CN103992467B - For the resin combination preparing thermoplastic polyester and the polyester resin prepared by said composition - Google Patents
For the resin combination preparing thermoplastic polyester and the polyester resin prepared by said composition Download PDFInfo
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- CN103992467B CN103992467B CN201310054969.2A CN201310054969A CN103992467B CN 103992467 B CN103992467 B CN 103992467B CN 201310054969 A CN201310054969 A CN 201310054969A CN 103992467 B CN103992467 B CN 103992467B
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- acid
- polyester resin
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- titanium
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 80
- 239000004645 polyester resin Substances 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title description 16
- 239000011347 resin Substances 0.000 title description 16
- 229920000728 polyester Polymers 0.000 title description 15
- 229920001169 thermoplastic Polymers 0.000 title description 2
- 239000004416 thermosoftening plastic Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- -1 diol compound Chemical class 0.000 claims abstract description 64
- 239000010936 titanium Substances 0.000 claims abstract description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 18
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002955 immunomodulating agent Substances 0.000 claims abstract description 15
- 229940121354 immunomodulator Drugs 0.000 claims abstract description 15
- 230000002584 immunomodulator Effects 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 239000006085 branching agent Substances 0.000 claims description 21
- ZPPUVHMHXRANPA-UHFFFAOYSA-N germanium titanium Chemical compound [Ti].[Ge] ZPPUVHMHXRANPA-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001869 cobalt compounds Chemical class 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical group O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004218 Orcein Substances 0.000 claims description 9
- 235000019248 orcein Nutrition 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 229940119177 germanium dioxide Drugs 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 3
- 229950003335 broxitalamic acid Drugs 0.000 claims description 3
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 3
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- ARWQHTZTOWMAEQ-UHFFFAOYSA-N (2-carboxyoxyphenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1OC(O)=O ARWQHTZTOWMAEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 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 claims 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- OLLMEZGFCPWTGD-UHFFFAOYSA-N hexane;methanol Chemical compound OC.OC.CCCCCC OLLMEZGFCPWTGD-UHFFFAOYSA-N 0.000 claims 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- SNZLRGHNGDZHTB-UHFFFAOYSA-N methyl 3-(4-bromophenyl)-3-oxopropanoate Chemical compound COC(=O)CC(=O)C1=CC=C(Br)C=C1 SNZLRGHNGDZHTB-UHFFFAOYSA-N 0.000 claims 1
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 55
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 238000000465 moulding Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 19
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000012634 fragment Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010257 thawing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- HGWOCGUIQUERSN-UHFFFAOYSA-N 3-acetamido-2,4,6-tribromo-5-(2-hydroxyethylcarbamoyl)benzoic acid Chemical compound CC(=O)NC1=C(Br)C(C(O)=O)=C(Br)C(C(=O)NCCO)=C1Br HGWOCGUIQUERSN-UHFFFAOYSA-N 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WMMGRPSGJRRNLN-UHFFFAOYSA-N 1-$l^{1}-phosphanylbutane Chemical compound CCCC[P] WMMGRPSGJRRNLN-UHFFFAOYSA-N 0.000 description 1
- DBYXKAVGJFMYDQ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;phosphoric acid Chemical compound OP(O)(O)=O.OCCOCCOCCO DBYXKAVGJFMYDQ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KQTVYYLEPGJHTK-UHFFFAOYSA-N [P].P(=O)(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound [P].P(=O)(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 KQTVYYLEPGJHTK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention provides a kind of compositionss for preparing polyester resin and the polyester resin prepared by said composition.Said composition, its diol compound is from 1.05 to 1.4 with the scope of the mol ratio of dicarboxylic acid compound, is wherein based on percetage by weight, said composition comprises the phosphorus of 5ppm to 50ppm（P）Compound, the cobalt of 10ppm to 40ppm（Co）Compound, the toner of 0.2ppm to 20ppm, and the titanium of 5ppm to 25ppm or 3ppm to 30ppm（Ti）Germanium（Ge）Composite catalyzing immunomodulator compounds.Preparing in the polyester resin for moulding container by using said composition, because compared with the situation using typical titanium catalyst compound, said composition has high intrinsic viscosity, it is harmless and eco-friendly to human body simultaneously, the compositionss for preparing polyester resin can be provided, its generation that can improve reaction rate during solid-state polymerization and reduce the acetaldehyde being caused by pyrolysis.
Description
Technical field
The present invention relates to for the compositionss preparing polyester resin, more particularly, to the group for preparing polyester resin
Compound, wherein this polyester resin have fabulous transparency, fabulous color and the high intrinsic viscosity being suitable to mould container
（I.V）.
Background technology
Polyester resin be a kind of most frequently be used for container, thin plate, the resinous type of film, fiber and injecting products, at it
Preparation during, most generally, stibium oxide or antimony triacetate are used as catalyst.
Antimony catalyst has fabulous advantage in terms of color, and due in esterification（ES）And polycondensation（P.C）Period
High activity, productivity ratio is high, but the toxicity due to it, control the antimony as harmful material, thus, extensively
Ground needs to develop new safe to the human body and eco-friendly catalyst.In Japan, by using germanium catalyst conduct
The alternative of such restriction is producing polyester resin.However, because the price of germanium catalyst can be ten times of antimony catalyst
Or higher, promptly create to cheap, harmless and eco-friendly new catalyst concern.
