TWI429701B - 製備聚酯奈米複合物之方法 - Google Patents
製備聚酯奈米複合物之方法 Download PDFInfo
- Publication number
- TWI429701B TWI429701B TW096131638A TW96131638A TWI429701B TW I429701 B TWI429701 B TW I429701B TW 096131638 A TW096131638 A TW 096131638A TW 96131638 A TW96131638 A TW 96131638A TW I429701 B TWI429701 B TW I429701B
- Authority
- TW
- Taiwan
- Prior art keywords
- poly
- polyester
- acid
- dicarboxylic acid
- ethylene
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 30
- 239000002114 nanocomposite Substances 0.000 title claims description 30
- 239000002105 nanoparticle Substances 0.000 claims description 50
- -1 o-decanoic acid Chemical compound 0.000 claims description 39
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- CHDRADPXNRULGA-UHFFFAOYSA-N naphthalene-1,3-dicarboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(C(O)=O)=C21 CHDRADPXNRULGA-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- 235000007586 terpenes Nutrition 0.000 claims 2
- ISUROAIHTKHKHH-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C(C(=C(C=C1)C=CC1=CC=C(C=C1)C1=CC=CC=C1)C(=O)O)C(=O)O Chemical compound C1(=CC=CC=C1)C1=C(C(=C(C=C1)C=CC1=CC=C(C=C1)C1=CC=CC=C1)C(=O)O)C(=O)O ISUROAIHTKHKHH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 229920002959 polymer blend Polymers 0.000 claims 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 41
- 239000001263 FEMA 3042 Substances 0.000 description 41
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 41
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 41
- 229940033123 tannic acid Drugs 0.000 description 41
- 235000015523 tannic acid Nutrition 0.000 description 41
- 229920002258 tannic acid Polymers 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 18
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 238000002411 thermogravimetry Methods 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 4
- WXANAQMHYPHTGY-UHFFFAOYSA-N cerium;ethyne Chemical compound [Ce].[C-]#[C] WXANAQMHYPHTGY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- XJEADTCCGSBPMV-UHFFFAOYSA-N 8-methyl-5-nitrononanoic acid Chemical group [N+](=O)([O-])C(CCCC(=O)O)CCC(C)C XJEADTCCGSBPMV-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- BOKFRKYTRPYRAP-UHFFFAOYSA-H [Bi+3].[Bi+3].[O-]C(=O)CCCCCCCCC([O-])=O.[O-]C(=O)CCCCCCCCC([O-])=O.[O-]C(=O)CCCCCCCCC([O-])=O Chemical compound [Bi+3].[Bi+3].[O-]C(=O)CCCCCCCCC([O-])=O.[O-]C(=O)CCCCCCCCC([O-])=O.[O-]C(=O)CCCCCCCCC([O-])=O BOKFRKYTRPYRAP-UHFFFAOYSA-H 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007560 sedimentation technique Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
- Developing Agents For Electrophotography (AREA)
- Silicon Polymers (AREA)
Description
此申請案主張2006年8月25日提出申請之美國專利申請案第60/840,091號之優先權，茲將該案以引用方式納入本文中。
本發明係關於聚酯奈米複合物及其製法。
