US20110288239A1 - Polymeric polyamines and method for producing the same - Google Patents
Polymeric polyamines and method for producing the same Download PDFInfo
- Publication number
- US20110288239A1 US20110288239A1 US13/195,022 US201113195022A US2011288239A1 US 20110288239 A1 US20110288239 A1 US 20110288239A1 US 201113195022 A US201113195022 A US 201113195022A US 2011288239 A1 US2011288239 A1 US 2011288239A1
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- US
- United States
- Prior art keywords
- linker
- anhydride
- amine
- polyoxyalkylene
- diisocyanate
- 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.)
- Abandoned
Links
- 229920000768 polyamine Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 46
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 7
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 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 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 125000006159 dianhydride group Chemical group 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- LOYDTBZMMPQJNI-UHFFFAOYSA-N 3a-methyl-5,6-dihydro-4h-2-benzofuran-1,3-dione Chemical compound C1CCC=C2C(=O)OC(=O)C21C LOYDTBZMMPQJNI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- XBRDVIRMHNWLRC-UHFFFAOYSA-N N=C=O.N=C=O.C=C1CC=CC=C1C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=C1CC=CC=C1C1=CC=CC=C1 XBRDVIRMHNWLRC-UHFFFAOYSA-N 0.000 claims description 3
- OLZFLXYNBWHDHZ-UHFFFAOYSA-N N=C=O.N=C=O.CC(C)C(C)=O Chemical compound N=C=O.N=C=O.CC(C)C(C)=O OLZFLXYNBWHDHZ-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 claims 2
- 229910052709 silver Inorganic materials 0.000 abstract description 18
- 239000004332 silver Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- -1 silver ions Chemical class 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 230000000087 stabilizing effect Effects 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 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 abstract description 5
- 230000006837 decompression Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 125000005647 linker group Chemical group 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 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 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 0 *C[3H].C.C=CC.CC(COC(C)(C)N1C(=O)C2=CC=C(C(=O)O)C=C2C1=O)N1C(=O)C2=C(C=C(C(=O)O)C=C2)C1=O.CC(COC(C)(C)N1C(=O)C2=CC=C(C(=O)[Na]O)C=C2C1=O)N1C(=O)C2=C(C=C(C(=O)O[Na])C=C2)C1=O.CC(COCC(C)NC(=O)C1=C(C(=O)O)C=CC(C(=O)O)=C1)NC(=O)C1=CC(C(=O)O)=CC=C1C(=O)O.CC(COCC(C)NC(=O)C1=C(C(=O)[Na]O)C=CC(C(=O)O[Na])=C1)NC(=O)C1=CC(C(=O)[Na]O)=CC=C1C(=O)O[Na].CC(COCCOCC(C)OC(C)(C)NC(=O)C1=CC(C(=O)O)=CC=C1C(=O)O)NC(=O)C1=C(C(=O)O)C=CC(C(=O)O)=C1.CC(N)COCCOCC(C)ON.O=C(O)C1=CC=C2C(=O)OC(=O)C2=C1 Chemical compound *C[3H].C.C=CC.CC(COC(C)(C)N1C(=O)C2=CC=C(C(=O)O)C=C2C1=O)N1C(=O)C2=C(C=C(C(=O)O)C=C2)C1=O.CC(COC(C)(C)N1C(=O)C2=CC=C(C(=O)[Na]O)C=C2C1=O)N1C(=O)C2=C(C=C(C(=O)O[Na])C=C2)C1=O.CC(COCC(C)NC(=O)C1=C(C(=O)O)C=CC(C(=O)O)=C1)NC(=O)C1=CC(C(=O)O)=CC=C1C(=O)O.CC(COCC(C)NC(=O)C1=C(C(=O)[Na]O)C=CC(C(=O)O[Na])=C1)NC(=O)C1=CC(C(=O)[Na]O)=CC=C1C(=O)O[Na].CC(COCCOCC(C)OC(C)(C)NC(=O)C1=CC(C(=O)O)=CC=C1C(=O)O)NC(=O)C1=C(C(=O)O)C=CC(C(=O)O)=C1.CC(N)COCCOCC(C)ON.O=C(O)C1=CC=C2C(=O)OC(=O)C2=C1 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 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
- 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- ZEWFACGLVNNTRZ-UHFFFAOYSA-N C.C.C.C.C.C.C=CC.CC(N)COCCOC/C=O(\C)N Chemical compound C.C.C.C.C.C.C=CC.CC(N)COCCOC/C=O(\C)N ZEWFACGLVNNTRZ-UHFFFAOYSA-N 0.000 description 1
- OJAHXQWOZSKBEP-UHFFFAOYSA-N C.C.C.C.C=CC.COCCOCC(C)ON Chemical compound C.C.C.C.C=CC.COCCOCC(C)ON OJAHXQWOZSKBEP-UHFFFAOYSA-N 0.000 description 1