Have been developed for the titanium compound catalyst of the alternative as antimony catalyst.However, being urged using disclosed titanium
Agent is prepared polyester resin aspect and be there may be restriction, and wherein this polyester resin can be unsuitable for molding appearance due to aetiolation
Device, during being not only due to solid-state polymerization reaction, low reaction rate can reduce productivity ratio, and due to forming molding product
During high pyrolysis can also produce substantial amounts of acetaldehyde, these mould product such as container, thin plate, film and fibers, and spy
Property viscosity（I.V）Too low, so that it cannot with acting on the resin moulding container.
In order to solve the aforementioned restriction with regard to titanium catalyst, in United States Patent (USP) No.6, it is proposed that will be using hydrocarbon in 143,837
Epoxide titanium（titanium alkoxide）, acetyl acetonate, dioxide, titanate and phosphate, and using all
Acid dianhydride, the method for improving the intrinsic viscosity during solid-state polymerization is prepared as by using titanium compound catalyst
The method of polyester.However, the information being related to branching agent is plan that is limited and can not improving color, it is logical
Cross and prepare polyethylene terephthalate using titanium catalyst compound（Hereafter, referred to as " PET "）Middle maximum restriction.
Equally, in United States Patent (USP) No.5, it is proposed that Alkyl titanate is used as titanium catalyst compound and many in 744,571
Plant toner to be used for improving color.However, can be by using the b value between organic color reagent minimizing color value and permissible
It is not recommended that making a plan for improving solid state polymerization rate and heat stability.
Further, in United States Patent (USP) No.4, suggested in 217,440 and be used for preparing branch by using poly functional reagent
Polyester multiple methods.However, the purpose of the method, as the technology of exploitation before producing titanium catalyst, can be not
Improve can the method for color and the inferior position that can improve the reaction rate of solid-state polymerization, titanium catalyst clearly and not
Technology.
United States Patent (USP) No.7,199,210 discloses by using titanium catalyst compound with utilize PMA
Dianhydride（PMDA）During the preparation PET of the measure that can improve solid state polymerization rate, add the blueness as color Reagent
Reagent and red agents, the method for improving color value.However, because this method utilizes organic color reagent, Essential colour
Reinforcing agent there may be restriction, and as the plan for improving solid state polymerization rate, only PMDA is used as poly functional reagent,
Thus, it can lack multiformity.
Equally, disclose in U.S. Patent application No.2007/0155947 by using titanium catalyst and magnesium compound,
For improving the feature of aetiolation and titanium catalyst, the method preparing polyester.However, answering in titanium catalyst cannot be improved
The restriction being occurred with period, the such as reduction of solid state polymerization rate and the generation of the substantial amounts of acetaldehyde being caused by fast pyrogenation.
Content of the invention
The present invention replaces antimony by using green catalyst, there is provided can solve the problem that restriction for preparation, such as solid-state polymerization
The reaction rate of period, the generation of acetaldehyde, the intrinsic viscosity being suitable to molding container and aetiolation, and harmless
Compositionss with eco-friendly polyester resin.
Present invention provides, during the preparation of polyester resin, in the application of green catalyst, by using with spy
Determine the new composite catalyst that the optimal composition of catalyst combines, especially there is best color and intrinsic viscosity and low
The polyester resin of preparation cost.
According to aspects of the present invention, there is provided for preparing the compositionss of polyester resin, its diol compound and dicarboxylic acids
The scope of the mol ratio of compound is from 1.05 to 1.4, is wherein based on percetage by weight, said composition includes 5ppm to 50ppm
Phosphorus（P）Compound（Amount based on P）, the cobalt of 10ppm to 40ppm（Co）Compound（Amount based on Co）, 0.2ppm to 20ppm
Toner and 5pm to 25ppm/3ppm to 30ppm titanium（Ti）- germanium（Ge）Composite catalyzing immunomodulator compounds（Based on Ti/Ge's
Amount）.
The branched of 10ppm to 500ppm can be comprised for preparation according to the compositionss of the polyester resin of the present invention further
Reagent.
For preparing in the compositionss according to the polyester resin of the present invention, branching agent can be selected from the following
One or more of group of composition：Trimellitic acid, trimellitic anhydride, PMA, pyromellitic acid dianhydride, benzophenone -3,3 ',
4,4 '-tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, sulfobenzide. tetrabasic carboxylic acid
Dianhydride, Pentamethylene. tetracarboxylic dianhydride, tetramethylolmethane, oxolane, tetracarboxylic dianhydride, hydroxyl terephthalic acids, resorcylic acid,
1,2,2 '-ethane tricarboxylic acids, glycerol and trimethylolpropane.
For preparing in the compositionss according to the polyester resin of the present invention, can pass through to dissolve titanium precursor in ethylene glycol
Form titanium germanium composite catalyzing immunomodulator compounds with the mixture of germanium precursor.