奈米粒子已被用來作為聚合物之填料，以改良諸如機械、熱、電和阻擋性質等各種性質。使用奈米填料的誘因在於當填料的尺寸降至低於100奈米時可達到的龐大比表面積。相較於它們的微米和大對應物，奈米粒子具有較高比表面積數量級。此可導致兩個相關的現象。第一，填料和基質之間的交互作用面積增加。第二，有一個環繞各粒子的區域，此區域中，聚合物的行為與整體不同。此”交互作用區(IZ)”的體積分率可大於粒子的體積分率，且IZ的性質有助於性質方面的改變。此增加的交互作用可具有多種影響。其會導致玻璃轉移溫度(Tg
)和聚合物至填料的載量轉移的變化。在半晶聚合物的例子中，增加的交互作用會導致結晶行為如結晶溫度(Tc
)之改變。
然而，這些變化的程度係取決於填料和聚合物之間的界面。通常，較強的界面導致較佳的載量轉移和較高的Tg
。達到強界面的途徑是藉由以可與聚合物分子相容或可與聚合物分子鍵結的分子塗覆奈米粒子而改變奈米粒子的表面。改變奈米粒子表面的大部分嘗試，包含以具有一個被吸附在粒子表面上之末端基團和可與聚合物分子相容之另一末端基團的偶合劑，如矽烷或膦酸，來塗覆奈米粒子表面。之後，藉由將聚合物接枝於填料上(此包含使偶合劑與單體分子反應，接著聚合反應)而形成鍵結。雖然此方法展現有希望的結果，但與前述者相關的問題包括難以控制分子量和分子量分佈。
已使用替代方法提高聚合物如聚酯的玻璃轉移溫度，以改良其熱安定性。一個方法係使聚酯與另一種具有較高Tg
的聚酯摻合。例如，PET(Tg
~80℃)曾被用以與聚萘酸乙二酯(PEN，其Tg
為130℃)摻合。此方法的缺點在於具有較高Tg
的聚酯之高成本。共聚反應為用以提高聚酯之Tg
的另一途徑。曾製備PET與PEN之共聚物且Tg
隨著萘單元的提高而提高。PET亦曾與5－硝基異酞酸單元(PETNI)共聚而於50% NI含量使得玻璃轉移溫度提高6℃。但是，此方法需要高百分比的共聚單體單元以獲致可觀的改變。
對於經奈米粒子填充的聚合物，即聚合物奈米複合物，及克服至少一個前述缺陷的聚合物奈米複合物之製法有需求存在。
本發明的一個方面係關於用以製備聚酯奈米複合物之方法，其包含：以二羧酸塗覆奈米粒子；使經二羧酸塗覆的奈米粒子與偶合劑合併，得到第一混合物；及使第一混合物與聚酯合併，形成聚酯奈米複合物，其玻璃轉移溫度高於聚酯且結晶溫度低於聚酯。
此專利說明書中，名詞和替代名稱於首次出現時定義並維持其定義。
根據本發明，提出用以製備聚酯奈米複合物之方法。此方法包含以二羧酸塗覆奈米粒子。使經二羧酸塗覆的奈米粒子與偶合劑合併，得到第一混合物。之後，使第一混合物與聚酯合併，形成聚酯奈米複合物。所得的聚酯奈米複合物尤其具有玻璃轉移溫度高於聚酯且結晶溫度低於聚酯的性質。
適用於本發明的奈米粒子包括選自金屬氧化物、非金屬氧化物、非金屬化合物、半金屬氧化物和半金屬化合物所組成之群組者。金屬氧化物的例子包括氧化鋁、氧化鈦、氧化鋯、氧化銻錫、氧化鈰、氧化銅、氧化銦、氧化銦錫、氧化鐵、二氧化矽、氧化錫、氧化釔、氧化鋅、氧化鋇、氧化鈣、氧化鉻、氧化鎂、氧化鉬、氧化鈮和氧化鍶。
非金屬氧化物或化合物的例子包括氧化矽、氮化矽、碳化矽、氮碳化矽、氮氧化矽、氮碳氧化矽、氧化鍺、氮化鍺、碳化鍺、氮碳化鍺和氮氧化鍺、氮碳氧化鍺。半金屬氧化物或化合物的例子包括氧化鉍、氮化鉍、碳化鉍、氮碳化鉍、氮氧化鉍、氮碳氧化鉍、氧化鈹、氮化鈹、碳化鈹、氮碳化鈹、氮氧化鈹和氮碳氧化鈹。
本發明中所用之奈米粒子的平均粒子大小是在1奈米至100奈米的範圍內。粒子大小可在由下限的10奈米、20奈米或30奈米至上限的70奈米、80奈米或90奈米的範圍內變化。所有的平均粒子大小範圍皆含括並可合併。”平均粒子大小”一詞是指藉電子顯微鏡法或藉表面積測量而測定的粒子大小。在以二羧酸塗覆之前，移除大粒子可以窄化奈米粒子的粒子大小分佈。大粒子可藉沉積或沉降技術，例如離心作用，而移除。
前述奈米粒子係經二羧酸塗覆。塗覆步驟包含：經由表面羥基使二羧酸化學吸附於奈米粒子表面上，使得各個二羧酸分子的一個羧酸基團是自由的。根據本發明使用的二羧酸的例子包括對酞酸、異酞酸、鄰酞酸、1,3－萘二羧酸、1,4－萘二羧酸、4,4’－二苯基二羧酸、4,4’－二苯基碸二羧酸和二苯基醚4,4’－二羧酸。通常，所用的是酞酸，例如對酞酸、異酞酸或鄰酞酸。
奈米粒子經二羧酸塗覆之後，將經塗覆的奈米粒子與偶合劑合併以提供第一混合物。偶合劑係選自碳化二醯亞胺、環氧化物和酐所組成之群組。通常，係將碳化二醯亞胺如聚碳化二醯亞胺與經塗覆的奈米粒子偶合。
之後，將第一混合物與聚酯合併以形成聚酯奈米複合物。存在於第一混合物中的偶合劑與二羧酸中化學吸附於奈米粒子上的自由羧基及聚酯的羧基末端二者反應。此反應於第一混合物與聚酯合併期間當場發生。合併機構藉由前述者之熔融混合而達成。通常，聚酯奈米複合物包含4%至10%的第一混合物。
適用於與第一混合物合併的聚酯選自下列所組成之群組：聚(對酞酸乙二酯)、聚(對酞酸伸環己基二甲酯)、聚(十二酸乙二酯)、聚(對酞酸丁二酯)、聚(萘酸乙二酯)、聚(2,7－萘酸乙二酯)、聚(異酞酸甲基苯酯)(poly(methaphenylene isophthalate))、聚(乙醇酸)、聚(丁二酸乙二酯)、聚(己二酸乙二酯)、聚(癸二酸乙二酯)、聚(壬二酸癸二酯)、聚(癸二酸癸二酯)、聚(二甲基丙內酯)、聚(異酞酸乙二酯)、聚(對酞酸丁二酯)、聚(對酞酸己二酯)、聚(對酞酸癸二酯)、聚(對酞酸1,4－環己烷二甲酯)(反式)、聚(1,5－萘酸乙二酯)、聚(2,6－萘酸乙二酯)和聚(對酞酸1,4－伸環己基二甲酯)。通常，用以與第一混合物合併的聚酯是聚(對酞酸乙二酯)。
平均粒子大小為38奈米且比表面積為50平方米/克的氧化鋁奈米粒子係得自Nanophase Technologies Corp.。二羧酸、對酞酸(TA)購自Aldrich chemicals，其為粉末形式且以購入時的狀態使用。乙醇(200度)得自Fisher chemicals且三氟醋酸(TFA)得自Sigma－Aldrich。所有的試劑皆以購入時的狀態使用。偶合劑，芳族聚羰化二醯亞胺(Stabaxol 100)得自Rheinchemie chemicals。
使用Mettler Toledo DSC822e儀器進行差示掃描量熱法(DSC)分析。使用DSC的玻璃轉移溫度之測量係在藉由從熔融物驟冷而製得的非晶樣品上進行。半晶聚合物的玻璃轉移溫度通常取決於基質的結晶度，且界面強度的真實呈現僅可藉由研究非晶樣品而獲致。這些測量使用10℃/分鐘的掃描速率。
加熱時的重量損耗係藉熱重分析法而分析並以Mettler Toledo TGA測量。這些測量中，樣品以10℃/分鐘的速率加熱。
實施例1：首先藉由同時以超音波探針聲裂及攪拌7分鐘，將氧化鋁奈米粒子分散於乙醇中。將所需量的TA加至分散液中並加熱至接近乙醇的沸點，以確保TA於乙醇中之最大溶解度。混合物於攪拌時持續回流4小時。之後，於劇烈攪拌的同時，加熱此混合物，藉此移除溶劑。在真空中乾燥至少24小時，確保溶劑完全被移除，並使得經TA塗覆的粒子以粉末形式被分離出來。