- MTHLAYBBJJZLGO-UHFFFAOYSA-N CC(C)C(=O)C(C)C(CC(C)C1=CC=CC=C1)C(=O)O Chemical compound CC(C)C(=O)C(C)C(CC(C)C1=CC=CC=C1)C(=O)O MTHLAYBBJJZLGO-UHFFFAOYSA-N 0.000 description 1
- BAGWYDYDJRVKOM-UHFFFAOYSA-N CC(CC(C(=O)O)C(C)C(=O)C(C)(C)C)C1=CC=CC=C1 Chemical compound CC(CC(C(=O)O)C(C)C(=O)C(C)(C)C)C1=CC=CC=C1 BAGWYDYDJRVKOM-UHFFFAOYSA-N 0.000 description 1
- GZZSBQIOPFZIFW-UHFFFAOYSA-N CC(CC1C(=O)OC(=O)C1C)C1=CC=CC=C1 Chemical compound CC(CC1C(=O)OC(=O)C1C)C1=CC=CC=C1 GZZSBQIOPFZIFW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- GZORJAFFPJJJQU-UHFFFAOYSA-N n,n-dimethylacetamide;1-methylpyrrolidin-2-one Chemical compound CN(C)C(C)=O.CN1CCCC1=O GZORJAFFPJJJQU-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000006353 oxyethylene group Chemical group 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 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 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
- 150000003388 sodium compounds Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
Images
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
Abstract
The present invention discloses a polymeric polyamine which can be produced by polymerizing polyoxyalkylene-amine and a linker. The linker can be anhydride, carboxylic acid, epoxy, isocyanate or poly(styrene-co-maleic anhydride) copolymers (SMA). The present invention also discloses a method for stabilizing the Ag nanoparticles with polymeric polyamine. The polymeric polyamine serving as a stabilizer or dispersant is mixed with a water solution of silver salt and then a reducer is provided to reduce the silver ions and form an organic or a water solution of Ag nanoparticles. Water or solvent of this solution can be further removed through a heating, freezing or decompression process, and thus solid content of the solution can be increased. The concentrated solution also can be diluted to obtain a stable dispersion without aggregation.
Description
- The present application is a division of prior U.S. application Ser. No. 12/140,507 filed Jun. 17, 2008, entitled “POLYMERIC POLYAMINES AND METHOD FOR STABILIZING SILVER NANOPARTICLE BY EMPLOYING THE SAME”. The prior U.S. Application claims priority of Taiwan Patent Application No. 096146929, filed on Dec. 7, 2007, the entirety of which is incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates to polymeric polyamines and a method for stabilizing Ag nanoparticles by employing the same. The produced Ag nanoparticles are in the form of silver slurry, silver gel or solid, and suitable for composite material or antimicrobial material. Fields of the present invention include electric industries, for example, conductive silver nanowires, parts and sensors, and biomedicine or medicinal industries. In addition, the Ag nanoparticles have both hydrophilic and hydrophobic properties and therefore can be dissolved in water and organic solvents, and are compatible with many kinds of polymers. Therefore, the product of the present invention is a good polymeric surfactant or dispersant suitable for dispersing nanoscale particles, for example, pigments and silver particles.
- 2. Related Prior Arts
- The application of Ag nanoparticles is one of the most important technologies in this century. The traditional methods for producing water solutions of Ag nanoparticles are primarily to reduce silver nitrate or other silver salts with organic surfactants, dispersants or stabilizers for stabilizing the Ag nanoparticles. To exhibit good effects in antimicrobial, pharmaceutical, biomedicine and electrical applications, the Ag particles have to keep in the nanoscale and large surface areas without aggregation. Therefore, it's very important to control size of the Ag particles in the nanoscale and maintain thermal stability thereof.
