TWI411637B - 無機-有機奈米複合材料 - Google Patents
無機-有機奈米複合材料 Download PDFInfo
- Publication number
- TWI411637B TWI411637B TW096101827A TW96101827A TWI411637B TW I411637 B TWI411637 B TW I411637B TW 096101827 A TW096101827 A TW 096101827A TW 96101827 A TW96101827 A TW 96101827A TW I411637 B TWI411637 B TW I411637B
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- TW
- Taiwan
- Prior art keywords
- inorganic
- group
- organopolyoxyalkylene
- organic
- organic nanocomposite
- Prior art date
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 33
- -1 caulks Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical group 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 9
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 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 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910052900 illite Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 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 5
- 239000000126 substance Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 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
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 229910052500 inorganic mineral 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
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920001291 polyvinyl halide Polymers 0.000 claims description 4
- 229910021647 smectite Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000768 polyamine 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
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920006216 polyvinyl aromatic Polymers 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000008376 fluorenones Chemical class 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229940094522 laponite Drugs 0.000 claims description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 239000003822 epoxy resin Substances 0.000 claims 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000057 synthetic resin Substances 0.000 claims 2
- 229920003002 synthetic resin Polymers 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000008425 anthrones Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims 1
- 239000001095 magnesium carbonate Substances 0.000 claims 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims 1
- 235000014380 magnesium carbonate Nutrition 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 235000002020 sage Nutrition 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 24
- 239000000565 sealant Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 239000004927 clay Substances 0.000 description 43
- 239000010410 layer Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 239000012802 nanoclay Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- CAWGQUPKYLTTNX-UHFFFAOYSA-N 3,4,5,6-tetrahydro-2,7-benzodioxecine-1,8-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=CC=C12 CAWGQUPKYLTTNX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910017089 AlO(OH) Inorganic materials 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- GJBIORPMWNOJFH-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)[N+](CCCCCCCCCCCCC(OC)(OC)OC)(C)C Chemical compound C(CCCCCCCCCCCCCCCCC)[N+](CCCCCCCCCCCCC(OC)(OC)OC)(C)C GJBIORPMWNOJFH-UHFFFAOYSA-N 0.000 description 1
- DBDMDFCVJCNXJG-UHFFFAOYSA-N CCC(CCCCCCCCCC(OC)(OC)OC)N(C(CC)CCCCCCCCCC(OC)(OC)OC)C(CC)CCCCCCCCCC(OC)(OC)OC Chemical compound CCC(CCCCCCCCCC(OC)(OC)OC)N(C(CC)CCCCCCCCCC(OC)(OC)OC)C(CC)CCCCCCCCCC(OC)(OC)OC DBDMDFCVJCNXJG-UHFFFAOYSA-N 0.000 description 1
- OYORHIHUKCKFJZ-UHFFFAOYSA-N CCC(CCCCCCCCCC(OCC)(OCC)OCC)N(C(CC)CCCCCCCCCC(OCC)(OCC)OCC)C(CC)CCCCCCCCCC(OCC)(OCC)OCC Chemical compound CCC(CCCCCCCCCC(OCC)(OCC)OCC)N(C(CC)CCCCCCCCCC(OCC)(OCC)OCC)C(CC)CCCCCCCCCC(OCC)(OCC)OCC OYORHIHUKCKFJZ-UHFFFAOYSA-N 0.000 description 1
- JNWIQGKSFPXDAF-UHFFFAOYSA-N CCCOC(CCCCCCCCCC(CC)N(C(CC)CCCCCCCCCC(OCCC)(OCCC)OCCC)C(CC)CCCCCCCCCC(OCCC)(OCCC)OCCC)(OCCC)OCCC Chemical compound CCCOC(CCCCCCCCCC(CC)N(C(CC)CCCCCCCCCC(OCCC)(OCCC)OCCC)C(CC)CCCCCCCCCC(OCCC)(OCCC)OCCC)(OCCC)OCCC JNWIQGKSFPXDAF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 1