藉聲裂及同時攪拌7分鐘，將經TA塗覆的奈米粒子分散於三氟醋酸(TFA)中。藉由在pCDI中緩慢地攪拌，將所需量的聚碳化二醯亞胺(pCDI)溶解於此溶液中。另藉攪拌，將用量足以使得奈米複合物母料具有20重量%奈米粒子的聚(對酞酸乙二酯)(PET)溶解於TFA中。之後，於劇烈攪拌的情況下，將此二溶液混合在一起。藉由將其逐滴添加至以冰水混合物冷卻的甲醇(反溶劑)中，使奈米複合物自所得的溶液中沉澱出來。於先前的步驟之後，以甲醇清洗數次。將此奈米複合物於真空中於110℃乾燥至少48小時。
將所得的奈米粒子作為母料，並藉由在Thermo Haake Poly Drive批料熔融混合機中，在氬氣環境下於260℃以80rpm的螺桿旋轉速率與PET粒熔融混合7分鐘，而稀釋至所需的濃度。在熔融混合程序期間內，於原處發生TA和pCDI之間的反應及同時發生pCDI和PET之間的反應。
實施例2：藉由同時以超音波探針聲裂及攪拌7分鐘，將氧化鋁奈米粒子分散於0.5%重量/體積(w/v)的乙醇中。持續攪拌的同時，以4%重量/重量(w/w)氧化鋁的濃度，將TA加至此分散液中。將此溶液於劇烈攪拌的情況下回流至少4小時，以確保完全吸附。之後，藉由於65℃蒸發而移除溶劑，將殘留的粉末於真空中於110℃乾燥至少24小時。藉聲裂及同時攪拌7分鐘，將經TA塗覆的奈米粒子分散於2%w/v TFA中。藉由在劇烈攪拌的條件下緩慢添加，將聚－CDI溶解於先前的溶液中。所用之pCDI與TA的比例為4：1。另藉攪拌將PET(用以使得奈米複合物母料具有20重量%奈米粒子)以10%重量/體積的濃度溶解於TFA中。完全溶解之後，於劇烈攪拌的情況下，將此二溶液混合在一起。藉由將其逐滴添加至甲醇(反溶劑)中，接著以甲醇清洗數次，使奈米複合物自所得的溶液中沉澱出來。將此奈米複合物於真空中於110℃乾燥至少48小時。之後，將此奈米複合物與適當量的PET粒混合，製得具有所需奈米粒子百分比之奈米複合物。
藉熱重分析定出在奈米粒子表面上之TA塗層的特徵。經7重量%TA塗覆的粒子之熱重分析示於圖1。TA於約300℃昇華。但是，就經7重量%TA塗覆的奈米粒子觀之，於約300℃僅發生2.5重量%損耗。此相當於自由的酞酸。約4重量%損耗發生於溫度高於500℃處。此指出此部分的TA未昇華且強烈吸附於粒子表面。
對於經2、4、6和7重量%TA塗覆的氧化鋁粒子之TGA曲線係示於圖2。就具有超過4重量%TA塗層的所有樣品觀之，有兩個重量損耗區域：一者出現於約300℃處而另一者開始於500℃處，於此處發生4重量%損耗。就經4重量%或以下之TA含量塗覆的粒子觀之，整體重量損耗發生於>500℃之溫度。此證實TA量於38奈米氧化鋁奈米粒子上之完全單層表面覆蓋度為4重量%。此相當於0.246毫莫耳TA/克氧化鋁或0.0492毫莫耳/平方米氧化鋁表面的覆蓋度。
以Kissinger分析估計化學吸附的TA於加熱時之移除動力學。圖3描繪經4重量%TA處理的氧化鋁於加熱速率為2、5、30和50℃/分鐘時之TGA重量損耗曲線。使用用於重量損耗的溫度值，計算出活化能為220千焦耳/莫耳。此高活化能值指出TA強烈地固著至氧化鋁表面且在氧化鋁表面上的最適表面覆蓋度相當於4重量%TA。
使用DSC追蹤介於TA和pCDI之間之反應。圖4描繪原樣TA和pCDI之混合物的DSC曲線。於約50℃的吸熱峰相當於混合物中之pCDI之熔化。有第二個峰位於約217℃處，其為放熱峰。TA未於此溫度昇華，此外，昇華是吸熱反應。此峰指出TA與pCDI於約217℃反應。藉積分此峰下方的面積而計算出反應熱。
就原樣TA對pCDI之不同比例測量的反應熱係描繪於圖5中。隨著TA與pCDI之比例提高，反應熱提高，在到達最高點之後開始降低。比例超過2：1時，TA已經與pCDI反應。
就化學吸附於氧化鋁表面上之TA而言，總羧酸基團中之僅半數可用以與pCDI反應(另一半係化學吸附於氧化鋁表面)。因此，化學吸附的TA對pCDI為1：4之比例將相當於與經吸附TA完全反應所需的最少pCDI。使用過量的pCDI以確保羧酸基團被完全利用。
在PET處理中使用聚CDI，以避免因水解反應而發生的降解情況。其藉由封住其羧酸末端基團而穩定PET。此介於pCDI和PET之間之反應在於約260℃熔融混合下發生。
具有不同重量分率之表面塗覆奈米粒子之PET的玻璃轉移溫度之DSC測量係描繪於圖6中。可見到Tg
隨著奈米粒子含量的提高而提高，顯示於奈米粒子和基質聚合物之間有強界面。作為對照組，將原樣奈米粒子亦與PET熔融混合。玻璃轉移溫度並不因添加原樣奈米粒子而改變。
使用DSC，以16℃/分鐘的冷卻速率自熔融物測量結晶曲線，藉此得知峰結晶溫度，此描繪於圖7。隨著填料含量增加，此峰結晶溫度偏移至逐漸較低的溫度，且於10重量%載量時，其比純PET低了27℃。文獻中之研究關於聚酯之結晶溫度降低的報導極少。在聚合物奈米複合物的範疇中，通常知道填料之存在會因為非均相成核作用而導致結晶溫度提高。本發明之方法的一個優點在於發生相反的情況。引入填料使得結晶溫度降低。
前文證實塗覆奈米粒子表面提供與基質聚合物之強化學鏈結。此與將單體接枝於已吸附在粒子上的偶合劑，接著進行聚合的常見技巧不同。此強鏈結係藉由聚合物末端基團和偶合劑之間的化學反應而獲致。此強界面使得高百分比的聚合物分子與奈米粒子作用，藉此而使得聚合物奈米複合物之玻璃轉移溫度實質上提高。
圖1為根據本發明，重量損耗百分比相對於溫度之熱重分析(TGA)圖；圖2為根據本發明，經對酞酸(TA)塗覆之具有不同TA百分比之奈米粒子之重量損耗百分比相對於溫度之熱重分析(TGA)圖；圖3為根據本發明，經TA塗覆的奈米粒子於改變的加熱速率下測得之重量損耗百分比相對於溫度之熱重分析(TGA)圖；圖4為根據本發明，熱流相對於TA和聚二碳化二醯亞胺(pCDI)溫度之差示掃描量熱法(DSC)圖；圖5為根據本發明，反應熱相對於TA對pCDI比率的圖；圖6為玻璃轉移溫度相對於在根據本發明之聚酯奈米複合物中之填料百分比的圖；和圖7為結晶溫度相對於在根據本發明之聚酯奈米複合物中之填料百分比的圖。
Claims (15)
- 一種製備聚酯奈米複合物之方法，其包含：以二羧酸塗覆顆粒大小為1奈米至100奈米之奈米粒子，其中該塗覆步驟由以下所構成：經由表面羥基基團使二羧酸化學吸附於奈米粒子表面上，使得各個二羧酸分子的一個羧酸基團是自由的；使經二羧酸塗覆的奈米粒子與偶合劑合併，得到第一混合物；及使第一混合物與聚酯合併以形成聚酯奈米複合物，其中該聚酯奈米複合物具有高於聚酯之玻璃轉移溫度及低於聚酯之結晶溫度。
- 根據申請專利範圍第1項之方法，其中奈米粒子係選自由金屬氧化物、非金屬氧化物、非金屬化合物、半金屬氧化物和半金屬化合物所組成之群。