For preparing in the compositionss according to the polyester resin of the present invention, titanium precursor can be titanium dioxide（TiO2）With
Silicon dioxide（SiO2）Composite oxides, and germanium precursor is germanium dioxide（GeO2）.
For preparing in the compositionss according to the polyester resin of the present invention, dicarboxylic acid compound can be selected from following
One or more in the group of every composition：Phthalic acid, p-phthalic acid, isophathalic acid, two broxitalamic acid, sulfoisophthalic acid
Sodium, phenylene dioxy dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-benzophenonedicarboxylic acid, 4,4 '-
Diphenoxyethanedicarboxylic acid, 4,4 '-sulfobenzide. dicarboxylic acids and 2,6 naphthalene dicarboxylic acid.
For preparing in the compositionss according to the polyester resin of the present invention, dicarboxylic acid compound can by 90mol% extremely
The isophathalic acid composition of the p-phthalic acid of 100mol% and 0mol% to 10mol%.
For preparing in the compositionss according to the polyester resin of the present invention, diol compound can be selected from following
One or more of group of item composition：Monoethylene glycol, diethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,4- hexamethylene two
Methanol and neopentyl glycol.
For preparing in the compositionss according to the polyester resin of the present invention, cobalt compound can be cobaltous acetate.
For preparing in the compositionss according to the polyester resin of the present invention, phosphorus compound can be selected from the following
One or more of group of composition：Phosphoric acid, trimethyl phosphate, triethyl phosphate, TRI N BUTYL PHOSPHATE, trioctyl phosphate, phosphorus
Triphenyl phosphate base ester, lindol, methyl orthophosphoric acid, etherophosphoric acid, p isopropylbenzoic acid ester, butylphosphoric acid ester, diethyl phosphate, phosphorus
Sour mono-n-butylester, dibutylphosphoric acid ester, phosphoric acid dioctyl ester and phosphoric acid triglycol ester（triethylene glycol acid
phosphate）.
For preparing in the compositionss according to the polyester resin of the present invention, toner can be blue dyess reagent or red
Color dye reagent.
According to another aspect of the present invention, there is provided by using the polyester resin of compositionss preparation, wherein chromaticity coordinates L
Value be more than 75.0, the value of chromaticity coordinates b is less than 0.0, and intrinsic viscosity（I.V）Scope in 0.70dl/g to 0.9dl/g
Interior.
Specific embodiment
Hereinafter, the present invention will be described in detail according to specific embodiment.Before describing the present invention it will be appreciated that
The word using in the specification and in the claims or term should not be construed as and the phase defined in the dictionary being usually used
Same meaning.Will be further understood that, the meaning of word or term can rightly be defined best to explain this based on inventor
The principle of invention, word or term should be construed to be had with them in the background technology of the present invention and the background of technical concept
The consistent meaning of meaning.
Consequently, because the embodiment providing in this specification is shown by embodiment, and do not represent the institute of the present invention
Some technical spirits it should be appreciated that when the present invention applies, embodiments of the present invention can have multiple modifications, equivalent,
And alternative.
The invention provides for preparing the compositionss of polyester resin, its diol compound and dicarboxylic acid compound mole
The scope of ratio is from 1.05 to 1.4, and wherein, based on percetage by weight, said composition comprises the phosphorus of 5ppm to 50ppm（P）Chemical combination
Thing（Amount based on P）, the cobalt of 10ppm to 40ppm（Co）Compound（Amount based on Co）, 0.2ppm to 20ppm toner and
The titanium of 5pm to 25ppm/3ppm to 30ppm（Ti）- germanium（Ge）Composite catalyzing immunomodulator compounds（Amount based on Ti/Ge）, and this
The bright compositionss for preparing polyester resin that the branching agent comprising 10ppm to 500ppm further can be provided.
By proposition in addition to phosphorus compound, cobalt compound, toner and titanium germanium composite catalyzing immunomodulator compounds, in conjunction with
The component of thing and optimum content comprises branching agent further, and the present invention can solve by the preparation phase in typical polyester resin
Between limit using titanium catalyst compound is produced, such as the aetiolation of color of resin, solid state polymerization rate, due to by profit
With preparation polyester resin molding product preparation during thermal decomposition produce poor chromaticity coordinates, the generation of acetaldehyde, with
And the reduction of transparency.Hereinafter, will be described in detail each component of the present invention.
For preparation according to the compositionss of the polyester resin of the present invention be by as primary raw material dicarboxylic acid compound and
Diol compound composition.
Dicarboxylic acid compound includes the aromatic molecules in diacid compounds as main component.In the present invention, permissible
Without limitation using phthalic acid, p-phthalic acid, isophathalic acid, two broxitalamic acid, sulfoisophthalic acid sodium, phenylene two
Oxygen dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-diphenylketone dicarboxylic acids, 4,4 '-hexichol oxygen second
Alkane dicarboxylic acids, 4,4 '-sulfobenzide. dicarboxylic acids and 2,6- naphthalene dicarboxylic acids, it is, for example possible to use p-phthalic acid and/or other
The mixture of dicarboxylic acid compound.In the situation using mixture, the content of p-phthalic acid can be total dicarboxylic
At least 90mol% of compound, can be more than 95mol%, for example, it may be more than 99mol%.The group of most preferred mixture
Conjunction is the mixture of p-phthalic acid and isophathalic acid.