- In processes for producing Ag nanoparticles, organic surfactants or stabilizers are an important operation factor. In addition, most silver slats, for example, silver nitrate, is more easily dissolved in water than organic solutions, and therefore the product is usually prepared in water solution. That is, the existing conditions will restrict applications of the Ag nanoparticles.
- The above problems have been discussed in some reports. In J. Phys. Chem. B 1998, 102, 10663-10666, the Ag particles are prepared in water solution and stabilized with molecular chains of sodium polyacrylate or polyacrylamide. In Chem. Mater. 2005, 17, 4630-4635, thioalkylated poly(ethylene glycol) is used as a stabilizer for stabilizing Ag particles in water. In Langmuir 1999, 15, 948-951, 3-aminopropyltrimethoxysilane (APS) is used as a stabilizer and N,N-dimethylformamide is used to reduce silver ions in water. In J. Phys. Chem. B 1999, 103, 9533-9539, sodium citrate is used to prevent the Ag particles from aggregation or agglomeration which results in larger particle size, wider size distribution or multiple-peak distribution. In Langmuir 1996, 12, 3585-3589, some nonionic surfactants (polyethylene oxide or ethoxylated block) are used to stabilize Ag nanoparticles which are in the form of gel-type particles covered with molecular chains of the surfactant, the examples include poly-(10)-oxyethylene oleyl ether and Tween 80 (polyoxyethylene-(20)-sorbitan monooleate) (available from Sigma). In Langmuir 1997, 13, 1481-1485, NaBH4 is used as a reducing agent, and the reaction equation is:
-
2AgNO3+2NaBH4+6H2O→2Ag+2NaNO3+2H3BO3+7H2 - In this reaction, the stabilizers are cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, sodium dodecyl sulfate (SDS) as an anionic surfactant and poly(oxyethylene)isooctylphenyl ether-TX-100 as a nonionic surfactant.
- As described in the above, the traditional method for stabilizing Ag particles is to add surfactants or stabilizers. However, the solutions of such Ag particles have solid contents less than 10% and can not be in the form of silver slurry, or have a higher solid content with aggregation.
- The object of the present invention is to provide a polymeric polyamine and a method for producing the same, wherein polymeric polyamine can be applied to producing Ag nanoparticles for stabilizing and dispersing.
- Another object of the present invention is to provide a method for stabilizing Ag nanoparticles with polymeric polyamine, so that the produced silver slurry, silver gel or solid silver has a high solid content and good stability, even after processing treatment or preservation.
- To achieve the above objects, polymeric polyamine of the present invention includes polyoxyalkylene-amine and a linker linking with an amino end thereof. The polyoxyalkylene-amine is preferably monoamine, diamine or triamine having a molecular weight about 200˜10,000, and the linker can be anhydride, carboxylic acid, epoxy, isocyanate or poly(styrene-co-maleic anhydride) copolymers (polystyrene-maleic anhydride polymers, SMA).
- The proper linker includes: (1) anhydride, for example, maleic anhydride, succinic acid anhydride, trimellitic anhydride (TMA), benzene tetracarboxylic dianhydride (PMDA), phthalic anhydride, tetrahydromethyl-1,3-isobenzofurandione and poly(styrene-co-maleic anhydride) copolymers; (2) carboxylic acid, for example, dicarboxylic acid, adipic acid, succinic acid, p-phthalic, isophthalic acid; (3) glycidyl or epoxide, for example, diglycidyl ether of bisphenol-A (DGEBA), 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate; (4) isocyanate or diisocyanate, for example, toluene diisocyanate, methylen-biphenyldiisocyanate, 1,6-cyclohexamethylene-diisocyanate, methyl isopropyl ketone diisocyanate; and (5) maleic anhydride or maleated polystyrene, for example, SMA. The preferred linker includes benzene tetracarboxylic dianhydride (PMDA), trimellitic anhydride (TMA) and adipic acid.
- The polymeric polyamine can have a structural formula: 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 or H2N—R—NH-(Linker-HN—R—NH)x—H; wherein x=1˜5, H2N—R—NH and HN—R—NH are polyoxyalkylene-amine, R can be dianhydride, diacid, epoxy, diisocyanate or poly(styrene-co-maleic anhydride) copolymers (SMA).
- The method for producing polymeric polyamine is to react polyoxyalkylene-amine with a linker having a reactive functional group. Segments of polymeric polyamine may chelate silver nanoparticles, and disperse in both water phase and an organic solvent. Accordingly, the Ag nanoparticles can be prepared as a stable concentrated gel, slurry or powders having a concentration more than 10 wt %. The polyoxyalkylene-amine and the linker are defined as the above.