- 根據申請專利範圍第2項之方法，其中金屬氧化物是氧化鋁。
- 根據申請專利範圍第2項之方法，其中非金屬氧化物是氧化矽。
- 根據申請專利範圍第1項之方法，其中二羧酸係選自由對酞酸、異酞酸、鄰酞酸、1,3-萘二羧酸、1,4-萘二羧酸、4,4’-二苯基二羧酸、4,4’-二苯基碸二羧酸和二苯基醚4,4’-二羧酸所組成之群。
- 根據申請專利範圍第5項之方法，其中二羧酸係選自由對酞酸、異酞酸和鄰-酞酸所組成之群。
- 根據申請專利範圍第1項之方法，其中偶合劑係選自由碳化二醯亞胺、環氧化物和酐所組成之群。
- 根據申請專利範圍第1項之方法，其中偶合劑是碳化二醯亞胺。
- 根據申請專利範圍第1項之方法，其中聚酯係選自由聚(對酞酸乙二酯)、聚(對酞酸伸環己基二甲酯)、聚(十二酸乙二酯)、聚(對酞酸丁二酯)、聚(萘酸乙二酯)、聚(2,7-萘酸乙二酯)、聚(異酞酸甲基苯酯)(poly(methaphenylene isophthalate))、聚(乙醇酸)、聚(丁二酸乙二酯)、聚(己二酸乙二酯)、聚(癸二酸乙二酯)、聚(壬二酸癸二酯)、聚(癸二酸癸二酯)、聚(二甲基丙內酯)、聚(異酞酸乙二酯)、聚(對酞酸丁二酯)、聚(對酞酸己二酯)、聚(對酞酸癸二酯)、聚(對酞酸1,4-環己烷二甲酯)(反式)、聚(1,5-萘酸乙二酯)、聚(2,6-萘酸乙二酯)和聚(對酞酸1,4-伸環己基二甲酯)所組成之群。
- 根據申請專利範圍第1項之方法，其中聚酯是聚(對酞酸乙二酯)。
- 根據申請專利範圍第1項之方法，其中經二羧酸塗覆的奈米粒子與偶合劑之合併比例在1：2至1：6的範圍內。
- 根據申請專利範圍第1項之方法，其中奈米粒子是氧化鋁，二羧酸是對酞酸，且偶合劑是聚碳化二醯亞胺。
- 根據申請專利範圍第1項之方法，其中聚酯奈米複合物包含4%至10%的含有經塗覆之奈米粒子和偶合試劑之混合物。
- 根據申請專利範圍第1項之方法，其中該聚酯係選自至少一種聚酯共聚物及聚酯-聚合物之混合物。
- 一種製備聚酯奈米複合物之方法，其包含：以二羧酸塗覆奈米粒子；使經二羧酸塗覆的奈米粒子與偶合劑合併，得到第一混合物；及使第一混合物與聚酯合併以形成聚酯奈米複合物，其中該聚酯奈米複合物具有高於單獨該聚酯之玻璃轉移溫度及低於單獨該聚酯之結晶溫度。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84009106P | 2006-08-25 | 2006-08-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200833751A TW200833751A (en) | 2008-08-16 |
| TWI429701B true TWI429701B (zh) | 2014-03-11 |
Family
ID=39107752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096131638A TWI429701B (zh) | 2006-08-25 | 2007-08-27 | 製備聚酯奈米複合物之方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US8436076B2 (zh) |
| EP (1) | EP2059562B9 (zh) |
| JP (1) | JP5073748B2 (zh) |
| KR (1) | KR101421313B1 (zh) |
| CN (1) | CN101528849B (zh) |
| BR (1) | BRPI0715732A2 (zh) |
| CA (1) | CA2661916C (zh) |
| MX (1) | MX2009002114A (zh) |
| NO (1) | NO20091140L (zh) |
| PL (1) | PL2059562T3 (zh) |
| RU (1) | RU2458080C2 (zh) |
| TW (1) | TWI429701B (zh) |
| WO (1) | WO2008025028A2 (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060205856A1 (en) * | 2004-12-22 | 2006-09-14 | Williamson David T | Compositions of polyesters and sepiolite-type clays |
| WO2007059128A1 (en) * | 2005-11-15 | 2007-05-24 | Wellman, Inc. | Alumina-enhanced polyester resins |
| JP5286322B2 (ja) * | 2009-04-20 | 2013-09-11 | 旭化成ケミカルズ株式会社 | 樹脂組成物 |
| RU2566756C2 (ru) * | 2013-06-17 | 2015-10-27 | Общество с ограниченной ответственностью "Торгово-Производственная Фирма "Антал" | Модифицированная полиэфирная композиция и способ ее получения |
| CA3055827A1 (en) * | 2017-03-08 | 2018-09-13 | Graphene 3D Lab Inc. | Electrically conductive adhesive compositions and kits and methods for using same |
Family Cites Families (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0076255A1 (en) * | 1981-04-07 | 1983-04-13 | BENTON, William M. | Transaction verification system using optical data communication link |
| US4727243A (en) * | 1984-10-24 | 1988-02-23 | Telenet Communications Corporation | Financial transaction system |
| US4823264A (en) * | 1986-05-27 | 1989-04-18 | Deming Gilbert R | Electronic funds transfer system |
