JPH04234428A - Manufacture of polyester - Google Patents
Manufacture of polyesterInfo
- Publication number
- JPH04234428A JPH04234428A JP3181569A JP18156991A JPH04234428A JP H04234428 A JPH04234428 A JP H04234428A JP 3181569 A JP3181569 A JP 3181569A JP 18156991 A JP18156991 A JP 18156991A JP H04234428 A JPH04234428 A JP H04234428A
- Authority
- JP
- Japan
- Prior art keywords
- antimony
- reaction
- titanate
- terephthalic acid
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 86
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims abstract description 7
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- -1 aminoethyl titanate Chemical compound 0.000 claims description 18
- 150000001463 antimony compounds Chemical class 0.000 claims description 16
- 150000003609 titanium compounds Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 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 claims description 6
- 239000005076 polymer ester Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 24
- 230000035484 reaction time Effects 0.000 abstract description 24
- 230000000704 physical effect Effects 0.000 abstract description 6
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 8
- 239000007809 chemical reaction catalyst Substances 0.000 description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 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 description 2
- KEUYHGXCOWNTEJ-UHFFFAOYSA-N trimethyl stiborite Chemical compound [Sb+3].[O-]C.[O-]C.[O-]C KEUYHGXCOWNTEJ-UHFFFAOYSA-N 0.000 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 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- RUZMUTWCUZLWQU-UHFFFAOYSA-N [ethoxy(hydroxy)phosphoryl] ethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OP(O)(=O)OCC RUZMUTWCUZLWQU-UHFFFAOYSA-N 0.000 description 1
- BPNLLIHZSAFABG-UHFFFAOYSA-N [hydroxy(methoxy)phosphoryl] methyl hydrogen phosphate Chemical compound COP(O)(=O)OP(O)(=O)OC BPNLLIHZSAFABG-UHFFFAOYSA-N 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical class O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 description 1
- PALVEAZBDSAOLL-UHFFFAOYSA-K antimony(3+);tribenzoate Chemical compound [Sb+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PALVEAZBDSAOLL-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HEGXHCKAUFQNPC-UHFFFAOYSA-N dicyclohexyl hydrogen phosphite Chemical compound C1CCCCC1OP(O)OC1CCCCC1 HEGXHCKAUFQNPC-UHFFFAOYSA-N 0.000 description 1
- CJJIDNVGCILLGW-UHFFFAOYSA-N dicyclohexyl phosphono phosphate Chemical compound C1CCCCC1OP(=O)(OP(O)(=O)O)OC1CCCCC1 CJJIDNVGCILLGW-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- YHRRLJVICROTOJ-UHFFFAOYSA-N diphenyl phosphono phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OP(O)(=O)O)OC1=CC=CC=C1 YHRRLJVICROTOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SJRXWMQZUAOMRJ-UHFFFAOYSA-N ethyl 2-hexenoate Chemical compound CCCC=CC(=O)OCC SJRXWMQZUAOMRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZJZKUISELYXHDV-UHFFFAOYSA-K triphenyl stiborite Chemical compound [Sb+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZJZKUISELYXHDV-UHFFFAOYSA-K 0.000 description 1
- HYPTXUAFIRUIRD-UHFFFAOYSA-N tripropan-2-yl stiborite Chemical compound [Sb+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HYPTXUAFIRUIRD-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
【0001】
【産業上の利用分野】ポリエステル、特にポリエチレン
テレフタレートは、結晶性が大きく高い軟化点を持ち、
強度、耐薬品性、耐熱性、耐候性及び電気絶縁性等です
ぐれた性質を有することから、繊維、フィルム及びその
他の産業用資材として広く使用されている。
【0002】本発明は、着色のない高品位ポリエステル
の製造方法に関する。
【0003】
【従来の技術】ポリエチレンテレフタレートの工業的な
製造方法としては、テレフタル酸とエチレングリコール
を常圧あるいは加圧下で加熱してジカルボン酸から直接
