TWI361812B - - Google Patents
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- Publication number
- TWI361812B TWI361812B TW096146929A TW96146929A TWI361812B TW I361812 B TWI361812 B TW I361812B TW 096146929 A TW096146929 A TW 096146929A TW 96146929 A TW96146929 A TW 96146929A TW I361812 B TWI361812 B TW I361812B
- Authority
- TW
- Taiwan
- Prior art keywords
- linker
- group
- silver
- maleic anhydride
- polyetheramine
- Prior art date
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 52
- 239000004332 silver Substances 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 38
- 239000003381 stabilizer Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 125000005647 linker group Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229920000768 polyamine Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001412 amines Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XAYJXAUUXJTOSI-UHFFFAOYSA-M silver;2,2,3,3,3-pentafluoropropanoate Chemical compound [Ag+].[O-]C(=O)C(F)(F)C(F)(F)F XAYJXAUUXJTOSI-UHFFFAOYSA-M 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- 150000002924 oxiranes Chemical class 0.000 claims 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229910021612 Silver iodide Inorganic materials 0.000 claims 1
- 229910052946 acanthite Inorganic materials 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000006159 dianhydride group Chemical group 0.000 claims 1
- 125000003147 glycosyl group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims 1
- 229940045105 silver iodide Drugs 0.000 claims 1
- 229940056910 silver sulfide Drugs 0.000 claims 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims 1
- 235000010288 sodium nitrite Nutrition 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- -1 poly(ethylene glycol) Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910017745 AgNP Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 239000005944 Chlorpyrifos Substances 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 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
- 239000004677 Nylon Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- CMBZEFASPGWDEN-UHFFFAOYSA-N argon;hydrate Chemical compound O.[Ar] CMBZEFASPGWDEN-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WVJVHUWVQNLPCR-UHFFFAOYSA-N octadecanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCC WVJVHUWVQNLPCR-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