| US5654392A (en) * | 1988-02-17 | 1997-08-05 | Maxdem Incorporated | Rigid-rod polymers |
| US5305196A (en) * | 1989-05-01 | 1994-04-19 | Credit Verification Corporation | Check transaction processing, database building and marketing method and system utilizing automatic check reading |
| GB9016028D0 (en) * | 1990-07-20 | 1990-09-05 | Ici Plc | Inorganic solid and polymer composition |
| US5237159A (en) * | 1991-07-17 | 1993-08-17 | J. D. Carreker And Associates | Electronic check presentment system |
| US5691524A (en) * | 1991-07-17 | 1997-11-25 | J.D. Carreker And Associates, Inc. | Electronic check presentment system having a non-ECP exceptions notification system incorporated therein |
| DE4233396A1 (de) * | 1992-10-05 | 1994-04-07 | Merck Patent Gmbh | Oberflächenmodifizierte Oxidpartikel und ihre Anwendung als Füll- und Modifizierungsmittel in Polymermaterialien |
| US5774882A (en) * | 1992-03-12 | 1998-06-30 | Keen; Regina D. | Credit approval system |
| US5393963A (en) * | 1992-03-17 | 1995-02-28 | Company Chex, Inc. | Check authorization system and process |
| US5491325A (en) * | 1992-08-25 | 1996-02-13 | Huang; Dorge O. | Method and system for payment and payment verification |
| US5504677A (en) * | 1992-10-15 | 1996-04-02 | Pollin; Robert E. | Automated payment system |
| US5794219A (en) * | 1996-02-20 | 1998-08-11 | Health Hero Network, Inc. | Method of conducting an on-line auction with bid pooling |
| US5475403A (en) * | 1992-11-25 | 1995-12-12 | Personal Electronic Products, Inc. | Electronic checking with printing |
| KR100216363B1 (ko) * | 1993-10-13 | 1999-08-16 | 윤종용 | 신용조회 서비스 시스템 및 방법 |
| US5583759A (en) * | 1993-11-22 | 1996-12-10 | Huntington Bancshares, Inc. | Mechanism for expediting the deposit, transport and submission of checks into the payment system |
| US5592377A (en) * | 1993-12-18 | 1997-01-07 | Lipkin; Edward B. | Check cashing system |
| US5774879A (en) * | 1993-12-27 | 1998-06-30 | First Data Corporation | Automated financial instrument processing system |
| US5590038A (en) * | 1994-06-20 | 1996-12-31 | Pitroda; Satyan G. | Universal electronic transaction card including receipt storage and system and methods of conducting electronic transactions |
| US5799157A (en) * | 1994-12-13 | 1998-08-25 | Elcom Systems, Inc. | System and method for creating interactive electronic systems to present information and execute transactions |
| US5472190A (en) * | 1994-12-19 | 1995-12-05 | Norling; Phillip | Racket handle grip |
| US5732400A (en) * | 1995-01-04 | 1998-03-24 | Citibank N.A. | System and method for a risk-based purchase of goods |
| US5826245A (en) * | 1995-03-20 | 1998-10-20 | Sandberg-Diment; Erik | Providing verification information for a transaction |
| US5677955A (en) * | 1995-04-07 | 1997-10-14 | Financial Services Technology Consortium | Electronic funds transfer instruments |
