JP2006188567A - Polycondensation catalyst for producing polyester and method for producing polyester using the same - Google Patents
Polycondensation catalyst for producing polyester and method for producing polyester using the same Download PDFInfo
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- JP2006188567A JP2006188567A JP2004383016A JP2004383016A JP2006188567A JP 2006188567 A JP2006188567 A JP 2006188567A JP 2004383016 A JP2004383016 A JP 2004383016A JP 2004383016 A JP2004383016 A JP 2004383016A JP 2006188567 A JP2006188567 A JP 2006188567A
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- Prior art keywords
- polyester
- polycondensation catalyst
- solid base
- polycondensation
- magnesium hydroxide
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- 229920000728 polyester Polymers 0.000 title claims abstract description 143
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 95
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 69
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 58
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 58
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 58
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 48
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 48
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000011247 coating layer Substances 0.000 claims description 33
- -1 titanium halide Chemical class 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052787 antimony Inorganic materials 0.000 abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 84
- 239000000203 mixture Substances 0.000 description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 18
- 239000002585 base Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000003513 alkali Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 150000003609 titanium compounds Chemical class 0.000 description 12
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 159000000003 magnesium salts Chemical class 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- AWWLNOYMFSDXPO-UHFFFAOYSA-L calcium;diacetate;dihydrate Chemical compound O.O.[Ca+2].CC([O-])=O.CC([O-])=O AWWLNOYMFSDXPO-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、ポリエステル製造用重縮合触媒とそのような重縮合触媒を用いるポリエステルの製造方法に関する。 The present invention relates to a polycondensation catalyst for producing polyester and a method for producing polyester using such a polycondensation catalyst.
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等に代表されるポリエステルは、機械的特性と化学的特性にすぐれており、それぞれの特性に応じて、例えば、衣料用や産業資材用の繊維、包装用や磁気テープ用等のフィルムやシート、中空成形品であるボトル、電気、電子部品のケーシング、その他の種々の成形品や部品等の広範な分野において用いられている。 Polyesters typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. have excellent mechanical and chemical properties. Depending on their properties, for example, textiles for clothing and industrial materials, and packaging It is used in a wide range of fields such as films and sheets for magnetic tapes, bottles that are hollow molded products, casings for electrical and electronic components, and other various molded products and components.
代表的なポリエステルである芳香族ジカルボン酸成分とアルキレングリコール成分を主たる構成成分とするポリエステル、例えば、ポリエチレンテレフタレートは、テレフタル酸とエチレングリコールとのエステル化反応や、テレフタル酸ジメチルとエチレングリコールとのエステル交換によってビス（２−ヒドロキシエチル）テレフタレート（ＢＨＥＴ）とこれを含むオリゴマーを製造し、これを重縮合触媒の存在下に真空中、高温下に溶融重縮合させることによって製造されている。 Polyesters mainly comprising an aromatic dicarboxylic acid component and an alkylene glycol component, which are typical polyesters, for example, polyethylene terephthalate is an esterification reaction between terephthalic acid and ethylene glycol, or an ester of dimethyl terephthalate and ethylene glycol. It is produced by producing bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer containing the same by exchange, and subjecting this to melt polycondensation in vacuum in the presence of a polycondensation catalyst at high temperature.
従来、このようなポリエステル製造用重縮合触媒としては、三酸化アンチモンが広く用いられている。三酸化アンチモンは、安価ですぐれた触媒活性をもつ触媒であるが、重縮合時に金属アンチモンが析出して、得られるポリエステルが黒ずんだり、また、得られるポリエステルに異物が混入するという問題があるほか（特許文献１参照）、本来、毒性を有するという問題があるので、近年においては、アンチモンを含まない触媒の開発が望まれている。 Conventionally, antimony trioxide has been widely used as such a polycondensation catalyst for producing polyester. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, there are problems that metal antimony precipitates during polycondensation, resulting in darkening of the resulting polyester, and contamination of the resulting polyester. (See Patent Document 1) Originally, there is a problem of toxicity, and in recent years, development of a catalyst containing no antimony has been desired.
そこで、例えば、すぐれた触媒活性を有し、すぐれた色調と熱安定性を有するポリエステルを与える触媒として、ゲルマニウム化合物からなる触媒が知られているが、この触媒は非常に高価であるのみならず、重合中に反応系から外へ留出しやすいので、反応系の触媒濃度が経時的に変化し、重合の制御が困難になるという問題を有している。 Therefore, for example, a catalyst made of a germanium compound is known as a catalyst that gives polyester having excellent catalytic activity and excellent color tone and thermal stability. However, this catalyst is not only very expensive. However, since it is easy to distill out of the reaction system during the polymerization, there is a problem that the catalyst concentration in the reaction system changes with time, making it difficult to control the polymerization.