The nonrestrictive example of diol compound can be monoethylene glycol, diethylene glycol, 1,3- propylene glycol, 1,4- fourth two
Alcohol, 1,4-CHDM and neopentyl glycol, it is, for example possible to use single monoethylene glycol and monoethylene glycol or diethyl
Glycol and/or the mixture of other diol compounds.In the situation using mixture, the content of monoethylene glycol or diethylene glycol
Can be at least 95mol% of total diol compound, for example, it may be more than 98mol%.The combination of most preferred mixture
It is monoethylene glycol or the mixture of diethylene glycol and neopentyl glycol.
In the present invention, based on molar ratio, the scope of diol compound and the content ratio of dicarboxylic acid compound is 1.05
To in 1.4.Now, in order to improve color and the intrinsic viscosity of the compositionss for preparing polyester resin, and prevent prepolymer
Physical property deterioration, the scope of content ratio can be in 1.1 to 1.3.
In the present invention, the phosphorus compound physics and chemical property acting on the resin preventing being caused by heating changes
Heat stabilizer, and the gross weight of the polyester and resin composition based on final preparation, comprise 5ppm to 50ppm（Amount based on P）
Amount phosphorus compound.The phosphorus compound of the amount of 25ppm to 35ppm can be comprised.It is less than 5ppm's in the content of phosphorus compound
In situation, heat stability can be reduced and yellow can occur, its content is more than in the situation of 50ppm wherein, in system
Standby become present aspect, it can be unfavorable, and during polycondensation, and by producing smog, phosphorus compound can be to having reacted phase
When unfavorable effect.
The nonrestrictive example of phosphorus compound can be phosphoric acid, trimethyl phosphate, triethyl phosphate, the positive fourth of tricresyl phosphate
Ester, trioctyl phosphate, Triphenyl phosphate, lindol, methyl orthophosphoric acid, etherophosphoric acid, p isopropylbenzoic acid ester, butyl phosphorus
Acid, diethyl phosphate, phosphoric acid mono-n-butylester, dibutylphosphoric acid ester, phosphoric acid dioctyl ester and triethylene glycol phosphoric acid, and can use
Phosphoric acid, triethyl phosphate and ethyl phosphonic acid, it is, for example possible to use triethyl phosphate.
In the present invention, for improving the coloring agent of color during the preparation that cobalt compound serves as polyester resin, based on
The gross weight of the polyester and resin composition of preparation, comprises the cobalt compound of the amount of 10ppm to 40ppm eventually（Amount based on Co）.Can
To comprise the cobalt compound of the amount of 25ppm to 35ppm.It is less than in the situation of 5ppm in the content of cobalt compound, face can be increased
The value of color b（The type of coloring agent/promoter）, wherein its content be more than 40ppm situation in, be prepared into we
Face, it can be unfavorable, and color L and color b can be made to become quite dark.
Although it does not have restricted, can by cobaltous acetate be used as cobalt compound.
In the present invention, toner is used for improving the color of the container by using polyester resin molding, is made based on final
The gross weight of standby polyester and resin composition, comprises the toner of the amount of 0.2ppm to 20ppm.Can comprise 5ppm's to 15ppm
The toner of amount.Toner content be less than 0.2ppm situation in, the effect improving color can be small, it
Content is more than in the situation of 20ppm, and color can be made somewhat dimmed.
Although it does not have restricted, blue dyess reagent or orchil reagent can be used as toner.
In the present invention, branching agent serves as the work for improving the physical property of the resin of preparation during solid-state polymerization
With, the gross weight of the polyester resin based on final preparation, the branching agent of the amount of 10ppm to 500ppm can be comprised.Can wrap
The branching agent of the amount containing 30ppm to 300ppm, for example, it is possible to comprise the branching agent of the amount of 50ppm to 150ppm.Branched
The content of reagent be less than 10ppm situation in, the increase degree of the intrinsic viscosity of the resin of preparation can be small, it
Content is more than in the situation of 500ppm, and color can be made to become quite dark.
The non-limiting examples of branching agent can be trimellitic acid（TMLA）, trimellitic anhydride（TMA）, PMA
（PMLA）, pyromellitic acid dianhydride（PMDA）, benzophenone -3,3 ', 4,4 '-tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 3,
3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, sulfobenzide. tetracarboxylic dianhydride, Pentamethylene. tetracarboxylic dianhydride, tetramethylolmethane, oxolane,
Tetracarboxylic dianhydride, hydroxyl terephthalic acids, resorcylic acid, 1,2,2 '-ethane tricarboxylic acids, glycerol and trimethylolpropane,
Trimellitic acid, trimellitic anhydride, PMA or pyromellitic acid dianhydride can be used, it is, for example possible to use trimellitic acid or inclined
Benzenetricarboxylic anhydride.
Different from only, using typical titanium catalyst compound, titanium germanium composite catalyzing immunomodulator compounds are used as the system in compositionss
The catalyst that standby period uses, wherein said composition are used for the polyester resin according to the present invention for the preparation.