| US5657389A (en) * | 1995-05-08 | 1997-08-12 | Image Data, Llc | Positive identification system and method |
| US5692132A (en) * | 1995-06-07 | 1997-11-25 | Mastercard International, Inc. | System and method for conducting cashless transactions on a computer network |
| US5802497A (en) * | 1995-07-10 | 1998-09-01 | Digital Equipment Corporation | Method and apparatus for conducting computerized commerce |
| US5826244A (en) * | 1995-08-23 | 1998-10-20 | Xerox Corporation | Method and system for providing a document service over a computer network using an automated brokered auction |
| US5710887A (en) * | 1995-08-29 | 1998-01-20 | Broadvision | Computer system and method for electronic commerce |
| US5699528A (en) * | 1995-10-31 | 1997-12-16 | Mastercard International, Inc. | System and method for bill delivery and payment over a communications network |
| US5757917A (en) * | 1995-11-01 | 1998-05-26 | First Virtual Holdings Incorporated | Computerized payment system for purchasing goods and services on the internet |
| US5781654A (en) * | 1996-01-18 | 1998-07-14 | Merrill Lynch & Co., Inc. | Check authentication system utilizing payee information |
| US5822737A (en) * | 1996-02-05 | 1998-10-13 | Ogram; Mark E. | Financial transaction system |
| US5835899A (en) * | 1996-03-01 | 1998-11-10 | Electronic Data Systems Corporation | System and method for deriving financial responsibility identification |
| US5832463A (en) * | 1996-03-28 | 1998-11-03 | Electronic Data Systems Corporation | Automated system and method for checkless check transaction |
| US5815665A (en) * | 1996-04-03 | 1998-09-29 | Microsoft Corporation | System and method for providing trusted brokering services over a distributed network |
| GB9610645D0 (en) * | 1996-05-21 | 1996-07-31 | Ncr Int Inc | Financial transaction system |
| US6023685A (en) * | 1996-05-23 | 2000-02-08 | Brett; Kenton F. | Computer controlled event ticket auctioning system |
| US5848400A (en) * | 1996-07-01 | 1998-12-08 | Sun Microsystems, Inc. | Electronic check exchange, clearing and settlement system |
| US6240396B1 (en) * | 1996-09-04 | 2001-05-29 | Priceline.Com Incorporated | Conditional purchase offer management system for event tickets |
| US5872844A (en) * | 1996-11-18 | 1999-02-16 | Microsoft Corporation | System and method for detecting fraudulent expenditure of transferable electronic assets |
| JP3299921B2 (ja) * | 1997-10-17 | 2002-07-08 | 協和化学工業株式会社 | 水酸化マグネシウムを含有する耐酸性熱可塑性樹脂組成物 |
| US6287992B1 (en) * | 1998-04-20 | 2001-09-11 | The Dow Chemical Company | Polymer composite and a method for its preparation |
| US6245428B1 (en) * | 1998-06-10 | 2001-06-12 | Cpfilms Inc. | Low reflective films |
| US6260024B1 (en) * | 1998-12-02 | 2001-07-10 | Gary Shkedy | Method and apparatus for facilitating buyer-driven purchase orders on a commercial network system |