- For the process, molar ratio of the polyamine to the linker can be changed to synthesize Linker-(HN—R—NH-Linker)x or H2N—R—NH-(Linker-HN—R—NH)x—H, having different end functional groups.
- After reaction of polyoxyalkylene-amine and the linker, the linker provides additional functional groups to enhance stability of silver in water or the organic solvent by chelating with silver. The solution will be more stable and the nanoparticles will not aggregate together.
- The molar ratio of the linker to polyoxyalkylene-amine is preferably (n+1):n, n=1˜5, the reaction temperature is preferably about 25˜150° C., and the reaction time is preferably about 1˜12 hours.
- In the present invention, the method for stabilizing Ag nanoparticles with polymeric polyamine includes steps of: (a) mixing polymeric polyamine and a water solution of silver salt; (b) reducing the Ag+ ions with a reducer to form a solution of Ag nanoparticles. The polymeric polyamine serves as a stabilizer or a dispersant and comprises polyoxyalkylene-amine and a linker linking with an amino end of polyoxyalkylene-amine.
- The polyoxyalkylene-amine has a molecular weight about 200˜10,000, and the linker is selected from the group consisting of anhydride, carboxylic acid, glycidyl, epoxide, isocyanate, diisocyanate, maleic anhydride and maleated polystyrene.
- The reducer can be NaBH4, methanol, ethanol, glycerin, ethylene glycol, dodecanol, H2N—NH2, formaldehyde, PVA or DMF. The weight ratio of polymeric polyamine to the silver salt is preferably about 1:10˜10:1. The silver salt can be AgNO3, AgI, AgBr, AgCl or silver pentafluoropropionate.
- The solution of Ag nanoparticles can be further dewatered to increase solid content thereof. An organic solvent can be also added to transfer the particles into the organic solvent.
- The solution of Ag nanoparticles can further comprise sodium hydroxide with a molar ratio to the Ag salt more than 1, so that water solubility of the solution will be increased.
-
FIG. 1 shows stable distribution of the Ag nanoparticles in the TEM picture; -
FIG. 2 shows the size distribution of the Ag nanoparticles in the AFM picture. - Materials used in the preferred embodiments of the present invention include:
- product of Huntsman Chemical Co., Jeffamine® Amines series, including:
- a. Jeffamine ED-2001: poly(oxypropylene-oxyethylene-oxypropylene)-bis-amines, polyoxyalkylene-amine with two functional groups, molecular weight=2000 (a.k.a. POE-2000), white color, hydrophilic, wax-like solid, mp. 35° C., amino content=0.95 mequiv./g, average oxyethylene/oxypropylene unit=39.5/5, structural formula:
- wherein a+c=6, b=38.7;
- b. Jeffamine M-2070: poly(oxypropylene-oxyethylene)-monoamine, polyoxyalkylene-amine with single functional group, molecular weight=2000 (a.k.a. POP-2000), hydrophobic, structural formula:
- wherein a=10, b=31.
2. Trimellitic anhydride (TMA) - product of Aldrich Chemical Co., purified with sublimation before using, structural formula:
- 3. Benzene tetracarboxylic dianhydride (PMDA)
- product of Aldrich Chemical Co. or Sino-Japan chemical Co.
- 4. Poly(styrene-co-maleic anhydride) copolymers (SMA)
- product of Aldrich Chemical Co. or Sino-Japan chemical Co., ratio of styrene/maleic anhydride or maleated polystyrene can be 1/1, 3/1, 6/1 or 11/1, average molecular weight=6,000 (SMA1000), 6,000 (SMA3000), 120,000 (SMA6000) and 140,000 (SMA11000).
- 5. 4,4′-methylenebis(phenyl isocyanate) (MDI)
6. Silver nitrate - AgNO3 (99.8%), product of Aldrich.
- a reducing agent.
- In the present invention, the method for producing polymeric polyamine is to polymerize hydrophilic or hydrophobic polyoxyalkylene-amine with the linker. The product could be hydrophilic or hydrophobic.