九、發明說明: 【發明所屬之技術領域】 本發明係關於-種高分子贱胺及以其穩定奈米絲子之方法,所得之各 米銀粒子域定的織、銀膠或gj體形式;可職複合材料或抗g材料,並: 用於電子產S之奈料電銀線、敎件材料及❹m,亦可翻於生醫及醫藥 產業,此外,奈練粒子目帶親油與親水性f,可分躲水或麵輔,並可 與多種高分子相容,亦作為高Ή型界祕性劑或分細制於各種粒子包括 顏料分散及其製程使用。 【先前技術】 奈米銀粒子之應用為未來21世紀產業重要技術之一。近來,製作奈米級銀 水溶液均為還原硝酸銀或其他種類之銀鹽,使用有機界面活性劑、分散劑或穩 定劑穩定銀粒子;銀粒子必須保持在奈米級或高表面積以期順利應用於抗菌、 藥物、生醫和電子材料。但因銀粒子易聚集的特性,一般控制奈米級粒子之大 小及其熱穩定性為兩個最重要之課題。 以製造奈米銀粒子而言’有機界面活性劑或穩定劑為一個相當重要的因 素,此外,由於銀之鹽類,例如硝酸銀在水中溶解度遠高於在有機溶液中,所 以產物通常也製造於水溶液中’因此’固有的條件限制住了奈米銀粒子往後的 應用。 關於此些問題的描述已經被廣泛的討論,以文獻為例,J. Phys. Chem. Β 1998,102,10663-10666’在水溶液中製造銀粒子,並且用sodiumpolyacrylate 或polyacrylamide的分子鏈穩定奈米銀;Chem. Mater. 2005,17,4630-4635, thioalkylated poly(ethylene glycol)在水中被用來做穩定銀粒子之穩定劑; Langmuir 1999,15,948-951,以3-aminopropyltrimethoxysi lane (APS)當做 1361812 穩定劑,而在室溫下,Ν,Ν-dimethylformamide可被用來還原銀粒子;j phys Chem, B 1999,103,9533-9539,檸檬酸納(sodium citrate)被用來防止凝聚 (aggregation or agglomeration)的銀粒子再度聚集而成為粒子較大或者分佈 較廣或者多peak分布;Langmuir 1996,12,3585-3589,一系列的非離子型界 面活性劑(polyethylene oxide or ethoxylated block)可用來穩定以產生各 米級銀粒子,因其移狀的粒子上包覆著界面活性劑之分子鏈,其中包括 P〇ly-(10)-oxyethylene oleyl ether 及 Tween 80 (polyoxyethylene-(20)-sorbitan monooleate)(均可於Sigma購買);Langmuir 1997,13,1481-1485,以NaBH4作為還原劑,其反應方程式為: 2AgN〇3 + 2NaBH4 + 6H2O 2Ag + 2NaN〇3 + 2H3B〇3 + 7Hz 其穩定劑為cetyltrimethylammonium bromide (CTAB)陽離子型界面活性劑, sodium dodecyl sulfate (SDS)為陰離子型界面活性劑與poly(〇xyethylene) isooctylphenyl ether-TX-100非離子型界面活性劑。 般穩疋銀粒子的的方法大多為以界面活性劑或穩定劑,然而,這此方式 製作出的銀粒子通常都無法做成銀漿或固含量少於1〇鵷,或者在高固含量銀漿 所組成之銀粒子仍然有聚集的傾向。
【發明内容】 本發明之主要目的為提供一種高分子型聚胺及其製造方法,該高分子型聚 胺可作為製造奈米銀粒子之穩定劑及分散效果。 本發明之另一目的為提供一種以高分子型聚胺穩定奈米銀粒子之方法,使 產生的銀襞' 銀膠或g]體具有高固含量及高穩定性,且經加卫或保存後仍具有 熱穩定性而不會聚集。 本發明之高分子型聚胺包括—W胺及與其末端胺官能基結合之連接劑; 該聚(PQlyQXyalkylene_amine)可為分子量範圍簡,,_之單胺、二胺
-6- < S 1361812 或三胺,連接劑可為酐、酸、環氧化物、異氰酸或苯乙烯/馬來酐共聚物 (polystyrene-maleic anhydride polymers > SMA)° 上述之連接劑之具體例包括:(1)酐(anhydride),例如順丁稀二酐、琥珀 酸酐、笨三甲酸針(TMA)、均苯四酸二酐(PMDA)、鄰苯二甲酐、甲基四氫鄰笨 二甲酸肝及苯乙稀/馬來針共聚物;(2)酸(carboxylic acid),例如二緩酸、己 二酸、琥珀酸、對苯二甲酸、間苯二曱酸;(3)二環氧化物(glycidyl 〇Γ epoxide),例如 diglycidyl ether of Bisphenol-A ( DGEBA )、 3, 4-epoxycyclohexyl-methyl-3, 4-epoxy cyclohexane carboxylate ; (4)二異