にエステル化物とするか、あるいはジメチルテレフタレ
ートとエチレングリコールを触媒の存在下で加熱反応さ
せエステル交換させて低重合体のエステル化物とし、継
続して重合触媒の存在下で重縮合反応させポリエステル
を得る方法が知られている。最近の工業製法としては、
経済的に非常に有利である直接にエステル化物を得る方
法が多く実施されている。
【0004】ポリエステルを製造するときには、反応を
円滑に進行させるために一般に触媒が使用される。触媒
としては、種々の金属化合物が知られ、触媒の種類によ
り反応速度が異なるだけでなく生成するポリエステルの
色相及び熱安定性が異なる。これらの反応は、金属を含
有した触媒存在下で高温で長時間行われるため、種々の
副反応をともない、生成した重合体が黄色に着色したり
、重合体中のジエチレングリコール含量及び末端カルボ
キシル基の濃度が適正水準以上に増加したりして、ポリ
エステルの融点及び強度低下などの物理的性質が低下す
ることがある。
【0005】現在、最も多く工業的に使用されている重
縮合触媒は、アンチモン化合物、特に価格も適切であり
触媒活性も比較的大きく熱安定性にもすぐれた3酸化ア
ンチモンである。しかしながら、3酸化アンチモンもエ
チレングリコールなどの反応溶液への溶解性が低く、反
応中に析出する傾向があり、生成したポリエステルが灰
色あるいは黄緑色に着色したり、透明性が低下したりす
ることがある。この様な現象は、生産性を増大させるた
めに触媒使用量を増加させたり、反応温度を高くしたり
すればさらに顕著になる。
【0006】従来、この様な問題点を改良するための種
々の方法が提案されているが満足すべきものはない。
【0007】例えば、反応時間を短縮させる方法として
、米国特許第3,927,052号明細書にはシリコン
化合物とチタニウム化合物を使用する方法が、特開昭5
3−51,295号公報には、3酸化アンチモンとコバ
ルト化合物及び燐化合物をエチレングリコールに溶解し
て使用する方法が、及び特開昭60−166,320号
公報には、アンチモン化合物と有機酸を共に使用する方
法などが記載されている。
【0008】しかしながら、このような方法においても
、エステル化反応時間と重縮合反応時間を共に短縮する
ことができず、生成した重合体の着色あるいは重合体中
のジエチレングリコール含量又は末端カルボキシル基の
含量が増加するなどの点は解決していない。
【0009】重合体の色相及び物性を改良する方法とし
ては、特開昭58−117,216号公報には、アンチ
モン化合物にコバルト化合物及びアルカリ金属化合物を
共に使用する方法が、特開昭49−31,317号公報
には、アンチモン化合物と錫化合物を共に使用する方法
が、及び特開昭62−265,324号公報には、アン
チモン、錫、コバルト、アルカリ金属化合物及び燐化合
物を共に使用する方法などが記載されている。
【0010】しかし、これらの方法でも重合体の色相や
透明性及び物性を同時に改良することができない。又、
反応時間の短縮についても大きな改善はみられない。
【0011】
【発明が解決しようとする課題】本発明は、色相及び物
性にすぐれた高品位ポリエステルの製造法、さらに生産
性の点から反応時間の短い製造法を提供することを目的
とする。
【0012】
【課題を解決するための手段】本発明は、直接エステル
化法又はエステル交換法によって、テレフタル酸又はこ
れを主成分とするジカルボン酸あるいはそれらの誘導体
と、エチレングリコール又はこれを主成分とするグルコ
ールを反応させて、ビス(β−ヒドロキシエチル)テレ
フタレート及び/又はその低重合体エステル化物を得、
さらにこれを重縮合反応させてポリエステルを製造する
方法において、アンチモン化合物とチタニウム化合物か
らなる複合触媒の存在下に反応させることを特徴とする
ポリエステルの製造方法である。
【0013】本発明のアンチモン化合物としては、例え
ば、3酸化アンチモン、4酸化アンチモンや5酸化アン
チモンの様な酸化アンチモン、3塩化アンチモンや3弗
化アンチモンの様なハロゲン化アンチモン、アンチモン
トリアセテート、アンチモン トリステアレート
、アンチモン トリベンゾエート、アンチモントリ2
−エチルヘキセノエートやアンチモン トリオクトエ
ートの様なアンチモンカルボン酸塩、アンチモントリメ
トキサイド、1,2−ジ(1,2−エタンジオキシアン
チモノオキシ)エチル、アンチモントリイソプロポキサ
イド、アンチモントリn−ブトキサイドやアンチモント
リフェノキサイドの様なエーテルが結合したアンチモン
化合物、及びアンチモン水酸化物や硫化物などがあげら
れる。これらのうち、好ましいアンチモン化合物は3酸
化アンチモン、アンチモン トリアセテート、及び1
,2−ジ(1,2−エタンジオキシアンチモノオキシ)
エチレンである。
【0014】本発明のチタニウム化合物としては、例え
ば、チタニウムテトラクロライドの様なハロゲン化チタ
ニウム、式(I)で示されるエーテル結合を有するチタ
ニウム化合物
【0015】Ti(OR1)4 (I)【00
16】(式中、R1 は同一又は異なり脂肪族基、シク
ロアルキル基、アリール基又はアラルキル基を表す)を
あげることができる。
【0017】R1 が表す脂肪族アルキル基としては、
メチル、エチル、n−プロピル、イソプロピル、n−ブ
チル、イソブチル、sec −ブチル、tert−ブチ
ル、n−アミル、ネオヘキシル、イソヘキシル、n−ヘ
キシル、ヘプチル、オクチル、デシル、ドデシル、オク
タデシルなどがあげられ、R1 が表すシクロアルキル
基としては、シクロペンチル、シクロヘキシルなどがあ
げられる。
又、アリール基及びアラルキル基としては、フェニル及
びベンジルなどがあげられる。これらのうち、R1 の
表す好ましい基は、炭素数8個以下のアルキル基である
。
【0018】本発明の異なるチタニウム化合物としては
、式(I)で示す化合物とホスファイト化合物[HP(
O)(OR2)2]が1:2でコーディネートした式(
II)で示されるチタニウム化合物をあげることができ
る。
【0019】
(R1 O)4 Ti[HP(O)(OR2)2]2
(II) 【0020】(式中、R1 は前述
と同じであり、R2 は、同一又は異なり脂肪族基、シ
クロアルキル基又はアリール基を表す。)
【0021】本発明の式(II)のチタニウム化合物の
具体的な例としては、テトライソプロピル ビス(ジ
メチルホスファイト)チタネート、テトラn−ブチル
ビス(ジイソプロピルホファイト)チタネート、テト
ライソプロピル ビス(ジオクチルホスファイト)チ
タネート、テトラオクチル ビス(ジステアリルホス
ファイト)チタネート、テトラオクチル ビス(ジト
リデシルホスファイト)チタネート及びテトラ(2,2
−ジ(アリルオキシメチル)ブチル) ビス(ジトリ
デシルホスファイト)チタネートの様なコーディネート
化合物があげられる。
【0022】また他のチタニウム化合物の例として、イ
ソプロピル トリイソオクタデシルチタネイト、イソ
プロピル トリス(2−N(2−アミノエチル)アミ
ノエチル)チタネートの様なアルコキシチタネイト化合
物;ビス(クミルフェニル) オキソエチレンチタネ
ート、ビス(ジオクチルオキシホスヒノイル) エチ
レンチタネートの様なキーレートチタネート化合物;2
,2−ジ(アリルオキシメチル)ブチル トリス(2
−N−(2−アミノエチル)アミノエチル)チタネート
、2,2−ジ(アリルオキシメチル)ブチル トリス
(4−ドデシルベンゼンスルホニル)チタネートの様な
ネオアルコキシチタネート化合物。ジオクチルオキシチ
タン(ジオクチル)ジホスフェート及びチタンビス(ジ
オクチル)ジホスフェートの様なチタネート化合物。
【0023】これらのチタニウム化合物のうち、テトラ
イソプロピル ビス(ジオクチルホスファイト)チタ
ネート、イソプロピル トリス(2−N(2−アミノ
エチル)アミノエチル)チタネート及びテトライソプロ
ピル チタネートなどが好適に使用される。
【0024】上述したアンチモン化合物類とチタニウム
化合物類を各々1種又は2種以上を共に使用することも
できる。
【0025】本発明で使用する複合触媒は、アンチモン
化合物に対するチタニウム化合物の割合が重量比で0.