- 229910001347 Stellite Inorganic materials 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
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-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 compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical group [Ru]=O ROZSPJBPUVWBHW-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
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005341 cation exchange 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
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 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 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 229910000273 nontronite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000013612 plasmid Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical group CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-M trichloroacetate Chemical compound [O-]C(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-M 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- C08L83/04—Polysiloxanes
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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Description
本發明概括地有關改良的奈米複合材料組成物及製造和使用彼之方法。更特別的，本發明係關無機-有機奈米複合材料及彼等的製備方法。本發明亦有關此等無機-有機奈米複合材料組成物在，例如，塗料、密封劑、填縫料、黏著劑、及塑料之用途。
無機-有機奈米複合材料可顯出較彼等之分開成分更優的物理性質。為了使此等材料之效能性質最優化，通常宜於將無機成分以奈米長度規模分散於有機基質之內。可破解成奈米級建築磚塊的黏土及層化無機材料可用於無機-有機奈米複合材料之製備。
黏土材料至聚合物之添加係技藝中已知者，不過，將黏土摻加於聚合物內可能在聚合物物理性質，特別是機械性質上，無法提供所期望的改良。此可能由於，例如，黏土與聚合物間的介面，或邊界，材料內的黏土與聚合物間缺乏親和性。經由讓黏土材料均勻地分散在整體聚合物之內，可使黏土與聚合物間之親和性改良所得奈米複合材料之物理性質。若均勻地分散，則該黏土之相對大的表面積，可能提供在黏土與聚合物間更多的介面，且經由減少聚合物鏈在此等介面中之移動性而可隨後改良物理性質。相異地，黏土與聚合物間親和性之缺乏可能會經由在聚合
物整體內具有濃集的黏土袋，而非均勻地分散，而可能不利地影響組成物的強度及均勻性。黏土與聚合物間之親和性係關聯於黏土，就本質而言，通常係親水性，而聚合物通常為疏水性之事實。
黏土材料典型地包含具有細粒和扁平習性的經水合矽酸鋁。典型黏土材料之晶狀結構係多層的結構，包括接合到AlO(OH)2八面體層之SiO4四面體層之組合。黏土材料會根據彼等的組成層及陽離子之組合而變異。黏土材料陽離子之同形性取代，諸如以Al3+或Fe3+取代四面體網絡中的Si4+離子，或以Al3+、Mg2+或Fe2+取代八面體網絡中的其他陽離子，係典型地會發生且可能賦予黏土結構上一負電荷。在黏土之孔道內的自然出現元素，諸如水分子或鈉或鉀陽離子，會因此等負電荷而被吸引到黏土層之表面。
為了提升在介面中黏土與聚合物間之親和性及提供黏土在聚合物內之均勻分散，可修改黏土之層間表面化學以使矽酸鹽層具有較低的親水性。