他方、グリコールチタネートやチタンアルコキシド等のチタン化合物も、ジメチルテレフタレートとエチレングリコールとのエステル交換によるポリエステル製造用重縮合触媒として用いることができることが既に知られている（例えば、特許文献２及び３参照）。例えば、テトラアルコキシチタネートからなる重縮合触媒が知られているが（特許文献４参照）、得られるポリエステルが溶融成形時に熱劣化して、着色しやすいという問題がある。 On the other hand, it is already known that titanium compounds such as glycol titanate and titanium alkoxide can also be used as a polycondensation catalyst for polyester production by transesterification of dimethyl terephthalate and ethylene glycol (see, for example, Patent Documents 2 and 3). . For example, although a polycondensation catalyst made of tetraalkoxy titanate is known (see Patent Document 4), there is a problem that the resulting polyester is thermally deteriorated during melt molding and easily colored.
そこで、近年、チタン化合物を重縮合触媒として用いて、高品質のポリエステルを高生産性にて製造する方法が種々、提案されている。例えば、ハロゲン化チタンやチタンアルコキシドを加水分解してチタン水酸化物を得、これを３０〜３５０℃の温度で加熱して、脱水、乾燥し、かくして得られる固体状のチタン化合物を重縮合触媒として用いることが提案されている（例えば、特許文献５及び６参照）。 In recent years, various methods for producing high-quality polyester with high productivity using a titanium compound as a polycondensation catalyst have been proposed. For example, titanium halide or titanium alkoxide is hydrolyzed to obtain titanium hydroxide, which is heated at a temperature of 30 to 350 ° C., dehydrated and dried, and the solid titanium compound thus obtained is polycondensation catalyst. It is proposed to use as (for example, refer to Patent Documents 5 and 6).
しかし、上記チタン化合物を含め、これまで知られているチタン酸からなる重縮合触媒は、なかには、金属の単位重量当たりに高い重合活性を有するものもあるが、しかし、多くの場合、重合活性は高いが、得られるポリエステルは、依然として、溶融成形時に熱劣化して、着色しやすく、また、透明性に劣る傾向があった。
本発明者らは、従来のポリエステル製造用重縮合触媒における上述した問題を解決するために鋭意研究した結果、チタン酸からなる被覆層を固体塩基の粒子の表面に形成させ、これをポリエステル製造用重縮合触媒として用いることによって、ポリエステルの製造時、分解が抑制されて、金属の単位重量当たり、高い重合活性にて高分子量のポリエステルを与え、しかも、このポリエステルは、溶融成形時、熱劣化による着色が殆どないことを見出して、本発明に至ったものである。 As a result of diligent research to solve the above-described problems in conventional polycondensation catalysts for polyester production, the present inventors have formed a coating layer made of titanic acid on the surface of solid base particles, which is used for polyester production. By using it as a polycondensation catalyst, decomposition is suppressed during the production of the polyester, giving a high molecular weight polyester with a high polymerization activity per unit weight of metal, and this polyester is caused by thermal degradation during melt molding. It has been found that there is almost no coloring, and the present invention has been achieved.
従って、本発明は、アンチモンを含まないながら、すぐれた触媒活性を有し、すぐれた色調と透明性を有するポリエステルを与える新規なポリエステル製造用重縮合触媒と、そのような重縮合触媒を用いるポリエステルの製造方法を提供することを目的とする。 Accordingly, the present invention relates to a novel polycondensation catalyst for producing a polyester which does not contain antimony, has excellent catalytic activity, and has excellent color tone and transparency, and polyester using such a polycondensation catalyst. It aims at providing the manufacturing method of.
本発明によれば、ジカルボン酸又はそのエステル形成性誘導体とグリコールとのエステル化反応又はエステル交換反応によるポリエステル製造用触媒であって、固体塩基１００重量部に対して、ＴｉＯ２換算で０．１〜５０重量部のチタン酸からなる被覆層を表面に有する固体塩基の粒子からなる重縮合触媒が提供される。According to the present invention, there is provided a catalyst for producing a polyester by esterification reaction or transesterification reaction of a dicarboxylic acid or an ester-forming derivative thereof with a glycol, and is 0.1 in terms of TiO 2 with respect to 100 parts by weight of a solid base. There is provided a polycondensation catalyst comprising solid base particles having a coating layer comprising ˜50 parts by weight of titanic acid on the surface.