氰酸(isocyanate or disocyanate),例如曱苯-二異氰酸、亞甲基-二苯二異氰 酸、1,6-環六亞曱基-二異氰酸、異甲基丙酮二異氰酸;及(5)馬來酐(maleic anhydride或maleated polystyrene),例如SMA。較佳為均笨四酸二肝、笨三甲 酸酐及己二酸。 本發明之高分子型聚胺之結構式可表示為Linker_HN_R—NH- Linker、 M-R.-Linker、H2N-R-NH-Linker、M-R-NH-Linker-NH-R- NH2 ' Linkei-(HN-R-NH-Linker)x或H2N-R-NH-(Linker-HN-R-NH)x-H,x=l〜5 ;其中
Linker為連接劑’ _-R-NH或HN-R-Μί皆為聚醚胺,R可為二酐、二酸、環氧化物、 二異氰酸或苯乙烯/馬來酐共聚物(SMA)。 本發明製造南分子型聚胺之料:崎赚與具有反應官能基的連接劑 反應,藉由尚分子型聚胺的段鏈可螯合(chelating)銀粒子(silver nanoparticle或AgNP)’且可同時分散於水相或有機溶劑,可製備高穩定性且含 奈米銀粒子10 w似上之高濃度膠體、糊狀物或粉狀物。_胺及連接劑之定 義同上。 製程上’聚胺與連接劑之莫耳比可變化,以合成
Linker-(HN-R-NH- Linker)x 或 H2N-R-NH-(Linker-HN-R-NH)x-H ,使 其尾部官能基隨之變化。 聚雜與連接劑反應後,連接劑所增加之官能基將促進與銀整合作用,於 ^61812 水或有機賴巾更穩定,可提高安滕和防止奈練子聚集。 連接劑與㈣紐紅莫耳比難為⑽)^,n 25,。(;,反麟間較㈣卜12小時。 度較佳為 =發_高分子型聚胺穩定奈綠粒子之方法包括:以高分子型聚胺為穩 疋劑或讀劑,與賴水溶液混合後,再以還原_原銀粒子。兑巾,還 (NaBHO ^ f S, ^ H2N;NH2st f ^ ; 两分子型驗與健之重量比較佳壯1(M(hl ;銀鹽可為俩銀、雜銀、漠 化銀、氯化銀或五氟丙酸銀。 含有還原銀粒子的溶液可進一步除去水,以增加固含量,再加入有機溶劑, 以轉換成有機溶劑相。 亦可以一倍以上莫耳比的氫氧化鈉鈉化成為鈉鹽,以增加其水溶性。 【實施方式】 本發明較佳實施例所使用的材料包括: I聚醚胺.選用商標名為Jeffamine* Amines系列產品,包括:
a. Jeffamine ED-2001 : P〇ly(〇xypropylene-〇xyethylene-〇xypr〇pyiene) -bis-amines ’雙官能基聚醚胺,分子量2000 (亦稱pOE_2000),親水性 白色臘狀固體,mp. 35°C ’胺含量0.95 mequiv. /g,平均 oxyethylene/oxypropylene unit 為 39. 5/5,結構式如下:
其中 a + c = 6,b = 38. 7;或 b. Jeffamine M-2070 : poly(oxypropylene-oxyethylene)-monoamine ,單 官能基聚醚胺,分子量2000 (亦稱POP-2000),疏水性,結構式如下: 1361812, H2NCHCH2-^OCHCH2)-(-〇CH2CH2j-〇CH3 CH3 CH3 a b 其中a = 10,b = 31。 2.苯三甲酸Sf : trimellitic anhydride (TMA),購自 Aldrich Chemical Co., 使用前先以昇華純化,其結構式如下。
〇
3.均苯四酸二酐:pyromelliticdianhydride (PMDA) ’ 購自 Aldrich Chemical Co.或 Sino-Japan chemical Co. 〇 4. 苯乙稀/馬來if共聚物:poly(styrene-co-maleic anhydride) copolymers (SMA) ’苯乙烯/馬來酐的比例可為1/卜3/i、6/i或ii/i,購自Aldrich
Chemical Co.或 Sino-Japan chemical Co.,平均分子量分別為 6,000 (SMA1000)、6, 000 (SMA3000)、120, 000 (SMA6000)及 140,000 (SMA11000)。 5. 4, 4’ -二苯甲基二異氰酸醋:4,4’ -methylenebis(phenyl isocyanate) (MDI) 6. 确酸銀:AgN〇3 (99.8 %),講自 Aldrich。
7. 四氫吱喃:Tetrahydrofuran (THF)。 8. 硼氫化鈉:NaBH4,還原劑。
9. 氩氧化納:NaOH 本發明製造高分子型聚胺之方法係使親水性或疏水性聚醚胺與連接劑進行 合成反應’所製備之衍生物將為親水性或疏水性。 以下舉例配合反應圖說明之,連接劑使用TMA,聚醚胺分別為親水性POE2000 或疏水性POP2000,反應後再加入氫氧化鈉作離子改質,則反應方程式如下: 1361812,
NH2CTCT2^〇raCH2^CCH2CH2^OCH2CT*|^NH2 POP2COO (a=33.« ): Mw* 2000 g/mol POE200CKa+c=5,b-39.5); Mw-2000 g/mo! ΗΟ-ϋ-|^^-ΝΗ-έΗ3αν^〇έΗ^Η2*^〇〇Η2〇Η3|ς|〇αί2έΗ 七NH—
POE2COO/4COOH Ο Ο Ο ο Ο Ο CK3 CHj Ο Ο
C-OH HO-C- 3 βΗ〇-〇-4^ -Ο
POP2000/2COOH
POP20QO/4COOH
NaO-C π 〇 ch3 CHj ο ο亡-ONa NaO-ϊ—寸 ΟΟ^ηΊ^Ή— -C-ONo * NaO-C— POP20〇a^2COONa POP2000/4COONa 連接劑使用PMDA,與疏水性聚醚胺POP2000反應,反應後再加入氫氧化鋼作 離子改質,則反應方程式如下: Ο 0
