碲化物、硼酸根、偏硼酸根、叠氮化物、四氟硼酸根、四苯基硼酸根、六氟磷酸根、甲酸根、乙酸根、丙酸根、草酸根、三氟乙酸根、三氯乙酸根或苯甲酸根。
本文所述的含铵的有机基聚硅氧烷化合物在宏观上为球形颗粒，直径为0.01-3.0mm，比表面积为0-1000m2/g，比孔容为0-5.0ml/g，堆密度为50-1000g/l，以及相对于体积的干物质为50-750g/l。
制备含铵的有机基聚硅氧烷的一种方法包括任选在催化剂存在下，将具有至少一个可水解的烷氧基的伯、仲或叔氨基硅烷与水反应，以进行水解并随后进行硅烷缩合，产生胺封端的有机基聚硅烷，随后使用合适的季铵化反应物(例如无机酸和/或烷基卤化物)将其季铵化，得到含铵的有机基聚硅氧烷。该类型的方法描述于上述美国专利5,130,396。关于这一点，美国专利6,730,766描述了通过环氧官能的聚硅氧烷的反应制造季铵化聚硅氧烷的方法，该专利的全部内容通过参考并入本申请。
在该方法的变型中，将具有可水解的烷氧基的伯、仲或叔氨基硅烷季铵化，随后进行水解缩合反应，提供有机基聚硅氧烷。例如，含铵的N-三甲氧基甲硅烷基丙基-N，N，N-三甲基氯化铵、N-三甲氧基甲硅烷基丙基-N，N，N-三-正丁基氯化铵和市售可得的含铵的三烷氧基硅烷十八烷基二甲基(3-三甲氧基甲硅烷基丙基)氯化铵(得自Gelest，Inc.)，在水解/缩合后，提供本文使用的含铵的有机基聚硅氧烷。
可用于制备含铵的有机基聚硅氧烷的其他合适的叔氨基硅烷包括三(三乙氧基甲硅烷基丙基)胺、三(三甲氧基甲硅烷基丙基)胺、三(二乙氧基甲基甲硅烷基丙基)胺、三(三丙氧基甲硅烷基丙基)胺、三(乙氧基二甲基甲硅烷基丙基)胺、三(三乙氧基苯基甲硅烷基丙基)胺等。
制备含铵的有机基聚硅氧烷的另一种方法要求使用季铵化反应物使含伯、仲或叔胺的有机基聚硅氧烷季铵化。可用的含胺的有机基聚硅氧烷包括以下通式的那些物质：
其中R1、R2、R6和R7各自独立为H、具有至多30个碳原子的烃基，例如烷基、环烷基、芳基、烷芳基、芳烷基等，或者R1和R2一起或R6和R7一起形成具有至多12个碳原子的二价桥连基团，R3和R5各自独立为具有至多30个碳原子的二价烃桥连基团，在链中任选包含一个或更多个氧和/或氮原子，例如具有1-8个碳原子的直链或支链亚烷基，例如-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2-C(CH3)-CH2-、-CH2CH2CH2CH2-等，R4各自独立为烷基，n为1-20，且优选为6-12。
这些和类似的含胺的有机基聚硅氧烷可通过已知和常规的方法制得，例如在如美国专利5,026,890中所述的硅氢化催化剂(例如含铂硅氢化催化剂)存在下，通过烯属胺(例如烯丙胺)与具有Si-H键的聚二有机基硅氧烷反应制得，该专利的全部内容通过参考并入本申请。
用于制备本文的含铵的有机基聚硅氧烷的具体的含胺的有机基聚硅氧烷包括以下工业混合物：
本发明的无机-有机纳米复合材料尤其可用作含固体聚合物或固体聚合物的混合物/共混物的组合物中的全部或部分填料。
有用的固体聚合物包括环氧树脂、聚碳酸酯、有机硅、聚酯、聚醚、聚烯烃、天然和合成橡胶、聚氨酯、尼龙、聚苯乙烯、聚乙烯芳族树脂、丙烯酸类树脂、丙烯酸酯树脂、聚酰胺、聚酰亚胺、酚醛树脂、聚卤乙烯、聚苯醚、聚酮、其共聚物和共混物。共聚物包括无规共聚物和嵌段共聚物二者。聚烯烃树脂包括聚丁烯、聚丙烯和聚乙烯，例如低密度聚乙烯、中密度聚乙烯、高密度聚乙烯和乙烯共聚物；聚卤乙烯树脂包括聚氯乙烯聚合物和共聚物，和聚偏氯乙烯聚合物和共聚物，含氟聚合物；聚乙烯基芳族树脂包括聚苯乙烯聚合物和共聚物；丙烯酸酯树脂包括丙烯酸酯和甲基丙烯酸酯的聚合物和共聚物，聚酰胺树脂包括尼龙6、尼龙11和尼龙12，以及聚酰胺共聚物及其共混物，聚酯树脂包括聚对苯二甲酸亚烷酯，例如聚对苯二甲酸乙二酯和聚对苯二甲酸丁二酯，以及聚酯共聚物；合成橡胶包括苯乙烯-丁二烯和丙烯腈-丁二烯-苯乙烯共聚物；和聚酮包括聚醚酮和聚醚醚酮。