| US6194489B1 (en) | 1999-01-20 | 2001-02-27 | Tohoku Munekata Co Ltd | Resin Additive |
| US7194437B1 (en) * | 1999-05-14 | 2007-03-20 | Amazon.Com, Inc. | Computer-based funds transfer system |
| EP1247829A1 (fr) * | 2001-04-06 | 2002-10-09 | University of Liege | Méthode de préparation de polyester nanocomposite |
| JP3791502B2 (ja) * | 2003-03-11 | 2006-06-28 | 日産自動車株式会社 | 樹脂組成物、及び樹脂組成物の製造方法 |
| US7309482B2 (en) * | 2003-09-08 | 2007-12-18 | E.I. Du Pont De Nemours And Company | Long lasting waterproof sunscreen comprising metal oxide and peptide conditioner |
| US20060083694A1 (en) * | 2004-08-07 | 2006-04-20 | Cabot Corporation | Multi-component particles comprising inorganic nanoparticles distributed in an organic matrix and processes for making and using same |
-
2007
- 2007-08-27 BR BRPI0715732-0A2A patent/BRPI0715732A2/pt not_active Application Discontinuation
- 2007-08-27 CN CN2007800386698A patent/CN101528849B/zh active Active
- 2007-08-27 RU RU2009107510/05A patent/RU2458080C2/ru active
- 2007-08-27 TW TW096131638A patent/TWI429701B/zh active
- 2007-08-27 EP EP07841398.6A patent/EP2059562B9/en active Active
- 2007-08-27 KR KR1020097005977A patent/KR101421313B1/ko active Active
- 2007-08-27 MX MX2009002114A patent/MX2009002114A/es active IP Right Grant
- 2007-08-27 US US11/845,497 patent/US8436076B2/en active Active
- 2007-08-27 WO PCT/US2007/076885 patent/WO2008025028A2/en active Application Filing
- 2007-08-27 JP JP2009526848A patent/JP5073748B2/ja active Active
- 2007-08-27 PL PL07841398T patent/PL2059562T3/pl unknown
- 2007-08-27 CA CA2661916A patent/CA2661916C/en active Active
-
2009
- 2009-03-17 NO NO20091140A patent/NO20091140L/no not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| PL2059562T3 (pl) | 2014-03-31 |
| WO2008025028A2 (en) | 2008-02-28 |
| JP2010501720A (ja) | 2010-01-21 |
| EP2059562B9 (en) | 2014-06-18 |
| NO20091140L (no) | 2009-03-17 |
| EP2059562A2 (en) | 2009-05-20 |
| CN101528849A (zh) | 2009-09-09 |
| KR20090074740A (ko) | 2009-07-07 |
| EP2059562B1 (en) | 2013-10-09 |
| KR101421313B1 (ko) | 2014-07-18 |
| MX2009002114A (es) | 2009-07-21 |
| CN101528849B (zh) | 2013-02-06 |
| WO2008025028A3 (en) | 2008-05-29 |
| RU2009107510A (ru) | 2010-09-10 |
| US20080113189A1 (en) | 2008-05-15 |
| RU2458080C2 (ru) | 2012-08-10 |
| TW200833751A (en) | 2008-08-16 |
| CA2661916C (en) | 2015-06-02 |
| CA2661916A1 (en) | 2008-02-28 |
| US8436076B2 (en) | 2013-05-07 |
| BRPI0715732A2 (pt) | 2013-09-24 |
| JP5073748B2 (ja) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI429701B (zh) | 製備聚酯奈米複合物之方法 | |
| Parvinzadeh et al. | Surface characterization of polyethylene terephthalate/silica nanocomposites | |
| Sinha Ray et al. | Effect of organoclay on the morphology and properties of poly (propylene)/poly [(butylene succinate)‐co‐adipate] blends | |