01〜100であり、好ましくは0.1〜9.0である
。又、復合触媒の使用量は、特に制限はないが、好まし
くは生成するポリエステルに対しアンチモン化合物とチ
タニウム化合物の合計量が100〜1,000ppm
であり、特に好ましくは250〜750ppm である
。
【0026】本発明の複合触媒は、アンチモン化合物と
チタニウム化合物をエチレングリコール又はエチレング
リコールを主成分とする溶媒に溶解させて得た複合触媒
溶液を20°〜200°、好ましくは30〜150℃に
加熱し、反応系に添加して使用できる。
【0027】アンチモン化合物、特に3酸化アンチモン
は、その安定性が低いためエチレングリコールに溶解し
た後長時間室温で放置した場合、沈澱物を生成すること
があるが、上記方法で製造した触媒系はこの様な沈澱物
の生成がなく、非常に安定性が高い触媒系である。例え
ば、マイナス10℃の温度で長時間保管しても沈澱物が
生成しなかった。
【0028】さらに、本発明の目的から逸脱しない範囲
で他の触媒を共に使用することもできる。例えば、酸化
ゲルマニウムの様なゲルマニウム化合物、ジブチルチン
オキサイド、n−ブチルヒドロキシチンオキサイドの様
な錫化合物、ジンクアセテート、マンガンアセテート、
リードアセテートの様な亜鉛、マンガン、鉛のカルボン
酸塩、ナトリウム又はカリウムの水酸化物及びカリウム
アセテートの様なアルカリ金属化合物、マグネシウム又
はカルシウムの水酸化物及びカルシウムアセテートの様
なアルカリ土類金属化合物をあげることができる。
【0029】本発明での触媒の添加時期はエステル化反
応開始前、反応中又は反応終了後、すなわち重縮合反応
前に添加してもよい。しかし、生産性の向上のため全反
応時間を短縮する目的にはエステル化反応開始前に添加
するのが有利である。
【0030】テレフタル酸とエチレングリコールから直
接エステル化物を得る場合は、テレフタル酸とエチレン
グリコールとのスラリーに触媒を添加し反応させるのが
有利である。又、エステル化反応開始前と重縮合反応開
始前に分割して添加しても反応は有利に進行する。
【0031】直接エステル化する反応は、常圧又は加圧
下で反応温度200〜280℃、好ましくは220〜2
60℃で行うのが有利である。エステル交換反応である
場合、反応温度160〜240℃で従来の触媒に代えて
本発明の触媒を使用する。
【0032】この様にして得たエステル化物を常圧又は
加圧下で反応温度260〜300℃で重縮合反応させる
ことができる。反応温度を徐々に上げるとともに、真空
度も徐々に高め、反応の最終段階では、反応温度は27
5〜290℃、真空度は1トール以下で行うのが有利で
ある。
【0033】本発明で使用することのできる代表的な酸
及びその誘導体は、テレフタル酸とジメチルテレフタレ
ートであり、代表的なグリコールはエチレングリコール
である。又、これ以外に少なくとも1種類以上の第3成
分を添加し反応させることもできる。しかし、第3成分
は40モルパーセントを超えないのが望ましい。
【0034】本発明の第3成分としては、例えば、フタ
ル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェ
ニルスルホンジカルボン酸、ジフェニルメタンジカルボ
ン酸、ジフェニルエーテルジカルボン酸、ジフェノキシ
エタンジカルボン酸、マロン酸、コハク酸、グルタル酸
、アジピン酸、アゼライン酸、セバシン酸、シクロヘキ
サンジカルボン酸、デカンジカルボン酸などの芳香族、
芳香脂肪族、脂肪族及び脂環式ジカルボン酸及び、これ
らの酸のメチルエステル、エチルエステル及びフェニル
エステルなどのエステル誘導体、及び1,3−プロパン
ジオール、1,2−プロパンジオール、1,4−ブタン
ジオール、1,3−ブタンジオール、1,5−ペンタン
ジオール、1,6−ヘキサンジオール、1,4−シクロ
ヘキサンジメタノール、1,4−シクロヘキサンジオー
ル、ビスフェノールA、ビスフェノールS、ビスヒドロ
キシエトキシビスフェノールA、テトラブロモビスフェ
ノールAなどの脂肪族、脂環式及び芳香族ジオールなど
のジオール類をあげることができる。
【0035】又、本発明は、トリメリット酸、トリメシ
ン酸、ピロメリット酸、トリメチロールプロパン、グリ
セリン、ペンタエリスリトールなどの多官能性架橋剤化
合物及びモノメトキシポリエチレングリコール、ステア
リルアルコール、パルミチン酸、安息香酸、ナフトエ酸
などの単官能性末端基終結剤を添加して反応させること
もできる。
【0036】さらに本発明は、ポリエステルを製造する
場合に、添加する熱安定剤、例えば、燐酸、亜燐酸、メ
タ燐酸、トリメチルホスフェート、トリエチルホスフェ
ート、トリフェニルホスフェート、トリオクチルホスフ
ェート、ジメチルホスファイト、ジエチルホスファイト
、ジシクロヘキシルホスファイト、ジフェニルホスファ
イト、ジオクチルホスファイト、ジメチルピロホスフェ
ート、ジエチルピロホスフェート、ジフェニルピロホス
フェート、ジシクロヘキシルピロホスフェート、ジオク
チルピロホスフェート、及び酸化防止剤、例えばイルガ
ノックス1010、イルガノックス1076、イルガノ
ックス1098などのチバ・ガイギー社製品なども必要
に応じ使用することができる。
【0037】その他、コバルトアセテートの様な保色剤
、ベンゾトリアゾールの様な紫外線吸収剤、トリエチル
アミンの様な軟化点低下防止剤、酸化チタニウムの様な
消光剤、シリカ及びアルミナの様な核剤、染料、螢光増
白剤、帯電防止剤及び難燃化剤なども使用できるものと
してあげることができる。
【0038】
【実施例】次に、本発明を実施例でより詳細に説明する
がこれらは本発明の方法を実施例に限定するものではな
い。実施例中で“部”と表示したのは重量部を意味する
。又、重合体の極限粘度[η]は、フェノール(6部)
とテトラクロロエタン(4部)の混合溶媒中30℃で測
定した。
【0039】又、ジエチレングリコール(DEG)含量
は重合体をヒドラジンヒドラートで分解しガスクロマト
グラフィーで測定した。重合体の色相は色差計を用いチ
ップ状態で測定した。ここで得たL値及びb値は各々重
合体の明度及び着色程度を表す尺度であり、普通L値が
大きい程、又b値が小さい程色相がすぐれていることを
示す。
【0040】実施例1
生成するポリエステルに対し、酸化アンチモン250p
pm とテトライソプロピル ビス(ジオクチルホス
ファイト)チタネート250ppm をエチレングリコ
ールに溶解した複合触媒溶液を60℃で1時間加熱した
のち、エチレングリコールとテレフタル酸で調製したス
ラリーに反応触媒として添加した。この時使用したエチ
レングリコールとテレフタル酸のモル比は最終的に1.