在本发明的树脂填充的组合物中，无机-有机纳米复合材料当然以提高气体阻挡性能的用量存在。在第一种实施方案中，无机-有机纳米复合材料的存在量可以是至多约90wt％，在第二种实施方案中，用量为至多约50wt％，和在第三种实施方案中，用量为至多约20wt％。
本发明的无机-有机纳米复合材料也优选在预计充当气体阻挡物的组合物中用作填料，例如在申请人同一天提交的标题为“室温可固化的有机基聚硅氧烷组合物”的悬而未决的申请中公开并要求保护的组合物中用作填料，该申请的内容在此全文并入。
通过下述非限定性实施例描述本发明：
实施例1
如下制备本发明的无机-有机纳米复合材料：首先将10g氨丙基封端的硅氧烷(＂GAP10＂，硅氧烷长度为10，得自GE Silicones，Waterford，USA)放置在100ml单颈圆底烧瓶中，并加入4ml甲醇(得自Merck)。在搅拌下非常缓慢地加入2.2ml浓盐酸。继续搅拌10分钟。将900ml水加至2000ml配备冷凝器和顶部机械搅拌器的三颈圆底烧瓶中。在搅拌下(搅拌速率为约250rpm)非常缓慢地将18g Cloisite Na+(天然蒙脱土，得自Southern ClayProducts)粘土加至水中。随后将氯化铵溶液(如上制备)非常缓慢地加至粘土-水混合物中。将该混合物搅拌1小时，静置过夜。通过Buckner漏斗过滤该混合物，制得的固体用800ml甲醇浆化，搅拌20分钟，随后将混合物过滤。将固体在80℃的烘箱中干燥约50小时。
尽管详细说明并描述了本发明的优选实施方案，但例如组分、材料和参数的各种更改对于本领域的技术人员来说是显而易见的，且意图在所附的权利要求中涵盖落在本发明范围内的所有这些更改与变化。
Claims (22)
1.一种无机-有机纳米复合材料，包括至少一种为层状无机纳米颗粒的无机组分和至少一种为季铵有机基聚硅氧烷的有机组分；其中所述层状无机纳米颗粒的以直径确定的粒度小于1000nm且能进行离子交换；所述季铵有机基聚硅氧烷是具有下式的至少一种含铵的二有机基聚硅氧烷：
MaDbD′c
其中″a″为2，″b″等于或大于1，且″c″为0或正数；M是
[R3 zNR4]3-x-yR1 xR2 ySiO1/2
其中″x″是0、1或2，和″y″是0或1，条件是x+y小于或等于2，″z″为2，R1和R2各自独立地为至多60个碳的单价烃基；R3选自H和至多60个碳的单价烃基；R4是至多60个碳的单价烃基；D是
R5R6SiO1/2
其中R5和R6各自独立地为至多60个碳原子的单价烃基；和D′是
R7R8SiO2/2
其中R7和R8各自独立地为具有下述通式的含胺的单价烃基：
[R9 aR10]
其中″a″为2，R9选自H和至多60个碳的单价烃基；R10为至多60个碳的单价烃基。
2.权利要求1的无机-有机纳米复合材料，其中层状无机纳米颗粒具有可交换阳离子，所述阳离子选自Na+、Ca2+、Al3+、Fe2+、Fe3+、Mg2+，及其混合物。
3.权利要求1的无机-有机纳米复合材料，其中层状纳米颗粒是选自以下物质中的至少一种：蒙脱土、蒙脱土钠、蒙脱土钙、蒙脱土镁、绿脱石、贝得石、铬岭石、合成粘土、锂蒙脱石、皂石、锌蒙脱石、水羟硅钠石、富镁蒙脱石、蛭石、多水高岭石、铝酸盐氧化物、水滑石、伊利石、累托石、三八面体伊利石、高岭石及其混合物。
4.权利要求1的无机-有机纳米复合材料，其中层状无机纳米颗粒的平均最大横向尺寸为0.01微米至10微米，和平均最大纵向尺寸为0.5纳米至10纳米。