.Nh2^〇S〇h^h2 Ο Ο PMDA ΡΟΡ2000 (x=33); Mw= 20(M)g/mole 〇
Ο Ο Ο Η <ρπ3 11 N-CHCH-,
CH3 Η Ο Ο Η ch3 9η3 V Q
Ο Ο Ο
〇Η 〇Η 〇 0
POP2000/COOH Θ Θ
Na 0·
Na Ο—r[ |Γ° Na Ο Ο ^ 9η3 Ch3 η ο ο η ch3 ch3 η Θ 0
Na Ο-τΤ >-0 Na Ο Ο © Φ Ο Na Ο
〇 Na° Ο Ν3Θ Ο POP20QO/COONa -10- S ) 1361.812. 以SMA為連接劑,與各種聚醚胺反應後,可得如下之梳狀聚合物:
SMA
Approx, ratio Approx. Μή
SMA1000 SMA3000 SMA6000 SMA11000 x/y= 1/1 6000 x/y= 3/1 6000 x/y= 6/1 12000 x/y=11/1 12000
Comb-Amphilic
SMA-POA ch3 ch3 NHCHCH2(OCHCH2>a(OCH2CH2)b(OCH2CH)cNH2 ch3 POP230 POP400 POP2000 POP4000 POE2000
Approx. ΛΑν a+c=2〜3 230 a+c=5〜6 400 a+c=33 2000 a+c=68 4000 a+c=6 b=38.7 2000 SMA-M-series
Approx. Mh M1000 a=3 b=9 1000 M2070 a=10 b=32 2000 < s) -11- 1361812 以MDI為連接劑,與各種聚醚胺反應之方程式如下: (step 1) h2n-poa-nh2
OCN-Ar 一 NCO (step 2) Ο ο OCN-(-Ar-NH-C-NH-POA-^-NH-C-NH-Ar-NCO (Α) Π (A) MPOE-NH,
Ο Ο O 〇 MPOE-NH-C-NH-f-Ar-NH-C-NH-POA-J-NH'C-NH-Ar-NH-C-NH-MPOE POA = POP2000 or POE2000 CH3 ch3 ch3 H2N-CHCH2-(〇CHCH2}-(〇CH2CH2^(〇CH2CH-^NH2 POP2000 diamines (a+c=33, b=0); Mw= 2000 g/mol POE2000 diamines (a+c=5,b=39.5); Mw=2000 g/mol MPOE = POE2000 monoamines CH3 ch3 H2N-CHCH2-(〇CHCH2)-(oCH2CH2V〇-CH3
Ar= POE2000 monoamines (a=10, b=31; random); Mw=2000 g/mol
實施例1
步驟A :製備穩定劑POE2000-TMA/4COOH 首先’昇華純化親水性POE2000 (Jeffamine*ED-2001 ),並以氫化妈將THF 除水’再以分子篩保存。接著,於5〇〇ml之三頸瓶中,將POE2000 (100 g,〇. 05 mol)溶於THF (150 ml) ’再逐滴加入單酐連接劑TMA (19. 2 g,0.1〇 mo卜先 溶於50 ml THF) ’使POE2000與TMA的莫爾比為1 : 2。反應物以機械授掉,並 全程充氮氣’以低於3(TC反應兩小時以上。反應以FT-IR光講監控,每隔一p 時間取樣,直至酐官能基波峰消失。反應完全後,再以減壓濃縮除去τ肪,得到 -12- < 3 1361812 • · POE2000-TMA/4COOH酰氨基酸產物為淡黃色黏稠液體》 步驟B :合成奈米銀粒子(AgNP) 於三頸瓶中,將穩定劑POE2〇〇0/4C〇〇H (0.069 g)溶於水(5〇 g)中,以 磁石攪拌,再加入AgN〇3 (0. 045 g)。兩小時後,分批加入調配好的NaBH4溶液 (〇· 015 g,先溶於50 g水中),並劇烈攪拌,溶液會立即呈現墨黑色,反應 全程通氮氣。 實施例2
| 步驟(A):製備穩定劑 p〇E2〇〇〇-TMA/2COOH 將實施例1的產物POE2000/4COOH,以150°C加熱3小時,由FT-IR監控亞 胺基確認’得產物POE2000/2COOH亞胺酸。 步驟(B):合成奈米銀粒子(AgNP) 同實施例1,但穩定劑改為P〇E2〇〇〇/4C〇〇H。 _實施例3
步驟(A):製備穩定劑P〇P2〇〇〇-tma/4COOH 將實施例1的親水性p〇E2〇〇〇改為疏水性的p〇p2〇〇〇,得產物p〇p2〇〇〇/4C〇〇H 亞胺酸。 步驟(B):合成奈米銀粒子(AgNp) 同實施例1,但穩定劑改為p〇p2〇〇〇_TMA /4C〇〇H。 -13- 1361812. 實施例4
步驟(A):製備穩定劑POP2000-TMA /2C00H 將實施例3的產物P〇P2〇〇〇/4COOH,以151TC加熱3小時,由FT-IR監控亞 胺基,得產物POP20O0/2COOH亞胺酸。 歩驟(B):合成奈米銀粒子(AgNP) 同實施例1,但穩定劑改為POP2000-TMA /2C00H »
實施例5 步驟(A):製備穩定劑 p〇p2〇〇〇_pMDA/8C〇〇Na