1になる様にした。この様にして反応触媒を添加したエ
チレングリコール/テレフタル酸スラリーを既にエステ
ル化物が存在しているエステル化反応装置に供給し、常
圧で反応温度240℃、反応時間3時間30分でエステ
ル化物を得た。このエステル化物をかきまぜ器及びトル
クメーターをもつ重縮合反応器に移送し、生成するポリ
エステルに対し、トリメチルホスフェート100ppm
を添加した。
次いで、重縮合反応器の温度を徐々に上げ最終温度28
5℃、反応器内の圧力を徐々に下げ、最終圧力を0.8
トールとし、反応時間1時間53分で反応を終結した。
反応終了後、反応器下部ノズルを通じ冷却水中に反応混
合物を押出し、チップ状態で重合体を得た。生成した重
合体の極限粘度、ジエチレングリコール(DEG)含量
、末端カルボキシル基濃度及び色相を表1に示した。
【0041】比較例1
エチレングルコール/テレフタル酸スラリーに反応触媒
を添加しないで実施例1と同様に、反応時間4時間45
分で直接エステル化反応を行った。次いで実施例1と同
様に、生成するポリエステルに対し3酸化アンチモン3
80ppm 、トリメチルホスフェート100ppm
を添加し2時間50分の間重縮合させ、実施例1と同様
に処理して重合体を得た。得られた重合体の結果を表1
に示した。
【0042】比較例2
エチレングリコール/テレフタル酸スラリーに反応触媒
としてテトライソプロピル ビス(ジオクチルホスフ
ァイト)チタネート380ppm を添加し、実施例1
と同様に、反応時間3時間35分で直接エステル反応を
行い、ついで実施例1と同一な重合条件で重縮合させた
。この場合、重縮合反応時間は2時間20分であった。
得られた重合体の結果を表1に示した。
【0043】実施例2
実施例1と同様に、エチレングリコール/テレフタル酸
スラリーに反応触媒としてアンチモントリアセテート3
00ppm とイソプロピル トリス(2−N−(ア
ミノエチル)アミノエチル)チタネート200ppm
の複合触媒溶液を120℃で30分間加熱し添加した。
実施例1と同一な条件でエステル化反応を行った。反応
時間3時間40分でエステル化反応を終結し、実施例1
と同一条件で重縮合させた。重縮合反応時間1時間50
分で反応が終結し、実施例1と同様にして重合体を得た
。その結果を表1に示した。
【0044】実施例3
実施例1と同様にエチレングリコール/テレフタル酸の
スラリーに、反応触媒として3酸化アンチモン350p
pm とテトライソプロピル チタネート150pp
m 、さらにジメチルホスファイト100ppm を添
加したエチレングリコール溶液を50℃で2時間加熱し
添加した。実施例1と同一な条件でエステル化反応させ
、反応時間3時間23分で得たエステル化物を実施例1
と同一条件で重縮合反応させた。1時間58分で重縮合
反応を終結させ、実施例1と同様にして重合体を得た。
その結果を表1に示した。
【0045】実施例4
実施例1と同様に、エステル化反応及び重縮合反応を触
媒濃度を各々300ppm に代え実施例1と同一な条
件で行った。この場合、エステル化反応時間は3時間1
8分であり、重縮合反応時間は1時間50分であった。
実施例1と同様に処理して得た重合体の結果を表1に示
した。
【0046】実施例5
実施例4と同様に、触媒濃度を各々150ppm と3
50ppm としてエステル化反応及び重縮合反応を行
った。この場合、エステル化反応時間は3時間43分で
あり、重縮合反応時間は1時間48分であった。その結
果を表1に示した。
【0047】実施例6
ジメチルテレフタレート970部とエチレングリコール
640部のスラリーに対して実施例1で使用した複合触
媒溶液を同じ濃度で添加し、実施例1と同様に最終温度
220℃で2時間15分エステル交換反応させた。この
エステル化物を、実施例1と同一な重縮合条件で反応さ
せた。1時間42分間の反応時間で得た重合体の結果を
表1に示した。
【0048】比較例3
実施例6と同一な条件で、反応触媒をマンガンアセテー
ト0.31部に代えエステル交換反応させた。反応時間
3時間30分で得たエステル化反応物を実施例1と同一
な重縮合条件で反応させた。反応時間2時間35分で重
合体を得た。この場合、触媒として生成するポリエステ
ルに対し3酸化アンチモン380ppmとトリフェニル
ホスフェート100ppm を添加した。得られた重合
体の結果を表1に示した。
【0049】
【発明の効果】本発明の方法は、ポリエステル製造に要
する反応時間を短縮し、生成した重合体の色相がすぐれ
、重合体中のジエチレングリコール含量及び末端カルボ
キシル基の濃度が低い高品位のポリエステルを製造する
方法である。
【0050】
【表1】Detailed Description of the Invention [0001] [Industrial Application Field] Polyester, especially polyethylene terephthalate, has high crystallinity and a high softening point.