Meanwhile, in the present invention, it is used alone in the compositionss for preparing polyester resin to improve further to work as
The aetiolation of polymer that occurred during typical titanium catalyst compound and glutinous due to not increasing during solid-state polymerization
The reduction of the productivity ratio of degree, using titanium germanium composite catalyzing immunomodulator compounds.
The solution being formed by dissolving titanium precursor in ethylene glycol and germanium precursor mixture can be combined as titanium germanium and urge
Agent compound.Now, the gross weight of the polyester and resin composition based on final preparation, by the mixing ratio of titanium precursor and germanium precursor
Rate controls in 5ppm to 25ppm or 3ppm to 30ppm（Amount based on Ti/Ge）In the range of.Can be by titanium dioxide（TiO2）/
Silicon dioxide（SiO2）Composite oxides be used as titanium precursor, can be by germanium dioxide（GeO2）As germanium precursor.
In the present invention, the gross weight of the polyester and resin composition based on final preparation, comprises 5ppm to 25ppm or 3ppm
To 30ppm（Amount based on Ti/Ge）Amount titanium germanium composite catalyzing immunomodulator compounds.5ppm to 15ppm or 10ppm can be comprised extremely
The titanium germanium composite catalyzing immunomodulator compounds of the amount of 20ppm, for example, it is possible to comprise the amount of 8ppm to 12ppm or 12ppm to 16ppm.Before
The content of the titanium germanium composite catalyzing immunomodulator compounds stated is that have best color perfecting degree and characteristic by identifying polyester resin
The result that the scope of viscosity is obtained, wherein utilizes and prepares polyester tree for preparation according to the compositionss of the polyester resin of the present invention
Fat.Specifically, the content in titanium is less than 5ppm and the content of germanium is less than in the situation of 3ppm, and reaction can not occur or can be
Slowly, the content of titanium is more than the content of 25ppm and germanium and is more than in the situation of 30ppm wherein, due to titanium and germanium catalyst
High activity, the color of polymer can not be very well.
If necessary, for preparation according to the compositionss of the polyester resin of the present invention can comprise further antioxidant,
UV blockers, antistatic additive, fire retardant and surfactant.
By using the compositionss for preparing the polyester resin according to the present invention, the method preparing polyester resin can be with base
In method known to art of the present invention, the method is not particularly restricted.For example, it is possible to by the following method, using interval
Formula reactor, prepares polyester resin.The method can continuously be carried out and the method is not particularly restricted.
That is, permissible by using the method preparing polyester resin according to the compositionss of the polyester resin of the present invention for preparation
Comprise the following steps：（A）The quantitative dicarboxylic acid compound of mixing and diol compound, to prepare serosity；（B）Titanium germanium is being combined
Catalyst compounds and branching agent are esterified after being added to serosity；（C）After the esterification, phosphorus compound, cobalt are added
Compound and toner, to prepare polymer；（D）Carry out the polycondensation of polymer；（E）Discharge the reactant being formed by polycondensation, to make
Standby thawing fragment；And（F）Thawing fragment is made to crystallize to carry out solid-state polymerization.
Herein, can be in step（A）Or step（B）And step（C）Between add titanium germanium composite catalyzing immunomodulator compounds.
It is also possible in step（A）Middle addition additive, such as phosphorus compound, cobalt compound and toner.
Another embodiment of the method for polyester resin of the preparation present invention will be described in further detail.First, will be used as master
Want dicarboxylic acids and the glycol of composition, and additive, such as catalyst, it is added in the agitator of preparation, stir to prepare serosity, so
Afterwards, mixture is transferred in esterifier, carry out at least up to more than 80% esterification, for example, more than 90%, so
After add other additives, such as heat stabilizer, mixture is transferred in polycondensation reactor to carry out polycondensation.Hereafter, contracted
Poly-, to obtain more than 100 condensation degree of dissolved, then cut in water, be there is scope from 0.5dl/g to 0.7dl/ to prepare
The thawing fragment of the intrinsic viscosity of g.After dicing, transfer in solid state polymerization reactor by melting fragment, tool can be prepared
The scope having intrinsic viscosity is the polyester resin for moulding container from 0.7dl/g to 0.9dl/g.
Equally, the scope in temperature is from 220 °C to 290 °C, for example, 245 °C to 265 °C, and the scope of pressure be from
0.1kg/cm2To 5kg/cm2, for example, 0.5kg/cm2To 3kg/cm2Under conditions of, can by stirring make esterification carry out about 1 to
10 hours.At this point it is possible to remove the water producing during being esterified immediately.
From 250 °C to 300 °C in temperature range, for example, 270 °C to 290 °C, and pressure relief ranges be from 0.1torr to
5torr, for example, under conditions of 0.5torr to 2torr, can make polycondensation carry out about 1 to 20 hour by stirring.At this point it is possible to
Remove the ethylene glycol producing during polycondensation and by-product immediately.
Similar to preceding method, any step after the esterification or before polycondensation can be neutralized in the step preparing serosity
Middle addition catalyst compounds, phosphorus compound, cobalt compound, toner and branching agent.However, for acid compound, permissible
Branching agent is added in serosity, for anhydride compound, branching agent can be added after the esterification or before polycondensation.