烷基銨離子，諸如鎓鹽，係常用來製備奈米複合材料所用之黏土分散體。典型烷基銨離子的基本化學式為CH3-(CH2)n-NH3 +其中n為從1至18。咸信該烷基銨離子可與在黏土小板(platelets)間天然出現的陽離子順利地交換而導致嵌入狀態。另外，也相信該烷基銨離子可能增加黏土層之間的空間且也可能降低黏土之表面能量，藉此使有機物種具有不同的極性而嵌在黏土層之間。
對於具有改良性質的奈米複合材料有其需要存在著。本文中所揭示的發明提供一種具成本效益且有效率的方法用以製造新穎無機-有機奈米複合材料組成物，其特別適合用於以柔軟性，可加工性和彈性等所欲特性為重要性能準則之密封劑中。
根據本發明，提供一種無機-有機奈米複合材料，其包含至少一種多層式無機奈米粒狀物之無機成分及至少一種季銨有機基聚矽氧烷之有機成分。
本發明新穎無機-有機奈米複合材料可用於多種含聚合物樹脂組成物作為填料，且特別者，用於預期供密封劑、塗料及黏著劑等應用所用的組成物中作為填料。
根據本發明，提供一種無機-有機奈米複合材料，其包含至少一種多層式無機奈米粒狀物之無機成分及至少一種季銨有機基聚矽氧烷之有機成分。在說明本發明時，除非有不同指示，否則下列術語具有下述之意義。
定義
術語“剝落(exfoliation)”於用於本文中之時係說明一種程序，其中小包的奈米黏土小板在聚合物基質中彼此分離。在剝落期間，在每一小包最外部的該等小板劈開分離，暴露更多的小板待分離。
術語“廊道(gallery)”於用於本文中之時係說明介於平
行的黏土小板層之間的空間。該廊道間距係視佔據該空間的分子或聚合物之本質而改變。介於個別奈米黏土小板之間的層間空間，再度地係視佔據該空間的分子分子之類型而變異。
術語“夾層物質(intercalant)”於用於本文中之時係包括能進入黏土廊道且結合到其表面之任何無機或有機化合物。
術語“夾入物(intercalate)”於用於本文中之時指稱一種黏土化距學複合物其中該黏土廊道間距由於表面改質之程序而增加。在溫度及切變(shear)之適當條件下，夾入物能夠在樹酯基質中剝落。
術語“夾入(intercalation)”於用於本文中之時係指稱一種形成夾入物之程序。
表達語“無機奈米粒狀物”於用於本文中之時係說明多層無機材料，例如，黏土，具有一或更多維，諸如長度、寬度或厚度，在奈米尺寸範圍內且其能進行離子交換。
表達語“改質黏土”於用於本文中之時係指稱一種黏土材料，例如，奈米黏土，其經使用能夠與在黏土間層表面上所含陽離子進行離子交換反應之任何無機或有機化合物處理過。
術語“奈米黏土”於用於本文中之時係說明多層奈米材料，其擁有一獨特的以其一維在奈米範圍內之形態。奈米黏土可與夾層物質形成化學複合物，其經離子性結合於構
成黏土粒子的層之間的表面。此種夾層物質與黏土粒子之締合導致一種材料，可與許多不同種類之主體樹脂相容而促成該黏土填料分散在其中。
術語“奈米粒狀物”於用於本文中之時，係指通常以直徑決定，通常小於約1000奈米(nm)的粒子尺寸。
術語“小板”於用於本文中之時係指稱多層材料之個別層。
無機-有機奈米複合材料之無機奈米粒狀物可為天然或合成者諸如綠土(smectite)黏土，且應該具有某些離子交換性質諸如在綠土黏土、累托石(rectorite)、蛭石(Vermiculite)、伊利石(illite)、雲母(micas)及彼等的合成類似物中者，包括合成鋰皂石(laponite)、合成雲母-蒙脫石及四矽酸系(tetrasilicic)雲母。
該奈米粒狀物可擁有在第一具體實例中係在約0.01微米與約10微米之間，在第二具體實例中係在約0.05微米與約2微米之間，及在第三具體實例中係在約0.1微米與約1微米之間的平均最大側向尺寸(寬度)。該奈米粒狀物之平均最大垂直尺寸(厚度)通常在第一具體實例中係在約0.5微米與約10微米之間且在第二具體實例中係在約1微米與約5微米之間變異。
本發明之可用的無機奈米粒子材料包含天然或合成的頁矽酸鹽(phyllosilicates)，特別的綠土黏土諸如蒙脫石、鈉蒙脫石、鈣蒙脫石、鎂蒙脫石、矽鐵石(nontronite)、貝德石(beidellite)、鉻膨潤石(volkonskoite)、合成鋰皂
石、鋰膨潤石(hectorite)、皂石(saponite)、鋅皂石(sauconite)、瑪噶地石(magadite)、斜水矽鈉石(kenyaite)、索保克石(sobockite)、司文朵石(svindordite)、斯蒂文石(stevensite)、滑石(talc)、雲母、高嶺石(kaolinite)、蛭石、埃洛石(halloysite)、氧化鋁、或菱水鋁鎂石(hydrotalcites)、雲母質礦物質諸如伊利石及混合的多層伊利石/綠土礦物質諸如累托石、塔洛索石(tarosovite)、三八伊來石(ledikite)、及伊來石與一或多種上述黏土礦物質之混合物。可以充足地吸收有機分子以增加在毗鄰頁矽酸鹽小板間之層間間距到至少約5埃(Angstroms)，或至少約10埃，(當頁矽酸鹽係乾燥測量時)的任何可膨脹的多層材料都可用於製造本發明無機-有機奈米複合材料。