Because it has excellent properties such as strength, chemical resistance, heat resistance, weather resistance, and electrical insulation, it is widely used as fibers, films, and other industrial materials. The present invention relates to a method for producing high-grade polyester without coloring. [0003] As an industrial method for producing polyethylene terephthalate, terephthalic acid and ethylene glycol are heated under normal pressure or pressure to form an esterified product directly from dicarboxylic acid, or dimethyl terephthalate and ethylene A method is known in which a glycol is heated and transesterified in the presence of a catalyst to obtain an esterified product of a low polymer, and then a polycondensation reaction is performed in the presence of a polymerization catalyst to obtain a polyester. Recent industrial manufacturing methods include
Many methods have been implemented to directly obtain esterified products, which are very economically advantageous. [0004] When producing polyester, a catalyst is generally used to facilitate the reaction. Various metal compounds are known as catalysts, and not only the reaction rate differs depending on the type of catalyst, but also the color and thermal stability of the polyester produced differ. These reactions are carried out at high temperatures for long periods of time in the presence of metal-containing catalysts, resulting in various side reactions that may cause the resulting polymer to turn yellow, or reduce the diethylene glycol content and terminal carboxyl groups in the polymer. If the concentration is increased beyond the appropriate level, physical properties such as melting point and strength reduction of the polyester may be degraded. [0005] Currently, the polycondensation catalyst most often used industrially is an antimony compound, especially antimony trioxide, which is reasonably priced, has relatively high catalytic activity, and is excellent in thermal stability. However, antimony trioxide also has low solubility in reaction solutions such as ethylene glycol and tends to precipitate during the reaction, resulting in the resulting polyester being colored gray or yellow-green or having reduced transparency. be. Such a phenomenon becomes more noticeable if the amount of catalyst used is increased or the reaction temperature is raised in order to increase productivity. Conventionally, various methods have been proposed to improve these problems, but none of them are satisfactory. For example, as a method for shortening the reaction time, US Pat. No. 3,927,052 describes a method using a silicon compound and a titanium compound.
3-51,295 discloses a method in which antimony trioxide, a cobalt compound, and a phosphorus compound are dissolved in ethylene glycol, and JP-A-60-166,320 discloses a method in which an antimony compound and an organic acid are used. It describes how to use them together. However, even with this method, both the esterification reaction time and the polycondensation reaction time cannot be shortened, and the resulting polymer may be colored or the diethylene glycol content or the content of terminal carboxyl groups in the polymer may be reduced. Issues such as an increase in demand have not been resolved. As a method for improving the hue and physical properties of polymers, JP-A-58-117,216 discloses a method of using an antimony compound together with a cobalt compound and an alkali metal compound. No. 31,317 discloses a method in which an antimony compound and a tin compound are used together, and JP-A-62-265,324 discloses a method in which antimony, tin, cobalt, an alkali metal compound, and a phosphorus compound are used together. Methods are described. However, even with these methods, it is not possible to simultaneously improve the hue, transparency and physical properties of the polymer. or,
No significant improvement was seen in the reduction of reaction time either. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing high-grade polyester with excellent hue and physical properties, and a method that requires a short reaction time from the viewpoint of productivity. [0012] Means for Solving the Problems [0012] The present invention is directed to the production of terephthalic acid or a dicarboxylic acid containing terephthalic acid as a main component, or a derivative thereof, and ethylene glycol or a dicarboxylic acid containing terephthalic acid as a main component, by a direct esterification method or a transesterification method. reacting glycol to obtain bis(β-hydroxyethyl) terephthalate and/or a low polymer ester thereof,
Further, in a method for producing polyester by subjecting the polycondensation reaction to polycondensation reaction, the method is characterized in that the reaction is carried out in the presence of a composite catalyst consisting of an antimony compound and a titanium compound. Examples of the antimony compound of the present invention include antimony oxides such as antimony trioxide, antimony tetraoxide and antimony pentoxide, antimony halides such as antimony trichloride and antimony trifluoride, antimony triacetate, and antimony triacetate. stearate, antimony tribenzoate, antimony tribenzoate
- Antimony carboxylates such as ethylhexenoate and antimony trioctoate, antimony trimethoxide, 1,2-di(1,2-ethanedioxyantimonooxy)ethyl, antimony triisopropoxide, antimony trimethoxide, Antimony compounds to which ethers are bonded, such as n-butoxide and antimony triphenoxide, as well as antimony hydroxides and sulfides, are included. Among these, preferred antimony compounds are antimony trioxide, antimony triacetate, and antimony triacetate.