5.权利要求1的无机-有机纳米复合材料，其中季铵基用式R6R7R8N+X-表示，其中R6、R7和R8中的至少一个是至多60个碳原子的烷氧基硅烷，和其余为至多60个碳原子的烷基或链烯基，和X是阴离子。
6.权利要求1的无机-有机纳米复合材料，其中所述季铵有机基聚硅氧烷通过以下方法获得：在水解/缩合条件下，使具有至少一个可水解基团的氨基硅烷与水反应，提供胺封端的有机基聚硅氧烷，之后季铵化该胺封端的有机基聚硅氧烷，从而提供铵有机基聚硅氧烷。
7.权利要求1的无机-有机纳米复合材料，其中所述季铵有机基聚硅氧烷通过以下方法获得：在水解/缩合之前，季铵化具有至少一个可水解烷氧基的氨基硅烷，从而提供铵有机基聚硅氧烷。
8.权利要求1的无机-有机纳米复合材料，其中所述季铵有机基聚硅氧烷通过以下方法获得：在硅氢化催化剂存在下，用烯丙基胺硅氢化氢封端的有机基聚硅氧烷，提供胺封端的有机基聚硅氧烷，之后季铵化该胺封端的有机基聚硅氧烷，从而提供铵有机基聚硅氧烷。
9.制备无机-有机纳米复合材料的方法，该方法包括下述步骤：
a)任选地在催化剂存在下，使具有至少一个可水解的烷氧基的氨基硅烷与水反应，提供胺封端的有机基聚硅氧烷；
b)季铵化该胺封端的有机基聚硅氧烷，提供季铵化的有机基聚硅氧烷；和
c)结合该季铵化的有机基聚硅氧烷与具有可交换阳离子的层状无机纳米颗粒，提供无机-有机纳米复合材料。
10.权利要求9的方法，其中氨基硅烷是具有至少一个可水解的烷氧基的伯氨基硅烷、仲氨基硅烷或叔氨基硅烷。
11.权利要求9的方法，其中催化剂选自有机金属化合物、酸、碱，及其混合物。
12.权利要求9的方法，其中用无机酸、烷基卤、或其混合物季铵化胺封端的有机基聚硅氧烷。
13.通过权利要求9的方法获得的无机-有机纳米复合材料。
14.通过权利要求10的方法获得的无机-有机纳米复合材料。
15.通过权利要求11的方法获得的无机-有机纳米复合材料。
16.通过权利要求12的方法获得的无机-有机纳米复合材料。
17.一种组合物，它包括至少一种固体合成树脂和作为用于其中的部分或全部填料的至少一种权利要求1的无机-有机纳米复合材料。
18.权利要求17的组合物，其中所述树脂为选自以下物质中的至少一种：环氧树脂、聚碳酸酯、有机硅、聚酯、聚醚、聚烯烃、天然橡胶和合成橡胶、聚氨酯、尼龙、聚苯乙烯、聚乙烯芳族树脂、丙烯酸类树脂、丙烯酸酯树脂、聚酰亚胺、酚醛树脂、聚卤乙烯、聚苯醚、聚酮、其共聚物和共混物。
19.权利要求17的组合物，其中所述无机-有机纳米复合材料的存在量为至多90wt％。
20.一种组合物，它包括至少一种固体合成树脂，和作为用于其中的部分或全部填料的至少一种通过权利要求9的方法获得的无机-有机纳米复合材料。
21.权利要求20的组合物，其中所述树脂是环氧树脂、聚碳酸酯、有机硅、聚酯、聚醚、聚烯烃、天然橡胶和合成橡胶、聚氨酯、尼龙、聚苯乙烯、聚乙烯芳族树脂、丙烯酸类树脂、丙烯酸酯树脂、聚酰亚胺、酚醛树脂、聚卤乙烯、聚苯醚、聚酮、其共聚物和共混物中的至少一种。
22.权利要求20的组合物，其中所述无机-有机纳米复合材料的存在量为至多90wt％。
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| KR20180036047A (ko) * | 2016-09-30 | 2018-04-09 | 주식회사 엘파니 | 전도성 유무기 복합체, 이의 제조 방법, 및 이를 포함하는 충진재 |