500ml之三頸瓶中加入聚醚二胺p〇p2〇〇〇 (4〇 g,〇 〇2 m〇1 ),使溶於w 的THF,再逐滴加入二酐PMDA (6· 54 g,〇 〇3 m〇卜先溶於1〇〇拊的顶^,使 POP2_與PMDA以2 : 3比例反應。反應溶液以機械攪拌,並全程充氮氣,反應 溫度控制在3G°C以f,反應3小時。反應以IR監控,每隔-段時陳樣,直至 酐官能基消失於FT-IR光譜。反應完全後,再以減壓濃縮除去THF,得到產物為 淡黃色黏稠液體。再將合成出之p〇p2〇〇〇_pMDA/8C〇〇H加入(3. 2 g ’ 〇. 〇8 m〇1) 之NaOH使之鈉化成水性之高分子鈉鹽。 步驟(B):合成奈米銀粒子(AgNp) 同實施例1,但穩定劑改為POP2000-PMDA/8COONa。 1361812. •實施例6
步驟(A):製備穩定劑 p〇E2〇〇〇-PMDA/4COOH 將實施例5的產物p〇E2〇〇〇-PMDA/8COOH加熱至15(TC,反應3小時,以FT-IR 監控生成醯胺的特性官能基,確認生成產物POE200Q- PMDA/4C〇〇H亞胺酸。 步驟(B) ··合成奈米銀粒子(AgNp) 同實施例1 ’但穩定劑改為P〇E2000_pMDA/4C〇〇H。
實施例7
步驟(A):製備穩定劑P〇p2〇〇〇_SMA/c〇〇H SMA 與 POP200〇 先以 12(TC抽真空除水 6 小時,SMA3000 (10. 0 g,24. 4 mmol of ΜΑ)、P〇P20〇〇(97. 6 g ’ 48. 8 mmol)分別溶於THF (50 mL)中。接著,將 SMA 逐次加入POP2000 t,為避免交聯,取p〇p2〇〇〇 —倍過量與SMA進反應。反應
過程以GPC與IR監控’確保合成之梳狀型高分子未交聯與反應之進行。過量之 POP2000利用梳狀型高分子與直鏈型聚醚胺鏈段之溶解度不同,以乙醇與水(或 甲苯)之混合溶劑進行純化分離,未反應的p〇p2〇〇〇可溶於混合溶劑中, POP2QOO-SMA/COOH 將沉殿分離。 步驟(B) ·合成奈米銀粒子(Agjyjp) 同實施例1,但穩定劑改為POP2000-SMA/COOH。 -15· < S ) 1361812.
實施例8 步驟(A):製備穩定劑 POE2000-POP2000-MDI 將Jeffamine* ED-2001及M2070放入l〇〇°C真空烘箱6小時除水,MDI以 減壓蒸餾純化。於100 ml三頸瓶中,加入連接劑MDI (1. 5g,6mm〇1,先溶於 15 g曱本中)’再逐滴加入ED-2001 (5. 99g,3刪〇1 ’先溶於10 g甲苯中), 以磁石不斷擾拌’最後加入M2070 (11.99g,6刪〇1,先溶於20 g甲笨),使 MDI、ED-20(U、M2070之莫耳比為2 : 1 : 2。反應全程通氮氣,並以FT-IR監控,
待MDI特性官能基消失碟定反應完成,最後置於8{rc真空烘箱12小時,除去溶 劑。產品為淡黃色黏稠液體。 步驟(B).合成奈求銀粒子(AgNp) 同實施例1,但穩定劑改為P〇E2〇〇〇-p〇P2〇〇〇-MDI。 比較例1 操作步驟同貫施例1,但以單純的p〇E2_代替p〇E2〇〇〇—覆/棚册當做 穩定舰雜’結果發現瓶身底部有大餘齡沉澱,證明使縣發明所合成 之穩定劑為必要的。 產物分析 以實施例1之產物為例,儀器分析結果如下·· 1·粒子生成.以UV觀察’在波長働面顯示出奈米銀顆粒的特徵吸收,證明 奈米銀粒子已生成。 粒子穩定_ .•在跳條件下供乾〗辦,依财制均—分佈的奈米銀粒 子’在TM _察下可魏_小於編的絲錄子,如第丨圖所示。 ,、中圖片3為,:|度O.Olwt.%;圖片b為濃度G.3wt%;圖片c為濃度0〇脱% 2. 1361,812. = 0.3 wU的溶液稀釋);圖片d亦為濃度0鳥t % (將水完全 稀釋絲齡,本發崎得的絲錄子溶㈣實財高穩定性。 3. 2粒圖 =、分佈:應更近一步可觀察到銀粒子的分布大約為㈣咖,如第 粒子濃縮液及寧藉 ^ , ^10
相較於傳統銀分散液只可達約5 wt%,且有高濃度沈澱或粒子聚集等缺點, 本發明以高分子魏时穩定賴原賴成為奈綠絲子,且时量可達至 少10減。分子量職反應基反應連結後約在5D(MM⑻,反應官能基包 括酐、羧酸基、環氧基、異氰酸鹽。 综上’本發明之優點包括: 1.利用合成之新型高分子分散劑,可經由控制高分子躲麟絲子之比例, 得到不同粒徑之奈米銀粒子。 % 2.所製備之銀分紐產物’在經職溫錢濃縮後可得高濃度之銀漿,並可再 度分散成穩定分散液。分散媒介包括水相中或其他有機溶劑如甲醇、乙醇、 IPA、丙鲷、THF、MEK等。應用廣泛。 3.由於可製備高濃度之奈米絲子,此應用對於有機高分子(包括ρι、細y、 Nylon、PP、ABS、PS…等)摻混,以提昇高分子之導電、抗菌等物理性質。 本發明之奈米銀粒子因帶親油與親水性質,均可與高分子相容,並達到均勻 分散單一銀粒子結構於高分子中達奈米尺度。 -17- 1361812. 【圖式簡單說明】 第1圖係以TEM觀察銀粒子之穩定情形; 第2圖係以AFM觀察銀粒子的粒徑分布。
Claims (1)
1361812 ,公告 十、申請專利範圍: /270年丨> 月日補充修正替換頁 |〇0年1^月P日修正本 1·一種高分子型聚胺,包括一聚醚胺及與其末端胺官能基結合之 連接劑,該聚醚胺為分子量範圍為200〜10,000之聚醚單胺或二胺, 且其主幹為乙婦基謎(oxyethylene)及/或丙稀基醚(oxypropylene),連 接劑係選自 if (anhydride)、幾酸(carboxylic acid)、二環氧化物(glycidyl 或 epoxide)、二異氰酸(isocyanate 或 disocyanate)及馬來酐(maleic anhydride或maleated polystyrene)所組之群,該高分子型聚胺分子量 範圍為 500-10,000 mol/g。