本発明によれば、上記固体塩基は、好ましくは、水酸化マグネシウム又はハイドロタルサイトである。 According to the invention, the solid base is preferably magnesium hydroxide or hydrotalcite.
更に、本発明によれば、ジカルボン酸又はそのエステル形成性誘導体とグリコールとを上記重縮合触媒の存在下でエステル化反応又はエステル交換反応させることを特徴とするポリエステルの製造方法が提供される。 Furthermore, according to the present invention, there is provided a method for producing a polyester, characterized in that a dicarboxylic acid or an ester-forming derivative thereof and glycol are subjected to esterification or transesterification in the presence of the polycondensation catalyst.
特に、本発明によれば、好ましい態様として、芳香族ジカルボン酸又はそのエステル形成性誘導体とアルキレングリコールとのエステル化反応又はエステル交換反応によって、上記芳香族ジカルボン酸ビス（ヒドロキシルアルキル）エステルを含むオリゴマーを製造し、次いで、上記重縮合触媒の存在下でこのオリゴマーを高真空下に高温で溶融重縮合させることを特徴とするポリエステルの製造方法が提供される。 In particular, according to the present invention, as a preferred embodiment, an oligomer containing the aromatic dicarboxylic acid bis (hydroxylalkyl) ester by an esterification reaction or transesterification reaction between an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alkylene glycol. And then a method for producing a polyester, characterized in that the oligomer is melt polycondensed at high temperature under high vacuum in the presence of the polycondensation catalyst.
ジカルボン酸又はそのエステル形成性誘導体とグリコールとのエステル化反応又はエステル交換反応によるポリエステル製造において、本発明によるポリエステル製造用重縮合触媒を用いることによって、ポリエステルの製造時、ポリエステルの黒ずみやポリエステル中への異物の混入なしに、また、ポリエステルの分解なしに、高い重合活性にて、すぐれた色調と透明性を有する高分子量ポリエステルを得ることができる。 In the polyester production by esterification reaction or transesterification reaction of dicarboxylic acid or its ester-forming derivative and glycol, by using the polycondensation catalyst for polyester production according to the present invention, the polyester is darkened or incorporated into the polyester during the production of the polyester. Thus, it is possible to obtain a high molecular weight polyester having excellent color tone and transparency with high polymerization activity without mixing of foreign substances and without decomposing the polyester.
本発明によるポリエステル製造用重縮合触媒は、ジカルボン酸又はそのエステル形成性誘導体とグリコールとのエステル化反応又はエステル交換反応によるポリエステル製造用触媒であって、固体塩基１００重量部に対して、ＴｉＯ２換算で０．１〜５０重量部のチタン酸からなる被覆層を表面に有する固体塩基の粒子からなるものである。The polycondensation catalyst for polyester production according to the present invention is a catalyst for polyester production by esterification reaction or transesterification reaction between a dicarboxylic acid or an ester-forming derivative thereof and glycol, and is based on TiO 2 with respect to 100 parts by weight of the solid base. It consists of solid base particles having a coating layer made of 0.1 to 50 parts by weight of titanic acid on the surface.
本発明において、固体塩基として、例えば、アルカリ金属やアルカリ土類金属の酸化物や水酸化物、種々の複合酸化物のほか、アルミニウム、亜鉛、ランタン、ジルコニウム、トリウム等の酸化物等や、これらの複合物を挙げることができる。これらの酸化物や複合物は、一部が炭酸塩等の塩類にて置換されていてもよい。従って、本発明において、固体塩基として、より具体的には、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、亜鉛等の酸化物や水酸化物、例えば、水酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化亜鉛等や、ハイドロタルサイト等の複合酸化物を例示することができる。なかでも、本発明によれば、水酸化マグネシウム又はハイドロタルサイトが好ましく用いられる。 In the present invention, as the solid base, for example, oxides or hydroxides of alkali metals or alkaline earth metals, various composite oxides, oxides of aluminum, zinc, lanthanum, zirconium, thorium, etc. Can be mentioned. These oxides and composites may be partially substituted with salts such as carbonates. Therefore, in the present invention, as the solid base, more specifically, oxides or hydroxides of magnesium, calcium, strontium, barium, aluminum, zinc, etc., for example, magnesium hydroxide, calcium oxide, strontium oxide, barium oxide Examples thereof include zinc oxide and complex oxides such as hydrotalcite. Among these, according to the present invention, magnesium hydroxide or hydrotalcite is preferably used.