,2-di(1,2-ethanedioxyantimonooxy)
It is ethylene. Examples of the titanium compound of the present invention include titanium halides such as titanium tetrachloride, titanium compounds having an ether bond represented by formula (I), and Ti(OR1)4 (I) 00
16] (wherein R1 is the same or different and represents an aliphatic group, a cycloalkyl group, an aryl group, or an aralkyl group). The aliphatic alkyl group represented by R1 is:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, neohexyl, isohexyl, n-hexyl, heptyl, octyl, decyl, dodecyl, octadecyl, etc. Examples of the cycloalkyl group represented by R1 include cyclopentyl and cyclohexyl. Furthermore, examples of the aryl group and aralkyl group include phenyl and benzyl. Among these, a preferable group represented by R1 is an alkyl group having 8 or less carbon atoms. Different titanium compounds of the present invention include the compound represented by formula (I) and the phosphite compound [HP(
O)(OR2)2] is coordinated in a 1:2 ratio (
Titanium compounds represented by II) can be mentioned. (R1 O)4 Ti[HP(O)(OR2)2]2
(II) [0020] (In the formula, R1 is the same as above, and R2 is the same or different and represents an aliphatic group, a cycloalkyl group, or an aryl group.) [0021] Titanium of the formula (II) of the present invention Specific examples of compounds include tetraisopropyl bis(dimethylphosphite) titanate, tetra n-butyl
Bis(diisopropylphosphite) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(distearylphosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate and tetra(2,2
-di(allyloxymethyl)butyl) bis(ditridecylphosphite) titanate. Examples of other titanium compounds include alkoxy titanate compounds such as isopropyl triisooctadecyl titanate and isopropyl tris(2-N(2-aminoethyl)aminoethyl)titanate; bis(cumylphenyl)oxoethylene titanate. , chelate titanate compounds such as bis(dioctyloxyphosphonoyl) ethylene titanate; 2
,2-di(allyloxymethyl)butyl tris(2
Neoalkoxytitanate compounds such as -N-(2-aminoethyl)aminoethyl)titanate, 2,2-di(allyloxymethyl)butyl tris(4-dodecylbenzenesulfonyl)titanate. Titanate compounds such as dioctyloxytitanium (dioctyl) diphosphate and titanium bis(dioctyl) diphosphate. Among these titanium compounds, tetraisopropyl bis(dioctylphosphite) titanate, isopropyl tris(2-N(2-aminoethyl)aminoethyl)titanate, and tetraisopropyl titanate are preferably used. [0024] The above-mentioned antimony compounds and titanium compounds can be used alone or in combination. The composite catalyst used in the present invention has a weight ratio of titanium compound to antimony compound of 0.
01 to 100, preferably 0.1 to 9.0. The amount of the decomposition catalyst used is not particularly limited, but preferably the total amount of the antimony compound and titanium compound is 100 to 1,000 ppm based on the polyester to be produced.
and particularly preferably 250 to 750 ppm. The composite catalyst of the present invention is prepared by heating a composite catalyst solution obtained by dissolving an antimony compound and a titanium compound in ethylene glycol or a solvent mainly composed of ethylene glycol at 20° to 200°C, preferably 30 to 150°C. It can be used by heating and adding it to the reaction system. Antimony compounds, especially antimony trioxide, have low stability and may form a precipitate if left at room temperature for a long time after being dissolved in ethylene glycol. However, the catalyst system produced by the above method This catalyst system does not generate such precipitates and is extremely stable. For example, no precipitate was formed even when stored for a long time at a temperature of -10°C. Additionally, other catalysts may be used without departing from the objectives of the invention. For example, germanium compounds such as germanium oxide, tin compounds such as dibutyltin oxide, n-butylhydroxytin oxide, zinc acetate, manganese acetate,
Carboxylate salts of zinc, manganese and lead such as lead acetate, alkali metal compounds such as sodium or potassium hydroxide and potassium acetate, alkaline earth metal compounds such as magnesium or calcium hydroxide and calcium acetate. can be given. In the present invention, the catalyst may be added before the start of the esterification reaction, during the reaction, or after the end of the reaction, that is, before the polycondensation reaction. However, for the purpose of shortening the total reaction time to improve productivity, it is advantageous to add it before the start of the esterification reaction. When obtaining an esterified product directly from terephthalic acid and ethylene glycol, it is advantageous to add a catalyst to a slurry of terephthalic acid and ethylene glycol for reaction. Furthermore, the reaction proceeds advantageously even if it is added in portions before the start of the esterification reaction and before the start of the polycondensation reaction. [0031] The direct esterification reaction is carried out at a reaction temperature of 200 to 280°C, preferably 220 to 280°C under normal pressure or increased pressure.
Advantageously, it is carried out at 60°C. In the case of transesterification, the catalyst of the present invention is used in place of the conventional catalyst at a reaction temperature of 160 to 240°C. The esterified product thus obtained can be subjected to a polycondensation reaction at a reaction temperature of 260 to 300° C. under normal pressure or increased pressure. The reaction temperature was gradually increased and the degree of vacuum was also gradually increased, and at the final stage of the reaction, the reaction temperature was 27.
It is advantageous to carry out the reaction at a temperature of 5 to 290° C. and a degree of vacuum of 1 Torr or less. Typical acids and derivatives thereof that can be used in the present invention are terephthalic acid and dimethyl terephthalate, and a typical glycol is ethylene glycol. In addition, at least one kind of third component can be added and reacted. However, it is preferred that the third component does not exceed 40 mole percent. Examples of the third component of the present invention include phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, malonic acid, succinic acid, and glutaric acid. Aromatic acids, such as adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid,
Aroaliphatic, aliphatic and cycloaliphatic dicarboxylic acids and ester derivatives of these acids, such as methyl esters, ethyl esters and phenyl esters, and 1,3-propanediol, 1,2-propanediol, 1,4- Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol S, bishydroxyethoxybisphenol A , tetrabromobisphenol A, and other aliphatic, cycloaliphatic, and aromatic diols. The present invention also provides polyfunctional crosslinking agent compounds such as trimellitic acid, trimesic acid, pyromellitic acid, trimethylolpropane, glycerin, and pentaerythritol, and monomethoxypolyethylene glycol, stearyl alcohol, palmitic acid, and benzoic acid. The reaction can also be carried out by adding a monofunctional end group terminator such as naphthoic acid or the like. Furthermore, the present invention provides thermal stabilizers to be added when producing polyester, such as phosphoric acid, phosphorous acid, metaphosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trioctyl phosphate, dimethyl phosphite, diethyl Phosphite, dicyclohexyl phosphite, diphenyl phosphite, dioctyl phosphite, dimethyl pyrophosphate, diethyl pyrophosphate, diphenyl pyrophosphate, dicyclohexyl pyrophosphate, dioctyl pyrophosphate, and antioxidants such as Irganox 1010, Irganox 1076, Irga Ciba-Geigy products such as Nox 1098 can also be used if necessary. In addition, color preservatives such as cobalt acetate, ultraviolet absorbers such as benzotriazole, softening point lowering inhibitors such as triethylamine, quenchers such as titanium oxide, nucleating agents such as silica and alumina, Dyes, fluorescent brighteners, antistatic agents, and flame retardants may also be mentioned as those that can be used. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the method of the present invention is not limited to these Examples. In the examples, "parts" means parts by weight. In addition, the intrinsic viscosity [η] of the polymer is phenol (6 parts)
and tetrachloroethane (4 parts) at 30°C. Further, the diethylene glycol (DEG) content was determined by decomposing the polymer with hydrazine hydrate and measuring it by gas chromatography. The hue of the polymer was measured in chip form using a colorimeter. The L value and b value obtained here are scales representing the lightness and degree of coloring of the polymer, respectively, and generally, the larger the L value and the smaller the b value, the better the hue. Example 1 250p of antimony oxide was added to the polyester to be produced.