本發明改質無機奈米粒狀物係經由令數種量的擁有可交換性陽離子，例如，Na+、Ca2+、Al3+、Fe2+、Fe3+、和Mg2+，之多層的無機奈米粒狀物與至少一種含銨有機基聚矽氧烷接觸而得。所得改質粒狀物係一種擁有經夾入的季銨有機基聚矽氧烷之無機-有機奈米複合材料。
該含銨有機基聚矽氧烷必須含有至少一個銨基且可含有二或多個銨基。季銨基可經配置於有機基聚矽氧烷的終端及/或沿著矽氧烷主鏈。一類可用的含銨有機基聚矽氧烷具有下面通式：MaDbD' c
其中“a”為2，且“b”為等於或大於1且“c”為0或正數；M為[R3 zNR4]3-x-yR1 xR2 ySiO1/2
其中“x”為0，1或2且“y”為0或1，但其限制條件為x+y為小於或等於2，“z”為2，R1及R2各自獨立地為一具有至多60個碳的單價烴基；R3係選自H及具有至多60個碳的單價烴基所組成之群組；R4係具有至多60個碳的單價烴基；D為R5R6SiO1/2
其中R5及R6各自獨立地為一具有至多60個碳原子的單價烴基；D'係R7R8SiO2/2
其中R7及R8各自獨立地為一含有具下面通式的胺之單價烴基：[R9 aNR10]
其中“a”為2，R9係選自H及具有至多60個碳的單價
烴基所組成之群組；R10係具有至多60個碳的單價烴基。
於本發明另一具體實例中，該含銨有機基聚矽氧烷係R11R12R13N，其中R11、R12、及R13各自獨立地為一烷氧基矽烷或具有至多60個碳的單價烴基。該烷氧基矽烷之通式係[R14O]3-x-yR15 xR16 ySiR17
其中“x”為0，1或2且“y”為0或1，但其限制條件為x+y為小於或等於2，R14係一具有30個碳的單價烴基；R15及R16各自獨立地為選自具有至多60個碳的單價烴基；R17係具有至多60個碳的單價烴基。可用來改質本發明無機成分的其他化合物為胺化合物或具有結構R18R19R20N之對應的銨離子，其中R18、R19、及R20各自獨立地為一具有至多30個碳原子的烷基或烯基，且在另一具體實例中各自獨立地為具有至多20個碳原子的烷基或烯基，彼等可相同或不同。於又另一具體實例中，該有機分子係長鏈第三胺，其R18、R19、及R20各自獨立地為一14碳至20碳烷基或烯基。
本發明多層式無機奈米粒子複合材料不需要轉化成質子交換形式。典型地，該季銨有機基聚矽氧烷進入多層式無機奈米粒子材料中之夾入係經由使用溶劑及無溶劑方法行陽離子交換而達成。在以溶劑為基的方法中，係將該有機基聚矽氧烷銨成分置於一對聚合或偶合反應呈惰性的溶
劑中。特別適合的溶劑係水或水-乙醇、水-丙酮及類似的水-極性共-溶劑系統。在移除溶劑之後，即得夾入形粒狀物濃縮物。在無溶劑方法中，通常需要一高剪力摻合機以執行夾入反應。該無機-有機奈米複合材料可呈懸浮液、凝膠、糊或固體形式。
一特殊類別之含銨有機\聚矽氧為載於美國專利第5,130,396號中者，該專利的整個內容以引用方式納入本文中，且可用包含市售者之已知材料予以製備。
美國專利第5,130,396號之含銨有機基聚矽氧烷係由下面通式(I)表之：
其中R1及R2係相同或不同者且表一式(II)基：
其中(I)中的氮原子係透過R5基接到(II)中的矽原子且R5表一具有1至10個碳原子的伸烷基、具有5至8個原子之伸環烷基或一下面通式的單位：
其中n係從1至6之數且表氮位置中之亞甲基數目，且m係從0至6之數且結合於矽原子之氧原子的自由價係經由式(II)中其他基的矽原子及/或一或多個下列交聯性結合鍵聯的金屬原子予以飽和如在氧化矽骨架中者：或或或或
其中M係矽、鈦或鋯原子且R’為具有1至5個碳原子之線型或分枝型烷基；且式(II)基中的矽原子對結合鍵聯中的金屬原子之比例為1：0至，且其中R3等於R1或R2、或氫、或有1至20個碳原子之線型或分枝型烷基，有5至8個碳原子之環烷基或為苯甲基，且R4等於氫，或具有1至20碳原子之線型或分枝型烷基，或為環烷基、苯甲基、烷基、炔丙基、氯乙基、羥乙基、或氯丙基，有5至8個碳原子，且X係具有價數x等於1至3之陰離子且係選自鹵離子、次氯酸根、硫酸根、氫硫酸
根、亞硝酸根、硝酸根、磷酸根、磷酸二氫根、磷酸氫根、碳酸根、碳酸氫根、氫氧根、氯酸根、過氯酸根、鉻酸根、重鉻酸根、氰離子、氰酸根、硫氰離子、硫離子、硫氫離子、硒離子、碲離子、硼酸根、偏硼酸根、疊氮離子、四氟硼酸根、四苯基硼酸根、六氟磷酸根、甲酸根、醋酸根、丙酸根、草酸根、三氟醋酸根、三氯醋酸根或苯甲酸根。
本文中所述含銨有機基聚矽氧烷為宏觀球狀粒子、具有0.01至3.0毫米之直徑，0至1000平方米/克之比表面積、0至5.0毫升/克之比孔積、50至1000克/升之容積密度以及50至750克/升之乾物質基對體積。