Under nitrogen atmosphere, the scope in temperature is from 195 °C to 230 °C and pressure relief ranges are from 0.2torr to 2torr
Under the conditions of, solid-state polymerization can be carried out.
For preparation according to the compositionss of the polyester resin of the present invention with according to prepared by the method preparing polyester resin gathering
Ester resin shows following physical property：Including more than 75.0 chromaticity coordinates L-value, less than 0.0 chromaticity coordinates b value and scope
It is the intrinsic viscosity from 0.70dl/g to 0.9dl/g（I.V）, thus, it is particularly suitable for moulding container.Herein, chromaticity coordinates L
Value is the index of the glossiness representing resin, i.e. the light levels of sample, and the value of chromaticity coordinates b represents the yellowing of resin.When
When the value of L is high, resin is brighter, and when the value of b is high, resin becomes slightly yellow.When two values are all low（Specifically, "-" value）,
Resin has blue color.
Equally, the example of polyester resin can be polyethylene terephthalate（PET）, polybutylene terephthalate
Ester（PBT）, glycol-modified polyester（PETG）, PEN（PEN）, PTT
（PPT）, and poly terephthalic acid 1.3- propylene glycol ester（PTT）, but polyester resin is not limited to wherein.
Hereinafter, this will be more fully described according to specific preparation embodiment, embodiment and comparing embodiment
Bright.
Preparation embodiment
By intermittence type polymerization reactor with acting on the thawing polymer reactor preparing polyester resin, including having an ester
Change the reactor of reactor, a polycondensation reactor and diced system.Esterification and polycondensation is made to carry out 3 to 4 hours and 2 to 3 respectively
Hour, reduce the final pressure that decompression obtains below 1.0torr by temperature is increased to 285 °C simultaneously, prepare polyester tree
Fat.Similarly, batch reactor is used as solid state polymerization reactor, wherein in 225 °C of reaction temperature and below 0.4torr
Pressure under make solid-state polymerization carry out 10 hours.
Embodiment 1
As main raw material, under 1.2 mol ratio, the diol compound that will be formed by the monoethylene glycol of 100mol%
It is added in the dicarboxylic acid compound being formed by the p-phthalic acid of 97mol% and the isophathalic acid of 3mol%.By weighing respectively
The phosphorus compound of 30ppm（Triethyl phosphate）, the cobalt compound of 30ppm（Cobaltous acetate）, the blue dyess reagent of 6.1ppm（Spherical
PRT, ColorMatrix Corporation）, the orchil reagent of 4.0ppm（Spherical PRT, ColorMatrix
Corporation）, and 10ppm/14ppm titanium-germanium composite catalyzing immunomodulator compounds（By in ethylene glycol dissolving titanium dioxide/
Silica composite oxide（C-94,Sachtleben GmBH,Germany）With germanium dioxide preparation）, and preparing serosity
Step in addition prepare polyester resin.
Embodiment 2
Except adding the branching agent of 100ppm further in embodiment 1（Pyromellitic acid dianhydride）Outside, with enforcement
In example 1, identical mode prepares polyester resin.
Comparing embodiment 1
Titanium catalyst compound except adding 13ppm replaces titanium-germanium complex chemical compound, and does not add in embodiment 1
Enter outside blue dyess reagent and orchil reagent, prepare polyester resin in the same manner as example 1.Herein, by
Know the compound titanium chelate compound with best activity（Chelate compounds by tetraisopropyl titanate and amino carboxylic acid preparation
Thing）As titanium catalyst compound, this is identical with following comparing embodiment.
Comparing embodiment 2
Titanium catalyst compound except adding 13ppm in embodiment 1 replaces titanium-germanium complex chemical compound, and adds
Outside the orchil reagent of the blue dyess reagent of 0.7ppm and 0.5ppm, prepare poly- in the same manner as in example 1
Ester resin.
Comparing embodiment 3
Titanium catalyst compound except adding 13ppm in embodiment 1 replaces titanium-germanium complex chemical compound, and enters one
Step adds blue dyess reagent, the orchil reagent of 0.7ppm and the branching agent of 100ppm of 1.2ppm（PMA two
Acid anhydride）Outside, prepare polyester resin in the same manner as example 1.
Comparing embodiment 4
Except add 13ppm titanium catalyst compound replace embodiment 1 in titanium-germanium complex chemical compound in addition to, with
In embodiment 1, identical mode prepares polyester resin.
Comparing embodiment 5
Except being added without titanium-germanium complex chemical compound, blue dyess reagent and orchil reagent in embodiment 1, and
Add the antimony catalyst compound of 230ppm（Stibium oxide）Outside, prepare polyester resin in the same manner as example 1.
Comparing embodiment 6
Titanium catalyst compound except adding 13ppm in embodiment 1 replaces titanium-germanium complex chemical compound, and adds
Outside the orchil reagent of the blue dyess reagent of 1.2ppm and 0.7ppm, prepare polyester in the same manner as example 1
Resin.