A composite catalyst solution containing 250 ppm of tetraisopropyl bis(dioctyl phosphite) titanate dissolved in ethylene glycol was heated at 60° C. for 1 hour, and then added as a reaction catalyst to a slurry prepared with ethylene glycol and terephthalic acid. The molar ratio of ethylene glycol and terephthalic acid used at this time was ultimately 1.
I set it to 1. The ethylene glycol/terephthalic acid slurry to which the reaction catalyst had been added in this manner was supplied to the esterification reactor in which the esterified product was already present, and the esterified product was produced at normal pressure, at a reaction temperature of 240°C, and for a reaction time of 3 hours and 30 minutes. Obtained. This esterified product is transferred to a polycondensation reactor equipped with a stirrer and a torque meter, and 100 ppm of trimethyl phosphate is added to the resulting polyester.
was added. Then, the temperature of the polycondensation reactor was gradually increased to a final temperature of 28
5℃, gradually lower the pressure in the reactor to a final pressure of 0.8
The reaction was completed after a reaction time of 1 hour and 53 minutes. After the reaction was completed, the reaction mixture was extruded into cooling water through the lower nozzle of the reactor to obtain a polymer in the form of chips. Table 1 shows the intrinsic viscosity, diethylene glycol (DEG) content, terminal carboxyl group concentration, and hue of the produced polymer. Comparative Example 1 The reaction time was 4 hours and 45 minutes in the same manner as in Example 1 without adding a reaction catalyst to the ethylene glycol/terephthalic acid slurry.
Direct esterification reaction was carried out in minutes. Next, in the same manner as in Example 1, antimony trioxide 3 was added to the polyester to be produced.
80ppm, trimethyl phosphate 100ppm
was added and polycondensed for 2 hours and 50 minutes, and treated in the same manner as in Example 1 to obtain a polymer. Table 1 shows the results of the obtained polymer.
It was shown to. Comparative Example 2 380 ppm of tetraisopropyl bis(dioctyl phosphite) titanate was added as a reaction catalyst to the ethylene glycol/terephthalic acid slurry.
In the same manner as in Example 1, a direct ester reaction was carried out for a reaction time of 3 hours and 35 minutes, and then polycondensation was carried out under the same polymerization conditions as in Example 1. In this case, the polycondensation reaction time was 2 hours and 20 minutes. Table 1 shows the results of the obtained polymer. Example 2 Similarly to Example 1, antimony triacetate 3 was added to the ethylene glycol/terephthalic acid slurry as a reaction catalyst.
00ppm and isopropyl tris(2-N-(aminoethyl)aminoethyl)titanate 200ppm
The composite catalyst solution was heated at 120° C. for 30 minutes and added. The esterification reaction was carried out under the same conditions as in Example 1. The esterification reaction was completed after a reaction time of 3 hours and 40 minutes, and Example 1
Polycondensation was carried out under the same conditions as . Polycondensation reaction time 1 hour 50
The reaction was completed in minutes, and a polymer was obtained in the same manner as in Example 1. The results are shown in Table 1. Example 3 Similarly to Example 1, 350p of antimony trioxide was added to the ethylene glycol/terephthalic acid slurry as a reaction catalyst.
pm and tetraisopropyl titanate 150pp
An ethylene glycol solution containing 100 ppm of dimethyl phosphite was heated at 50° C. for 2 hours and then added. The esterification reaction was carried out under the same conditions as in Example 1, and the esterified product obtained in a reaction time of 3 hours and 23 minutes was used as Example 1.