| Mehrabzadeh et al. | Polymer‐clay nanocomposites based on blends of polyamide‐6 and polyethylene | |
| Awad et al. | Improvement of the chemical, thermal, mechanical and morphological properties of polyethylene terephthalate–graphene particle composites | |
| TW200825136A (en) | Compatibilizing agent for polymer alloy, polymer alloy and masterbatch for preparation of polymer alloy | |
| WO1999023162A1 (fr) | Compositions de resines de polyester et leur procede de preparation | |
| US20190031810A1 (en) | Composite compositions and modification of inorganic particles for use in composite compositions | |
| WO2004096912A1 (ja) | ポリエステル樹脂組成物 | |
| Gao et al. | Preparation and characterization of BaSO4/poly (ethylene terephthalate) nanocomposites | |
| Mallakpour et al. | Surface coating of α-Al2O3 nanoparticles with poly (vinyl alcohol) as biocompatible coupling agent for improving properties of bio-active poly (amide-imide) based nanocomposites having l-phenylalanine linkages | |
| Mukhopadhyay et al. | Synthesis, characterization and properties of self-healable ionomeric carboxylated styrene–butadiene polymer | |
| Goffin et al. | From polyester grafting onto POSS nanocage by ring-opening polymerization to high performance polyester/POSS nanocomposites | |
| Liao et al. | New biodegradable blends prepared from polylactide, titanium tetraisopropylate, and starch | |
| Xu et al. | Preparation and enhanced properties of poly (propylene)/silica‐grafted‐hyperbranched polyester nanocomposites | |
| Mincheva et al. | Preparation of narrowly dispersed stereocomplex nanocrystals: a step towards all-poly (lactic acid) nanocomposites | |
| Hassan et al. | Enhanced thermal, mechanical and fire-retarding properties of polystyrene sulphonate-grafted-nanosilica/polypropylene composites | |
| Hatui et al. | Modification of CNT and its effect on thermo mechanical, morphological as well as rheological properties of Polyether Imide (PEI)/Liquid Crystalline Polymer (LCP) blend system | |
| Mishra et al. | Preparation and characterization of rubber‐toughened poly (trimethylene terephthalate)/organoclay nanocomposite | |
| Yao et al. | Synthesis, thermal, and rheological properties of poly (trimethylene terephthalate)/BaSO4 nanocomposites | |
| Nayak et al. | Effect of modified MWCNT on the properties of PPO/LCP blend | |
| Kulkarni et al. | In Situ synthesis of poly (styrene–butylacrylate–acrylic acid) latex/barium sulfate nanocomposite and evaluation of their film properties | |
| JP4352773B2 (ja) | ポリエステル樹脂組成物 | |
| Valenza et al. | Radiation grafting functionalization of poly (vinylidene fluoride) to compatibilize its blends with polyolefin ionomers | |
| Göçmen et al. | Multifunctional PP-based nanocomposites incorporated with organoclays, poly (MA-alt-1-dodecene)-g-SiO2 nanoparticles and bioengineering polyesters in melt by reactive extrusion |