Comparing embodiment 7
Titanium catalyst compound except adding 13ppm in embodiment 1 replaces titanium-germanium complex chemical compound, and enters one
Step adds blue dyess reagent, the orchil reagent of 0.7ppm and the branching agent of 50ppm of 1.2ppm（PMA two
Acid anhydride）Outside, prepare polyester resin in the same manner as example 1.
Following table 1 is listed in the polyester resin according to embodiment and comparing embodiment preparation except dicarboxylic acids chemical combination
The content of the additive outside thing and diol compound（Unit：ppm）.
[table 1]
EXPERIMENTAL EXAMPLE
Measurement melts the intrinsic viscosity of fragment and solid debris, color L, face according to embodiment and comparing embodiment preparation
Color a and color b, summarize the result of its physical property and the evaluation result of process characteristic in table 2 below.By intrinsic viscosity
Comprehensive detection evaluation process characteristic with the result of color property.
[table 2]
Reference table 2, in the situation comprising titanium-germanium composite catalyzing immunomodulator compounds, toner, phosphorus compound and cobalt compound
In（Embodiment 1）And in the situation adding branching agent further thereto（Embodiment 2）It should be appreciated that obtaining optimal group
Become thing, wherein melt fragment and the intrinsic viscosity of solid debris and the value of color L and color b is suitable for moulding container.Now,
It should be understood that intrinsic viscosity can be improved by adding branching agent further.
On the contrary, the titanium catalyst compound in the catalyst compounds that only will be equivalent to embodiment is used as catalyst compounds
And except phosphorus compound and cobalt compound are added without in the situation of other additives（Embodiment 1）It will be understood that reducing solid
Color L of body fragment, color b and intrinsic viscosity.Similarly, adding the increasing having with embodiment identical content further
In the situation of toner（Comparing embodiment 4）It will be understood that compared with embodiment, reducing color L and color b, adding further
Enter in the situation of branching agent（Comparing embodiment 3 and 7）It will be understood that increased intrinsic viscosity, but compared with embodiment,
Also deteriorate color property.Additionally, the titanium catalyst compound in the catalyst compounds that only will be equivalent to embodiment is used as to urge
In agent compound, and the somewhat low situation of the content of toner（Comparing embodiment 2 and 6）It will be understood that reducing color
b.
Meanwhile, in the situation only antimonial being used as catalyst compounds（Comparing embodiment 5）, aggregate performance goes out pole
Good physical property, but, as described above, it is not favourable in terms of environmental friendliness.
As described above, for by using poly- according to the compositionss preparation of the polyester resin of the present invention for preparation
Ester resin, compared with the situation wherein only using typical titanium catalyst compound, can be by using titanium-germanium composite catalyst
Compound obtains fabulous intrinsic viscosity, color L and color b together with titanium catalyst compound.Thus, according to the present invention
Polyester resin can further compensate for polyester chips and molding product yellow, its be typical titanium catalyst compound bad
Gesture, is harmless and eco-friendly simultaneously to human body, can improve the phenomenon of the solid state polymerization rate of reduction further, it is
Another inferior position of typical titanium catalyst compound.
Prepare in the polyester resin for moulding container in the compositionss by using the present invention, because typical with utilizing
The situation of titanium catalyst compound is compared, and has high characteristic for preparation according to the compositionss of the polyester resin of the present invention and sticks
Degree, is harmless and eco-friendly to human body it is provided that being used for preparing the compositionss of polyester resin, it can improve simultaneously
Reaction rate during solid-state polymerization, and reduce the generation of the acetaldehyde being caused by pyrolysis.
Similarly, since using the titanium-germanium composite catalyst chemical combination with optimal composition in the application of green catalyst
Thing, is compared with using the situation of typical titanium catalyst compound, can keep the chromaticity coordinates value more improved, thus, can
To provide, there is the aetiolation of improvement and the polyester resin of economy.
Although by reference to its preferred implementation is particularly shown and the description present invention, those skilled in the art will manage
Solution, in the case of without departing substantially from the spirit and scope of the present invention being defined by appended claims, wherein can make various
Change in form and in details.
Claims (11)
1. a kind of compositionss for preparing polyester resin, the scope of the mol ratio of diol compound and dicarboxylic acid compound be from
1.05 to 1.4,
Wherein it is based on percetage by weight, described compositionss include the phosphorus compound of the amount 5ppm to 50ppm based on phosphorus, based on cobalt
The cobalt compound of amount 10ppm to 40ppm, the toner of 0.2ppm to 20ppm, and the amount 8ppm to 15ppm/ based on titanium/germanium
The titanium of 3ppm to 16ppm-germanium composite catalyzing immunomodulator compounds, the value of wherein chromaticity coordinates L is more than 75.0, and the value of chromaticity coordinates b is 0.0
Hereinafter, and intrinsic viscosity scope in 0.70dl/g to 0.9dl/g.
2. the compositionss for preparing polyester resin according to claim 1, wherein said for preparing polyester resin
Compositionss comprise the branching agent of 10ppm to 500ppm further.