2.如申請專利範圍第1項所述之高分子型聚胺,其中該連接劑 係苯三甲酸酐(TMA)。 3.如申請專利範圍第1項所述之高分子型聚胺,其中該連接劑係 苯乙烯/馬來酐共聚物(SMA)。 4. 如申請專利範圍第1項所述之高分子型聚胺,其中該連接劑係 均苯四酸二酐(PMDA)。 5. 如申請專利範圍第1項所述之高分子型聚胺,其中該連接劑係 4,4’-二苯曱基二異氰酸酯(MDI)。 6. —種高固含量之奈米銀粒子,包括—如申請專利範圍第丨項所 述之高分子型聚胺、銀及一溶劑’其莫耳比組成為:高分子胺分散劑: 銀=1 : 10〜10 : 1 ’銀:溶劑=1 : 1000〜10 : 1,即銀之固含量為100 ppm至90 wt·% ’其中該溶劑為水或有機溶劑。 7. 如申凊專利範圍第6項所述之南固含量之奈米銀粒子,其中該 有機溶劑為乙醇、丙酮、乙二醇、二甲基甲醯胺、N,N—二甲基乙醯 胺或N—甲基吡咯烷酮。 8. —種製造高分子型聚胺的方法,係以聚醚胺與具有反應官能基 的連接劑反應’該反應係於聚醚胺中逐滴加入連接劑並濃合,或於連 接劑中逐滴加入聚醚胺並混合,其中該聚醚胺為分量範圍為 1361812 1 /夕P年月 y曰補充修正替換頁 200〜10,000之聚醚單胺或二胺,且其主幹為乙烯基醚(oxyethylene)及 /或丙稀基謎(oxypropylene),該連接劑係選自針(anhydride)、缓酸 (carboxylic acid)、二環氧化物(glycidyl 或 epoxide)、二異氰酸 (isocyanate 或 disocyanate)及馬來 if (maleic anhydride 或 maleated polystyrene)所組之群,該高分子型聚胺分子量範圍為500〜10,000 mol/g。
9. 如申請專利範圍第8項所述之方法,其中聚醚胺可表示為H2N —R—NH2,R係選自二針、二酸、環氧化物、二異氰酸或苯乙歸^馬 來酐共聚物(SMA)所組之群,H2N或NH2為胺官能基。 10. 如申請專利範圍第8項所述之方法,其中聚醚胺與連接劑之 莫耳比為 n : (n+ 1)或(n+ 1) : 1,n = 1〜5。 11·如申請專利範圍第8項所述之方法,其反應溫度為 25°C~150°C,反應時間為1〜12小時。 12.如申請專利範園第8項所述之方法,其中該連接劑係選自均 苯四酸二酐(PMDA)、苯三甲酸酐(TMA)、4,4’-二苯曱基二異氰酸酯 (MDI)及苯乙烯/馬來酐共聚物(SMA)所組之群。
13·—種穩定奈米銀粒子之方法,係以高分子型聚胺為穩定劑或 分散劑,與銀鹽水溶液混合後,再以還原劑還原銀粒子,形成一含有 奈米銀粒子的溶液;其中該高分子型聚胺包括一聚醚胺及與其末端胺 官能基結合之連接劑,該聚謎胺為分子量範圍為200〜1〇,〇〇〇之聚醚 單胺或二胺’且其主幹為乙稀基韃(0Xyethylene)及/或丙稀基謎 (oxypropylene) ’ 連接劑係選自酐(anhydride)、叛酸(carboxylic acid)、 一環氧化物(glycidyl 或 epoxide)、二異氰酸(isocyanate 或 disocyanate) 及馬來酐(maleic anhydride 或 maleated polystyrene)所組之群。 14.如申請專利範圍第13項所述之方法,其中該銀鹽為硝酸銀、 碘化銀、溴化銀、氣化銀或五氟丙酸銀。 20 1361812 _ . » . /夕汐年以月曰補充修正替換頁 .15.如申請專利範圍第項所述《方法,其中高分子型聚胺與銀 之重量比為1 ·· 10〜10 : 1。 ΐ6·如申請專利範圍第η項所述之方法,其中該還原劑為棚氮化 納(NaBEU)、甲醇、乙醇、丙三醇、乙二醇、十二醇、η,νη2、甲 路、PVA._yvinyl alcohol ’ 聚乙稀醇)或 (dimethyif〇r_ide, 二甲基甲醯胺)。 17. 如申sf專利範圍第13項所述之方法,其中該還原反應之溫度 為0〜80〇C。
18. 如申請專利範圍第13項所述之方法,其中該還原反應之時間 為1〜24小時。 19.如申請專利範圍第13項所述之方法,其中該含有奈米銀粒子 的溶液尚可以一倍以上莫耳比的氫氧化鈉鈉化成為鈉鹽,以增加其水 溶性。 20.如申請專利範圍第13項所述之方法,其中該連接劑係選自苯 三甲酸酐(TMA)、均苯四酸二酐(PMDA)、苯乙烯/馬來酐共聚物(SMA) 及4,4’-二苯曱基二異氰酸酯(MDI)所組之群。 21.—種高分子型聚胺,其結構式係選自Linker — HN — R — NH — Linker、H2N — R — NH — Linker、H2N — R — NH — Linker、H2N — R — NH — Linker NH — R — NH2' Linker — (HN — R — NH — Linker)x 及 H2N —R — NH—(Linker—HN — R — NH)x — H 所組之群;其中 Linker 係選 自 gf (anhydride)、缓酸(carboxylic acid)、二環氧化物(glycidyl 或 epoxide)、二異氰酸(isocyanate 或 disocyanate)及馬來 If (maleic anhydride 或 maleated polystyrene)所組之群,R 係選自二酐、二酸、 環氧化物、二異氰酸及苯乙烯/馬來酐共聚物(SMA)所組之群’ x = 1〜5,H2N、NH2、HN或NH為胺官能基。 21