- The reaction is exemplified with schemes. When the linker is TMA, polyoxyalkylene-amine is hydrophilic POE2000 or hydrophobic POP2000, and sodium hydroxide is added for modifying the ions after the reaction, the reaction equations are as follows:
- When the linker is PMDA, polyoxyalkylene-amine is hydrophobic POP2000, and sodium hydroxide is added for modifying the ions after reaction, the reaction equations are as follows:
- When the linker is SMA and polyoxyalkylene-amine is various, comb-like polymers can be obtained as follows:
- When the linker is MDI and polyoxyalkylene-amine is various, the reaction equations are as follows:
- (step 1)
- (step 2)
- First, hydrophilic POE2000 (Jeffamine® ED-2001) is purified with sublimation. THF is dewatered with calcium hydride and then preserved with molecular sieves. Next, to a three-necked bottle (500 ml), POE2000 (100 g, 0.05 mol) is added and dissolved in THF (150 ml), and then anhydride linker TMA (19.2 g, 0.10 mol, previously dissolved in THF (50 ml)) is added drop by drop, so that molar ratio of POE2000 to TMA is 1:2. The reactant is mechanically stirred and filled with nitrogen during the whole reaction. The reaction is performed at 30° C. for 2 hours or longer. FT-IR spectrum is used for monitoring progress of the reaction by sampling every period of time until the anhydride functional groups disappear. After the reaction is completed, THF is removed by decompression to obtain creamy glue product, amido acid POE2000-TMA/4COOH.
- To a three-necked bottle, the stabilizer POE2000/4COOH (0.069 g) is dissolved in water (50 g) which is stirred with a magnetic stirrer. AgNO3 (0.045 g) is then added later. After 2 hours, a NaBH4 solution (0.015 g, previously dissolved in water (50 g)) is added incontinuously and vigorously agitated. The solution immediately becomes black. The reactor is filled with nitrogen during whole reaction.
- The product POE2000/4COOH of Example 1 is heated at 150° C. for 3 hours. Progress of the reaction is monitored with FT-IR for identifying imido functional groups. The product is imido acid POE2000/2COOH.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POE2000/2COOH.
- Repeat Step (A) of Example 1, but hydrophilic POE2000 is replaced with hydrophobic POP2000 to obtain product imido acid POP2000/4COOH.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POE2000/4COOH.
- The product POP2000/4COOH of Example 3 is heated at 150° C. for 3 hours. Progress of the reaction is monitored with FT-IR for identifying imido functional groups. The product is imido acid POP2000/2COOH.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with—POP2000/2COOH.
- To a three-necked bottle (500 ml), POP2000 (40 g, 0.02 mol) is added and dissolved in THF (100 ml), and then the dianhydride linker TMA (6.54 g, 0.03 mol, previously dissolved in THF (100 ml)) is added drop by drop, so that molar ratio of POP2000 to PMDA is 2:3. The reactant is mechanically stirred and filled with nitrogen during the whole reaction. The reaction is performed below 30° C. for 3 hours. FT-IR spectrum is used for monitoring progress of the reaction by sampling every period of time until the anhydride functional groups disappear. After the reaction is completed, THF is removed by decompression to obtain creamy glue product, amido acid POP2000-PMDA/8COOH. Into the product POP2000-PMDA/8COOH (3.2 g, 0.08 mol), NaOH is added to form a water-soluble polymeric sodium compound.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POP2000-PMDA/8COOH.
- The product POE2000-PMDA/8COOH of Example 5 is heated at 150° C. for 3 hours. Progress of the reaction is monitored with FT-IR for identifying amido functional groups. The product is amido acid POE2000-PMDA/4COOH.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POE2000-PMDA/4COOH.
- SMA and POP2000 are previously dewatered in vacuum at 120° C. for 6 hours. SMA3000 (10.0 g, 24.4 mmol of MA) and POP2000 (97.6 g, 48.8 mmol) are respectively dissolved in THF (50 mL). Next, SMA is incontinuously added into POP2000. To prevent cross-linking, the molar ratio of POP2000 to SMA is more than 1. Progress of the reaction is monitored with GPC and IR to confirm no cross-linking between the synthesized comb-like polymers. The excess POP2000 is isolated with a solvent mixture of water (or toluene) and ethanol due to different solubilities of the comb-like polymer and the straight-chain polyoxyalkylene-amine. The unreacted POP2000 can be dissolved in the solvent mixture and POP2000-SMA/COOH precipitates.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POP2000-SMA/COOH.