| RU2667178C2 (ru) * | 2016-12-27 | 2018-09-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ростовский государственный университет путей сообщения" (ФГБОУ ВО РГУПС) | Полиуретановое связующее для армированных минерал-полимерных композитов и способ его получения |
| CN108659944A (zh) * | 2018-05-28 | 2018-10-16 | 界首市金龙机械设备有限公司 | 一种用于油漆喷涂设备零件制造的磨削液的加工方法 |
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| CN112823189A (zh) * | 2018-10-26 | 2021-05-18 | 株式会社艾迪科 | 复合材料 |
| JP2023156701A (ja) * | 2022-04-13 | 2023-10-25 | 信越化学工業株式会社 | ゲル化剤とゲル化剤の製造方法及び化粧料 |
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2006
- 2006-01-20 US US11/336,948 patent/US7531613B2/en active Active
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137198C (zh) * | 2001-03-21 | 2004-02-04 | 中科纳米技术工程中心有限公司 | 一种聚合物/蒙脱土纳米复合材料及其制法 |
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| JP2009523891A (ja) | 2009-06-25 |
| US20070173598A1 (en) | 2007-07-26 |
| EP1981937B1 (en) | 2018-06-27 |
| JP2013064148A (ja) | 2013-04-11 |
| PL1981937T3 (pl) | 2019-01-31 |
| RU2434893C2 (ru) | 2011-11-27 |
| RU2008134121A (ru) | 2010-02-27 |
| HK1130275A1 (en) | 2009-12-24 |
| JP5671516B2 (ja) | 2015-02-18 |
| KR20080093992A (ko) | 2008-10-22 |
| EP1981937A1 (en) | 2008-10-22 |
| US7531613B2 (en) | 2009-05-12 |
| CN101405334A (zh) | 2009-04-08 |
| TWI411637B (zh) | 2013-10-11 |
| CA2637066A1 (en) | 2007-07-26 |
| TW200801095A (en) | 2008-01-01 |
| KR101383206B1 (ko) | 2014-04-09 |
| WO2007084563A1 (en) | 2007-07-26 |
| ES2688604T3 (es) | 2018-11-05 |
| CA2637066C (en) | 2014-09-16 |
| BRPI0706696A2 (pt) | 2011-04-05 |
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