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI579074B (zh) * | 2013-05-24 | 2017-04-21 | 田中貴金屬工業股份有限公司 | 銀粒子之製造方法 |
US10213758B2 (en) | 2015-11-05 | 2019-02-26 | Industrial Technology Research Institute | Polymer and dispersion |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI374568B (en) * | 2008-11-27 | 2012-10-11 | Univ Yuan Ze | Fabrication of metal meshes/carbon nanotubes/polymer composite bipolar plates for fuel cell |
TWI403373B (zh) * | 2009-07-16 | 2013-08-01 | Univ Nat Taiwan | 應用乙醇胺以製造奈米銀粒子之方法 |
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US8268359B2 (en) * | 2009-08-26 | 2012-09-18 | Indian Institute Of Technology Madras | Organic polymer-inorganic fine particle antimicrobial composites and uses thereof |
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FI20115816L (fi) | 2011-08-22 | 2013-02-23 | Silverphase Oy | Antimikrobinen ionomeerikoostumus sekä sen käyttösovellukset |
EP2900409B1 (en) | 2012-09-27 | 2019-05-22 | Rhodia Operations | Process for making silver nanostructures and copolymer useful in such process |
US9243203B2 (en) * | 2012-11-30 | 2016-01-26 | Chevron Oronite Company Llc | Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation |
US9085699B2 (en) * | 2013-01-22 | 2015-07-21 | Eastman Kodak Company | Silver metal nanoparticle composition |
US8828275B2 (en) * | 2013-02-04 | 2014-09-09 | Eastman Kodak Company | Metal nanoparticle composition with water soluble polymer |
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US10066299B2 (en) * | 2013-02-24 | 2018-09-04 | Rohm And Haas Electronic Materials Llc | Plating catalyst and method |
WO2014143383A1 (en) | 2013-03-13 | 2014-09-18 | Agilent Technologies, Inc. | Transposome tethered to a gene delivery vehicle |
TWI492965B (zh) * | 2013-12-31 | 2015-07-21 | Ind Tech Res Inst | 聚合物與分散液 |
CN105242492A (zh) * | 2014-07-10 | 2016-01-13 | 碁达科技股份有限公司 | 钻孔用辅导片的感旋光性涂覆树脂及其应用 |
JP6428339B2 (ja) | 2015-02-13 | 2018-11-28 | 三菱マテリアル株式会社 | 銀粉及びペースト状組成物並びに銀粉の製造方法 |
US10361575B2 (en) * | 2015-02-17 | 2019-07-23 | Murata Manufacturing Co., Ltd. | Power storage module, power storage apparatus, power storage system, control method, electronic apparatus, electric vehicle, and electric power system |