- Jeffamine® ED-2001 and M2070 are first dewatered in a vacuum oven at 100° C. for 6 hours, and MDI is purified with decompressing distillation. To a three-necked bottle (100 ml), the linker MDI (1.5 g, 6 mmol, previously dissolved in toluene (15 g)) is added, and then ED-2001 (5.99 g, 3 mmol, previously dissolved in toluene (10 g)) is added drop by drop. The solution is continuously mixed with a magnetic stirrer. Next, M2070 (11.99 g, 6 mmol, previously dissolved in toluene (20 g)) is added into the solution. The molar ratio of MDI:ED-2001:M2070 is 2:1:2. The reactor is filled with nitrogen during the whole reaction. Progress of the reaction is monitored with FT-IR until the characteristic functional groups of MDI disappear. The solvent is removed from the solution by heating in a vacuum oven at 80° C. for 12 hours. The product is creamy glue.
- Repeat Step (B) of Example 1, but the stabilizer is replaced with POE2000-POP2000-MDI.
- Repeat the procedures of Example 1, but the stabilizer POE2000-TMA/4COOH is replaced with POE2000. After the reaction, a lot of silver particles precipitate on the bottom of the bottle, which shows that the stabilizer synthesized by the method of the present invention is required.
- Properties and features of the product of Example 1 are analyzed with instruments and results are as follows:
- 1. Formation of the Ag nanoparticles
- The Ag nanoparticles are identified by UV absorbance at wave length 400 nm.
- 2. Stability of the Ag nanoparticles
-
FIG. 1 shows TEM pictures of the products concentrated with a rotary evaporator or a drier to have concentrations of 0.01 wt. % (picture a), 0.3 wt. % (picture b), 0.01 wt. % (picture c, diluted from the slurry of 0.3 wt. %), and 0.01 wt. % (picture d, diluted after evaporated). As shown inFIG. 1 , the Ag nanoparticles uniformly distribute and have diameters less than 30 nm after heating at 80° C. for 1 hour. That is, the solution containing Ag nanoparticles of the present invention is highly stable. - 3. Diameter distribution
-
FIG. 2 shows AFM pictures and distribution of the Ag nanoparticles, in which diameters of the Ag particles range about 33˜25 nm. - The Ag nanoparticles of the present invention can be concentrated to 10 wt % or higher with an evaporator or a drier, for example, decompression at 80° C. or freezing at 0° C. The highly concentrated solution can be also diluted and the dilution also exhibits good dispersibility and thermal stability.
- The traditional silver solution has a concentration limit of 5 wt % and easily forms participate or aggregation. Contractively, by means of the present invention, solid content of the solution containing Ag nanoparticles can be promoted to 10 wt % or even higher. The most important factor is that a novel stabilizer, polymeric polyamine, is provided in the reduction reaction of silver salt into Ag nanoparticles. Molecular weight of the Ag nanoparticles is about 500˜10,000 mol/g, and the functional groups may include anhydride, carboxylic acid, epoxy and isocyanate.
- According to the above, features or advantages of the present invention at least include:
- 1. Different sizes of Ag nanoparticles can be obtained by using a synthesized polymeric dispersant and controlling the ratio of polymeric polyamine to silver.
- 2. The prepared silver dispersion can be concentrated as a silver slurry which can be also diluted as a stable dispersion. The dispersing media can be water or other suitable organic solvents, for example, methanol, ethanol, IPA, acetone, ethylene glycol, dimethylformamide, N,N-dimethylacetamide N-methyl-2-pyrrolidinone, THF, MEK, etc.
- 3. The Ag nanoparticles of the present invention are both hydrophilic and hydrophobic and thus are compatible with polymer in nanoscale. The highly concentrated solution of Ag nanoparticles can be applied to blending with organic polymer (for example, PI, Epoxy, Nylon, PP, ABS, PS, etc.), so as to improve conductivity, antimicrobial (properties) thereof.
Claims (12)
1. A polymeric polyamine, comprising a polyoxyalkylene-amine and a linker linking with an amino end of the polyoxyalkylene-amine, wherein polyoxyalkylene-amine has a molecular weight of 200˜10,000, and the linker is selected from the group consisting of anhydride, carboxylic acid, glycidyl, epoxide, isocyanate, diisocyanate, maleic anhydride and maleated polystyrene.
2. The polymeric polyamine as claimed in claim 1 , which has a structural formula selected from the group consisting of 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 and H2N—R—NH-(Linker-HN—R—NH)x—H, wherein R is selected from the group consisting of dianhydride, diacid, epoxy, diisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA), x=1˜5.