The polycondensation reaction was carried out under the same conditions as . The polycondensation reaction was completed in 1 hour and 58 minutes, and a polymer was obtained in the same manner as in Example 1. The results are shown in Table 1. Example 4 Similar to Example 1, the esterification reaction and polycondensation reaction were carried out under the same conditions as in Example 1 except that the catalyst concentration was changed to 300 ppm. In this case, the esterification reaction time is 3 hours 1
The polycondensation reaction time was 1 hour and 50 minutes. Table 1 shows the results of the polymer obtained by the same treatment as in Example 1. Example 5 Same as Example 4, the catalyst concentration was 150 ppm and 3
The esterification reaction and polycondensation reaction were carried out at a concentration of 50 ppm. In this case, the esterification reaction time was 3 hours and 43 minutes, and the polycondensation reaction time was 1 hour and 48 minutes. The results are shown in Table 1. Example 6 The same concentration of the composite catalyst solution used in Example 1 was added to a slurry of 970 parts of dimethyl terephthalate and 640 parts of ethylene glycol, and the mixture was heated at a final temperature of 220° C. for 2 hours in the same manner as in Example 1. A transesterification reaction was carried out. This esterified product was reacted under the same polycondensation conditions as in Example 1. Table 1 shows the results of the polymer obtained with a reaction time of 1 hour and 42 minutes. Comparative Example 3 A transesterification reaction was carried out under the same conditions as in Example 6 except that 0.31 part of manganese acetate was used as the reaction catalyst. The esterification reaction product obtained after a reaction time of 3 hours and 30 minutes was reacted under the same polycondensation conditions as in Example 1. A polymer was obtained in a reaction time of 2 hours and 35 minutes. In this case, 380 ppm of antimony trioxide and 100 ppm of triphenyl phosphate were added to the polyester produced as a catalyst. Table 1 shows the results of the obtained polymer. Effects of the Invention The method of the present invention shortens the reaction time required to produce polyester, produces a high-grade polymer with excellent hue, and has a low diethylene glycol content and a low concentration of terminal carboxyl groups. This is a method for producing polyester. [Table 1]
Claims (6)
ジカルボン酸あるいはそれらの誘導体と、エチレングリ
コール又はこれを主成分とするグリコールを反応させて
、ビス(β−ヒドロキシエチル)テレフタレート及び/
又はその低重合体エステル化物を得、さらにこれを重縮
合反応させてポリエステルを製造する方法において、ア
ンチモン化合物とチタニウム化合物からなる複合触媒の
存在下に反応させることを特徴とするポリエステルの製
造方法。Claim 1: Bis(β-hydroxyethyl) terephthalate and/or bis(β-hydroxyethyl) terephthalate is produced by reacting terephthalic acid, a dicarboxylic acid containing terephthalic acid as a main component, or a derivative thereof with ethylene glycol or a glycol containing terephthalic acid as a main component.
Or a method for producing a polyester by obtaining a low polymer ester thereof and further subjecting it to a polycondensation reaction, the method comprising reacting in the presence of a composite catalyst consisting of an antimony compound and a titanium compound.
又はアンチモントリアセテートである請求項1の製造方
法。2. The method according to claim 1, wherein the antimony compound is antimony trioxide or antimony triacetate.
ル ビス(ジオクチルホスファイト)チタネート、イ
ソプロピル トリス(2−N−(2−アミノエチル)
アミノエチル)チタネート又はテトライソプロピルチタ
ネートである請求項1の製造方法。[Claim 3] The titanium compound is tetraisopropyl bis(dioctylphosphite) titanate, isopropyl tris(2-N-(2-aminoethyl)
2. The method according to claim 1, wherein the titanate is aminoethyl titanate or tetraisopropyl titanate.
ステルに対し100〜1,000ppm である請求項
1の製造方法。4. The manufacturing method according to claim 1, wherein the amount of the composite catalyst used is 100 to 1,000 ppm based on the polyester to be produced.
とチタニウム化合物の重量比が0.01〜100である
請求項1の製造方法。5. The manufacturing method according to claim 1, wherein in the composite catalyst, the weight ratio of the antimony compound to the titanium compound is 0.01 to 100.
、20〜200℃に加熱し、反応系に添加する請求項1
の製造方法。Claim 6: Claim 1, wherein the glycol solution in which the composite catalyst is dissolved is heated to 20 to 200°C and added to the reaction system.
manufacturing method.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR16698/1990 | 1990-10-19 | ||
KR1019900016698A KR950006132B1 (en) | 1990-10-19 | 1990-10-19 | Method for producing polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04234428A true JPH04234428A (en) | 1992-08-24 |
JPH0742349B2 JPH0742349B2 (en) | 1995-05-10 |
Family
ID=19304869
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3181569A Expired - Lifetime JPH0742349B2 (en) | 1990-10-19 | 1991-06-27 | Method for producing polyester |
Country Status (2)
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JP (1) | JPH0742349B2 (en) |
KR (1) | KR950006132B1 (en) |
Families Citing this family (1)
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KR101726511B1 (en) * | 2015-09-09 | 2017-04-12 | 롯데케미칼 주식회사 | Composite catalyst for polyester resin systhesis and method for manufacturing polyester resin using the same |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4998498A (en) * | 1973-01-09 | 1974-09-18 | ||
JPS504712A (en) * | 1972-02-24 | 1975-01-18 | ||
JPS5239791A (en) * | 1975-09-25 | 1977-03-28 | Teijin Ltd | Preparation of polyesters |
JPS52137490A (en) * | 1976-05-14 | 1977-11-16 | Teijin Ltd | Preparation of polyesters |
JPS52144092A (en) * | 1976-05-27 | 1977-12-01 | Teijin Ltd | Preparation of polyesters |
JPS5530532A (en) * | 1978-08-25 | 1980-03-04 | Saitama Kiki Kk | Torque rod bush |
JPS6021172A (en) * | 1983-07-15 | 1985-02-02 | Hitachi Ltd | Method for controlling cooling body of continuous casting device |
-
1990
- 1990-10-19 KR KR1019900016698A patent/KR950006132B1/en not_active IP Right Cessation
-
1991
- 1991-06-27 JP JP3181569A patent/JPH0742349B2/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS504712A (en) * | 1972-02-24 | 1975-01-18 | ||
JPS4998498A (en) * | 1973-01-09 | 1974-09-18 | ||
JPS5239791A (en) * | 1975-09-25 | 1977-03-28 | Teijin Ltd | Preparation of polyesters |
JPS52137490A (en) * | 1976-05-14 | 1977-11-16 | Teijin Ltd | Preparation of polyesters |
JPS52144092A (en) * | 1976-05-27 | 1977-12-01 | Teijin Ltd | Preparation of polyesters |
JPS5530532A (en) * | 1978-08-25 | 1980-03-04 | Saitama Kiki Kk | Torque rod bush |
JPS6021172A (en) * | 1983-07-15 | 1985-02-02 | Hitachi Ltd | Method for controlling cooling body of continuous casting device |
Also Published As
Publication number | Publication date |
---|---|
JPH0742349B2 (en) | 1995-05-10 |
KR950006132B1 (en) | 1995-06-09 |
KR920008107A (en) | 1992-05-27 |
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