KR102264701B1 (ko) * | 2016-07-20 | 2021-06-11 | 삼성에스디아이 주식회사 | 이차전지 |
CN106041352B (zh) * | 2016-08-17 | 2018-05-01 | 武汉工程大学 | 一种有机酸银包覆纳米银颗粒及其制备方法和应用 |
CN108479632B (zh) * | 2018-04-10 | 2020-08-11 | 佛山市贝特尔化工有限公司 | 一种具有颜料通用性的水性分散剂的制备方法 |
CN108948426A (zh) * | 2018-07-05 | 2018-12-07 | 胡果青 | 一种塑料增塑剂的制备方法 |
CN108907228A (zh) * | 2018-07-24 | 2018-11-30 | 郑州阿弗雷德化工科技有限公司 | 纳米银溶液及其低成本合成方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3666788A (en) * | 1969-08-22 | 1972-05-30 | Jefferson Chem Co Inc | Cyanoalkylated polyoxyalkylene polyamines |
US4689051A (en) * | 1986-05-28 | 1987-08-25 | Texaco Inc. | Storage-stabilizing additives for middle distillate fuels |
US4761465A (en) * | 1987-07-27 | 1988-08-02 | Texaco Inc. | Difunctional isocyanate-terminated polyoxyalkylene diamine prepolymers and polymer coatings applications |
US4826995A (en) * | 1987-11-25 | 1989-05-02 | Texaco Inc. | Bismaleimide derivatives of higher molecular weight polyoxyalkyleneamines |
US5064571A (en) * | 1989-08-11 | 1991-11-12 | Texaco Chemical Company | Mixtures of fatty amido-amines from polyoxyalkyleneamines |
EP0459245A3 (en) * | 1990-05-30 | 1993-01-07 | General Electric Company | Blow mouldable copolyetherimide ester compositions |
US5308882A (en) * | 1993-09-07 | 1994-05-03 | Texaco Chemical Company | Preparation of polyurethane foam without a tertiary amine catalyst |
US20040166088A1 (en) * | 2003-01-15 | 2004-08-26 | Shalaby Shalaby W. | Polymeric precursors of non-absorbable, in situ-forming hydrogels and applications thereof |
US20050215730A1 (en) * | 2004-03-24 | 2005-09-29 | Rainer Schoenfeld | Polycarboxy-functionalized prepolymers |
US20060034899A1 (en) * | 2004-08-12 | 2006-02-16 | Ylitalo Caroline M | Biologically-active adhesive articles and methods of manufacture |
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2007
- 2007-12-07 TW TW096146929A patent/TW200925178A/zh unknown
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Cited By (2)
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US10213758B2 (en) | 2015-11-05 | 2019-02-26 | Industrial Technology Research Institute | Polymer and dispersion |
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