一種製備含銨有機基聚矽氧烷之方法包括令擁有至少一個可水解性烷氧基的第一、第二、或第三胺基矽烷與水，隨意地於觸媒存在中，反應以達到將矽烷水解及隨後縮合而產生胺終端有機基聚矽氧烷，其後將其用一適當的季鹼化(quarternizing)反應物諸如礦酸及/或鹵化烷予以季鹼化而提供該含銨有機基聚矽氧烷。此類型方法載於上述美國專利第5,130,396號中。在此關聯中，美國專利第6,730,766號(其整個內容以引用方式納入本文)述及經由環氧官能聚矽氧烷之反應製造經季鹼化的聚矽氧所用方法。
於此方法之一變異形式中，係在水解縮合反應提供有機基聚矽氧烷之前，將擁有可水解烷氧基的第一、第二、或第三胺基矽烷予以季鹼化。例如，含銨之氯化N-三甲
氧矽烷基丙基-N,N,N-三甲基銨、氯化N-三甲氧矽烷基丙基-N,N,N-三-正丁基銨，及市售含銨之氯化三烷氧矽烷十八烷基二甲基(3-三甲氧矽烷基丙基)銨(可得自Gelest,Inc.)，在彼等之水解/縮合之後可提供本發明中所用之含銨有機基聚矽氧烷。
可用來製備含銨有機基聚矽氧烷的其他適當第三胺基矽烷包括三(三乙氧基矽烷基丙基)胺、三(三甲氧基矽烷基丙基)胺、三(二乙氧基甲基矽烷基丙基)胺、三(三丙氧基矽烷基丙基)胺、三(乙氧基二甲基矽烷基丙基)胺、三(三乙氧基苯基矽烷基丙基)胺，及類似者。
還有另一種製備含銨有機基聚矽氧烷的方法需要用季鹼化劑將具有含第一、第二、或第三胺的有機基聚矽氧烷季鹼化。可用的含銨有機基聚矽氧烷包括具有下面通式者：
其中R1、R2、R6、及R7各自獨立地為H，有至多30個碳原子之烴基，例如，烷基、環烷基、芳基、烷芳基、芳烷基，等，或R1和R2一起或R6和R7一起形成有至多12個碳原子之二價烴橋聯基，R3及R5各自獨立地為有至多30碳原子之二價烴橋聯基，在鏈中隨意地含有一或更
多個氧及/或氮原子，例如，有從1至8個碳的線型或支鏈型伸烷基諸如-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2-C(CH3)-CH2-、-CH2CH2CH2CH2-，等，各R4係獨立地為烷基，n為從1至20且有利者從6至12。
此等及類似的含胺有機基聚矽氧烷可經由已知及慣用的程序獲得例如，經由用烯烴胺諸如烯丙胺與擁有Si-H鍵的聚二有機基矽氧烷於矽氫化觸媒，諸如，含鉑矽氫化觸媒存在中反應，如載於美國專利第5,026,890號中者，該專利的整個內容以引用方式納入本文中。
可用於製備本發明含銨有機基聚矽氧烷的特別含胺有機基聚矽氧烷包括含下列之商業混合物
和
本發明無機-有機奈米複合材料皆可用為，與其他一起者，包含固體聚合物或固體聚合物混合物/摻合物的組成物所用的唯一或部份填料。
可用的固體聚合物包括環氧樹脂、聚碳酸酯、矽酮、聚酯、聚醚、聚烯烴、天然和合成橡膠、聚胺基甲酸脂、
尼龍、聚苯乙烯、聚乙烯基芳族化合物、丙烯酸系樹脂、丙烯酸酯、聚醯胺、聚醯亞胺、酚樹脂、聚鹵乙烯、聚苯醚、聚酮類，彼等的共聚物及彼等的摻合物。共聚物包括無規共聚物及嵌段共聚物兩者。聚烯烴樹脂包括聚丁烯、聚丙烯及聚乙烯，諸如低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、及乙烯共聚物；聚鹵乙烯樹脂包含聚氯乙烯聚合物和共聚物及聚偏氯乙烯聚合物與共聚物、氟聚合物；聚乙烯芳族化合物樹脂包括聚苯乙烯聚合物及共聚物；丙烯酸酯樹脂包括丙烯酸酯和甲基丙烯酸酯之聚合物及共聚物；聚醯胺樹脂包括尼龍6、尼龍11、及尼龍12，以及聚醯胺共聚物及其摻合物；聚酯樹脂包括聚對苯二甲酸伸烷基酯，諸如聚對苯二甲酸乙二酯及聚對苯二甲酸丁二酯，以及聚酯共聚物；合成橡膠包括苯乙烯-丁二烯及丙烯腈-丁二烯-苯乙烯共聚物；聚酮類包括聚醚酮及聚醚醚酮。
在本發明樹脂填充組成物中，該無機-有機奈米複合材料的含量，當然，為可提高其中的氣體障壁性質者。在第一具體實例中，無機-有機奈米複合材料的含量可為高達約90重量%，在第二具體實例中，其含量可為高達約50重量%，且於第三具體實例中高達約20重量%。
本發明之無機-有機奈米複合材料亦可有利地用於預期有氣體障壁功能的組成物，例如，在申請人的，在相同日期提出申請，申請中之申請案，名稱“ROOM TEMPERATURE CUBABLE ORGANOPOLYSILOXANE
COMPOSITION”(其整體內容以引用方式納入本文中)中所揭示且申請專利的組成物中做為填料。
本發明要以下面非限制性實施例予以闡明：
根據本發明之無機-有機奈米複合材料之製備係經由首先將10克之胺基丙烯終端矽氧烷(“GAP 10，”，矽氧烷長度10，得自GE Silicones,Waterford,USA)放置在一100-毫升單頸圓底燒瓶內且添加4毫升可得自Merck之甲醇。於慢慢攪拌下添加2.2毫升之濃HCl。繼續攪拌10分鐘。將900毫升水添加到裝有冷凝器及高架機械攪拌器之2000-毫升三頸圓底燒瓶內。將18克鋅鉛石Na+(天然蒙脫石，可得自Southern Clay Products)黏土非常慢地(攪拌速率約250 rpm)攪拌加到該水中。接著將氯化銨溶液(上面製備者)非常慢地加到黏土-水混合物中。將該混合物攪拌1小時後使其靜置整夜。將該混合物過濾過一Buckner漏斗且將所得固體用800毫升甲醇攪和，攪拌20分鐘，接著過濾該混合物。將該固體在80℃烤箱中乾燥約50小時。