3. the compositionss for preparing polyester resin according to claim 2, wherein said branching agent be selected from
One or more of group of lower every composition：Trimellitic acid, trimellitic anhydride, PMA, pyromellitic acid dianhydride, benzene first
Ketone -3,3 ', 4,4 '-tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, diphenyl
Sulfone tetracarboxylic dianhydride, Pentamethylene. tetracarboxylic dianhydride, tetramethylolmethane, oxolane, tetracarboxylic dianhydride, hydroxyl terephthalic acids, dihydroxy
Yl benzoic acid, 1,2,2 '-ethane tricarboxylic acids, glycerol and trimethylolpropane.
4. the compositionss for preparing polyester resin according to claim 1, before wherein passing through dissolving titanium in ethylene glycol
The mixture of body and germanium precursor forms described titanium-germanium composite catalyzing immunomodulator compounds.
5. the compositionss for preparing polyester resin according to claim 4, wherein said titanium precursor be titanium dioxide and
The composite oxides of silicon dioxide, and described germanium precursor is germanium dioxide.
6. the compositionss for preparing polyester resin according to claim 1, wherein said dicarboxylic acid compound is to be selected from
One or more of group being made up of the following：Phthalic acid, p-phthalic acid, isophathalic acid, two broxitalamic acid, sulfo group
M-phthalic acid sodium, phenylene dioxy dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acids, 4,4 '-diphenyl
Keto-dicarboxylic acid, 4,4 '-diphenoxyethanedicarboxylic acid, 4,4 '-sulfobenzide. dicarboxylic acids and 2,6 naphthalene dicarboxylic acid.
7. the compositionss for preparing polyester resin according to claim 6, wherein right by 90mol% to 100mol%
The isophathalic acid of phthalic acid and 0mol% to 10mol% forms described dicarboxylic acid compound.
8. the compositionss for preparing polyester resin according to claim 1, wherein said diol compound is to be selected from
One or more of group of the following composition：Monoethylene glycol, diethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,4- ring
Hexane dimethanol and neopentyl glycol.
9. the compositionss for preparing polyester resin according to claim 1, wherein said cobalt compound is cobaltous acetate.
10. the compositionss for preparing polyester resin according to claim 1, wherein said phosphorus compound be selected from
One or more of group of lower every composition：Phosphoric acid, trimethyl phosphate, triethyl phosphate, TRI N BUTYL PHOSPHATE, tricresyl phosphate are pungent
Ester, Triphenyl phosphate, lindol, methyl orthophosphoric acid, etherophosphoric acid, p isopropylbenzoic acid ester, butylphosphoric acid ester, p diethylaminobenzoic acid
Ester, mono phosphoric acid ester butyl ester, dibutylphosphoric acid ester, phosphoric acid dioctyl ester and phosphoric acid triglycol ester.
11. compositionss for preparing polyester resin according to claim 1, wherein said toner is blue dyess examination
Agent or orchil reagent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310054969.2A CN103992467B (en) | 2013-02-20 | 2013-02-20 | For the resin combination preparing thermoplastic polyester and the polyester resin prepared by said composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310054969.2A CN103992467B (en) | 2013-02-20 | 2013-02-20 | For the resin combination preparing thermoplastic polyester and the polyester resin prepared by said composition |
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| CN103992467A CN103992467A (en) | 2014-08-20 |
| CN103992467B true CN103992467B (en) | 2017-03-01 |
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| KR102553939B1 (en) * | 2018-02-07 | 2023-07-11 | 에스케이케미칼 주식회사 | Saturated copolyester resin and coating compositon comprising same |
| CN110054763B (en) * | 2019-04-08 | 2020-11-17 | 浙江恒逸石化有限公司 | Titanium-germanium composite catalyst for polyester synthesis and application thereof |
| CN113603874B (en) * | 2021-07-28 | 2022-11-01 | 武汉科技大学 | Polyester based on vanillyl alcohol derivatives, preparation and use as pesticide slow-release agents |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807486A (en) * | 2005-12-06 | 2006-07-26 | 中国石油天然气股份有限公司 | Preparation method for modified copolyester for non-fiber |
| CN102167803A (en) * | 2010-02-26 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of polyethylene terephthalate-1,3-propanediol copolyester |
| CN102300903A (en) * | 2008-12-30 | 2011-12-28 | 沙伯基础创新塑料知识产权有限公司 | Poly(butylene Terephthalate) Compositions, Methods Of Manufacture, And Articles Thereof |
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|---|---|---|---|---|
| JPH01259027A (en) * | 1988-04-08 | 1989-10-16 | Kanebo Ltd | Production of polyester |
| JPH1087808A (en) * | 1996-09-13 | 1998-04-07 | Nippon Ester Co Ltd | Production of polyester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807486A (en) * | 2005-12-06 | 2006-07-26 | 中国石油天然气股份有限公司 | Preparation method for modified copolyester for non-fiber |
| CN102300903A (en) * | 2008-12-30 | 2011-12-28 | 沙伯基础创新塑料知识产权有限公司 | Poly(butylene Terephthalate) Compositions, Methods Of Manufacture, And Articles Thereof |
| CN102167803A (en) * | 2010-02-26 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of polyethylene terephthalate-1,3-propanediol copolyester |
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