3. The polymeric polyamine as claimed in claim 1 , wherein the linker is selected from the group consisting of maleic anhydride, succinic acid anhydride, trimellitic anhydride (TMA), benzene tetracarboxylic dianhydride (PMDA), phthalic anhydride, tetrahydromethyl-1,3-isobenzofurandione, dicarboxylic acid, adipic acid, succinic acid, p-phthalic, isophthalic acid, diglycidyl ether of bisphenol-A (DGEBA), 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate, toluene diisocyanate, methylen-biphenyldiisocyanate, 1,6-cyclohexamethylene-diisocyanate, methyl isopropyl ketone diisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA).
4. The polymeric polyamine as claimed in claim 1 , wherein the linker is selected from the group consisting of benzene tetracarboxylic dianhydride (PMDA), trimellitic anhydride (TMA) and adipic acid.
5. The polymeric polyamine as claimed in claim 1 , which serves as a stabilizer or a dispersant of the Ag nanoparticles.
6. A method for producing a polymeric polyamine, comprising a step of reacting the polyoxyalkylene-amine with a linker having a reactive functional group, wherein the polyoxyalkylene-amine has a molecular weight of 200˜10,000, and the linker is selected from the group consisting of anhydride, carboxylic acid, glycidyl, epoxide, isocyanate, diisocyanate, maleic anhydride and maleated polystyrene.
7. The method as claimed in claim 6 , wherein the polyoxyalkylene-amine has a structural formula H2N—R—NH2, wherein R is selected from the group consisting of dianhydride, diacid, epoxy, diisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA).
8. The method as claimed in claim 6 , wherein the molar ratio of the polyoxyalkylene-amine to the linker is n: (n+1) or (n+1):1, n=1˜5.
9. The method as claimed in claim 6 , which is performed at 25° C.˜150° C. for 1˜12 hours.
10. The method as claimed in claim 6 , wherein the linker is selected from the group consisting of benzene tetracarboxylic dianhydride (PMDA), trimellitic anhydride (TMA), adipic acid, maleic anhydride, succinic acid anhydride, phthalic anhydride, tetrahydromethyl-1,3-isobenzofurandione, dicarboxylic acid, succinic acid, p-phthalic, isophthalic acid, diglycidyl ether of bisphenol-A (DGEBA), 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate, toluene diisocyanate, methylen-biphenyldiisocyanate, 1,6-cyclohexamethylene-diisocyanate, methyl isopropyl ketone diisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA).
11. The method as claimed in claim 6 , wherein the linker is selected from the group consisting of benzene tetracarboxylic dianhydride (PMDA), trimellitic anhydride (TMA) and adipic acid.
12. The method as claimed in claim 6 , wherein the polymeric polyamine produced is a stabilizer or dispersant of the Ag nanoparticles.
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US20040166088A1 (en) * | 2003-01-15 | 2004-08-26 | Shalaby Shalaby W. | Polymeric precursors of non-absorbable, in situ-forming hydrogels and applications thereof |
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/en unknown
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2008
- 2008-06-17 US US12/140,507 patent/US8013048B2/en active Active
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2011
- 2011-08-01 US US13/195,022 patent/US20110288239A1/en not_active Abandoned
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2012
- 2012-09-12 US US13/612,052 patent/US20130005918A1/en not_active Abandoned
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110011208A1 (en) * | 2009-07-16 | 2011-01-20 | National Taiwan University | Method for preparing silver nanoparticles by employing ethanolamine |
US8491699B2 (en) * | 2009-07-16 | 2013-07-23 | National Taiwan University | Method for preparing silver nanoparticles by employing ethanolamine |
US20140155308A1 (en) * | 2012-11-30 | 2014-06-05 | Chevron Oronite Company Llc | Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation |
US9243203B2 (en) * | 2012-11-30 | 2016-01-26 | Chevron Oronite Company Llc | Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation |
CN104744693A (en) * | 2013-12-31 | 2015-07-01 | 财团法人工业技术研究院 | Polymers and Dispersions |
Also Published As
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US8013048B2 (en) | 2011-09-06 |
US20090149583A1 (en) | 2009-06-11 |
TWI361812B (en) | 2012-04-11 |
US20130005918A1 (en) | 2013-01-03 |
TW200925178A (en) | 2009-06-16 |
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