雖然已經詳細闡示且說明過本發明較佳具體實例，不過對於諳於此技者都可明白在，例如，成分、材料及參數，上的各種修飾，且後附申請專利範圍理應涵蓋所有此等落於本發明範圍內的修飾及改變。
Claims (23)
- 一種無機-有機奈米複合材料，其包含至少一種多層式無機奈米粒狀物之無機成分和至少一種季銨有機基聚矽氧烷之有機成分，其中該季銨基係定位於有機基聚矽氧烷的終端及沿著矽氧烷主鏈。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該多層式無機奈米粒狀物擁有選自Na+、Ca2+、Al3+、Fe2+、Fe3+、Mg2+及彼等的混合物所組成之群組之可交換陽離子。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該多層式無機奈米粒狀物係至少一種選自蒙脫石、鈉蒙脫石、鈣蒙脫石、鎂蒙脫石、矽鐵石、貝德石、鉻膨潤石、合成鋰皂石、鋰膨潤石、皂石、鋅皂石、瑪噶地石(magadite)、斜水矽鈉石、索保克石(sobockite)、司文朵石(svindordite)、斯蒂文石、蛭石、埃洛石、氧化鋁、菱水鋁鎂石、伊利石、累托石、塔洛索石(tarosovite)、三八伊來石、高嶺石及，彼等的混合物所組成之群組中之成員。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該多層式無機奈米粒狀物具有在約0.01微米與約10微米之間的平均最大側向尺寸及在約0.5奈米與約10奈米之間的平均最大垂直尺寸。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該季銨有機基聚矽氧烷係至少一種具有下式的含 銨二有機基聚矽氧烷：MaDbD' c其中“a”為2，且“b”為等於或大於1且“c”為0或正數；M為[R3 zNR4]3-x-yR1 xR2 ySiO1/2其中“x”為0，1或2且“y”為0或1，但其限制條件為x+y為小於或等於2，“z”為2，R1及R2各自立地為具有至多60個碳之單價烴基；R3係選自H及具有至多60個碳的單價烴基所組成之群組；R4係具有至多60個碳的單價烴基；D為R5R6SiO1/2其中R5及R6各自獨立地為具有至多60個碳原子的單價烴基；且D'為R7R8SiO2/2其中R7及R8各自獨立地為含有具下面通式的胺之單價烴基： [R9 aNR10]其中“a”為2，R9係選自H及具有至多60個碳的單價烴基所組成之群組；R10係具有至多60個碳的單價烴基。
- 如申請專利範圍第5項之無機-有機奈米複合材料，其中該季銨基係由化學式R6R7R8N+X-所表，其中至少一R6、R7及R8係具有至多60個碳原子的烷氧基矽烷且其餘為具有至多60個碳原子的烷基或烯基且X係陰離子。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該季銨有機基聚矽氧烷係經由令擁有至少一個可水解基的胺基矽烷與水在水解/縮合條件下反應以提供胺終端有機基聚矽氧烷及其後將該胺終端有機基聚矽氧烷季鹼化(quarternizing)以提供銨有機基聚矽氧烷而獲得。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該季銨有機基聚矽氧烷係經由在水解/縮合提供銨有機基聚矽氧烷之前將擁有至少一個可水解烷氧基的胺基矽烷季鹼化而獲得。
- 如申請專利範圍第1項之無機-有機奈米複合材料，其中該季銨有機基聚矽氧烷係經由將氫終端有機基聚矽氧烷用烯丙胺在矽氫化觸媒存在中予以矽氫化以提供胺終端有機基聚矽氧烷及其後將該胺終端有機基聚矽氧烷予以季鹼化以提供銨有機基聚矽氧烷而獲得。
- 一種製備無機-有機奈米複合材料之方法，其包括下列步驟：a)令擁有至少一個可水解烷氧基的胺基矽烷與水，隨意地於觸媒存在時，反應以提供胺終端有機基聚矽氧烷；b)將該胺終端有機基聚矽氧烷季鹼化以提供一經季鹼化的有機基聚矽氧烷；及，c)將該經季鹼化的有機基聚矽氧烷與擁有可交換性陽離子的多層式無機奈米粒狀物組合以提供無機-有機奈米複合材料。
- 如申請專利範圍第10項之方法，其中該胺基矽烷係擁有至少一個可水解烷氧基的一級、二級或三級胺基矽烷。
- 如申請專利範圍第10項之方法，其中該觸媒係選自有機金屬化合物、酸、鹼、及彼等的混合物所組成的群組。
- 如申請專利範圍第10項之方法，其中該胺終端有機基聚矽氧烷係用礦酸、烷基鹵化物、或彼等的混合物予以季鹼化。
- 一種以申請專利範圍第10項之方法獲得之無機-有機奈米複合材料。
- 一種以申請專利範圍第11項之方法獲得之無機-有機奈米複合材料。
- 一種以申請專利範圍第12項之方法獲得之無機- 有機奈米複合材料。
- 一種以申請專利範圍第13項之方法獲得之無機-有機奈米複合材料。
- 一種組成物，其包含至少一種固體合成樹脂及，作為其所用的部分或全部填料的至少一種申請專利範圍第1項之無機-有機奈米複合材料。
- 如申請專利範圍第18項之組成物，其中該樹脂係選自環氧樹脂、聚碳酸酯、矽酮、聚酯、聚醚、聚烯烴、天然和合成橡膠、聚胺基甲酸脂、尼龍、聚苯乙烯、聚乙烯基芳族化合物、丙烯酸系樹脂、丙烯酸酯、聚醯胺、聚醯亞胺、酚樹脂、聚鹵乙烯、聚苯醚、聚酮，彼等的共聚物及彼等的摻合物所組成的群組中之至少一者。
- 如申請專利範圍第18項之組成物，其中該無機-有機奈米複合材料在其中的含量為至多約90重量%。
- 一種組成物，其包含至少一種固體合成樹脂及，作為其所用的部分或全部填料的至少一種以申請專利範圍第10項之方法獲得之無機-有機奈米複合材料。
- 如申請專利範圍第21項之組成物，其中該樹脂係選自環氧樹脂、聚碳酸酯、矽酮、聚酯、聚醚、聚烯烴、天然和合成橡膠、聚胺基甲酸脂、尼龍、聚苯乙烯、聚乙烯基芳族化合物、丙烯酸系樹脂、丙烯酸酯、聚醯胺、聚醯亞胺、酚樹脂、聚鹵乙烯、聚苯醚、聚酮，彼等的共聚物及彼等的摻合物所組成的群組中之至少一者。
- 如申請專利範圍第21項之組成物，其中該無機- 有機奈米複合材料在其中的含量為至多約90重量%。
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| US11/336,948 US7531613B2 (en) | 2006-01-20 | 2006-01-20 | Inorganic-organic nanocomposite |
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| EP (1) | EP1981937B1 (zh) |
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| RU (1) | RU2434893C2 (zh) |
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- 2007-01-17 TW TW096101827A patent/TWI411637B/zh not_active IP Right Cessation
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- 2007-01-17 JP JP2008551358A patent/JP2009523891A/ja active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2013064148A (ja) | 2013-04-11 |
| ES2688604T3 (es) | 2018-11-05 |
| CA2637066C (en) | 2014-09-16 |
| RU2008134121A (ru) | 2010-02-27 |
| US20070173598A1 (en) | 2007-07-26 |
| KR20080093992A (ko) | 2008-10-22 |
| TW200801095A (en) | 2008-01-01 |
| JP5671516B2 (ja) | 2015-02-18 |
| HK1130275A1 (en) | 2009-12-24 |
| JP2009523891A (ja) | 2009-06-25 |
| KR101383206B1 (ko) | 2014-04-09 |
| WO2007084563A1 (en) | 2007-07-26 |
| CA2637066A1 (en) | 2007-07-26 |
| RU2434893C2 (ru) | 2011-11-27 |
| CN101405334B (zh) | 2012-07-04 |
| EP1981937B1 (en) | 2018-06-27 |
| EP1981937A1 (en) | 2008-10-22 |
| BRPI0706696A2 (pt) | 2011-04-05 |
| US7531613B2 (en) | 2009-05-12 |
| PL1981937T3 (pl) | 2019-01-31 |
| CN101405334A (zh) | 2009-04-08 |
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