本発明において、チタン酸とは、一般式
ＴｉＯ２・ｎＨ２Ｏ
（式中、ｎは０＜ｎ≦２を満たす数である。）
で表される含水酸化チタンであって、このようなチタン酸は、例えば、後述するように、ある種のチタン化合物をアルカリ加水分解することによって得ることができる。In the present invention, titanic acid has the general formula TiO 2 · nH 2 O
(In the formula, n is a number satisfying 0 <n ≦ 2.)
The hydrous titanium oxide represented by the formula, and such titanic acid can be obtained, for example, by alkaline hydrolysis of a certain kind of titanium compound as described later.
固体塩基１００重量部に対して、チタン酸からなる被覆層の割合がＴｉＯ２換算で０．１重量部よりも少ないときは、得られる重縮合触媒の重合活性が低く、高分子量のポリエステルを生産性よく得ることができず、他方、固体塩基１００重量部に対して、チタン酸からなる被覆層の割合がＴｉＯ２換算で５０重量部よりも多いときは、ポリエステルの製造に際して、ポリエステルの分解が起こりやすく、また、得られたポリエステルの溶融成形時に熱劣化による着色が生じやすい。When the ratio of the coating layer made of titanic acid is less than 0.1 parts by weight in terms of TiO 2 with respect to 100 parts by weight of the solid base, the polymerization activity of the resulting polycondensation catalyst is low, and high molecular weight polyester is produced. On the other hand, when the ratio of the coating layer made of titanic acid is more than 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of the solid base, the polyester is decomposed during the production of the polyester. It tends to occur, and coloration due to thermal degradation tends to occur during melt molding of the obtained polyester.
このような本発明による重縮合触媒は、固体塩基の粒子の水性スラリーを５〜１００℃、好ましくは、２５〜４０℃の温度に保持しつつ、これに固体塩基１００重量部に対してＴｉＯ２換算にて０．１〜５０重量部のチタン化合物を加え、得られた混合物にアルカリを加えて、上記スラリーをｐＨ５〜１２、好ましくは、７〜１０で加水分解して、固体塩基の粒子の表面にチタン酸からなる被覆層を形成し、このような被覆層を有する固体塩基の粒子を乾燥し、粉砕することによって得ることができる。上記乾燥温度は、好ましくは、６０〜１８０℃の範囲であり、特に好ましくは、１００〜１３０℃の範囲である。Such a polycondensation catalyst according to the present invention maintains an aqueous slurry of solid base particles at a temperature of 5 to 100 ° C., preferably 25 to 40 ° C., while maintaining TiO 2 with respect to 100 parts by weight of the solid base. 0.1 to 50 parts by weight of a titanium compound in terms of conversion is added, an alkali is added to the resulting mixture, and the slurry is hydrolyzed at pH 5 to 12, preferably 7 to 10 to obtain solid base particles. It can be obtained by forming a coating layer made of titanic acid on the surface, and drying and pulverizing solid base particles having such a coating layer. The drying temperature is preferably in the range of 60 to 180 ° C, and particularly preferably in the range of 100 to 130 ° C.
本発明による重縮合触媒の調製において、上記アルカリ加水分解によってチタン酸被覆を形成し得るチタン化合物としては、例えば、四塩化チタン等のようなチタンハロゲン化物、シュウ酸チタニルアンモニウム塩等のようなチタン酸塩、テトライソプロポキシド等のようなチタンアルコキシド等を挙げることができるが、しかし、これら例示に限定されるものではない。また、上記加水分解に用いる上記アルカリとしては、例えば、アンモニアや水酸化ナトリウムを例示することができるが、アルカリもまた、上記例示に限定されるものではない。 In the preparation of the polycondensation catalyst according to the present invention, examples of the titanium compound capable of forming a titanic acid coating by alkaline hydrolysis include titanium halides such as titanium tetrachloride and titanium such as titanyl ammonium oxalate. Examples thereof include titanium alkoxides such as acid salts and tetraisopropoxide, but are not limited to these examples. Examples of the alkali used for the hydrolysis include ammonia and sodium hydroxide, but the alkali is not limited to the above examples.
本発明によるポリエステルの製造方法は、ジカルボン酸又はそのエステル形成性誘導体とグリコールとを上記重縮合触媒の存在下にエステル化反応又はエステル交換反応させることからな。 本発明において、ジカルボン酸としては、琥珀酸、グルタル酸、アジピン酸、ドデカンジカルボン酸等によって例示される脂肪族ジカルボン酸やそのエステル形成性誘導体、例えば、ジアルキルエステルや、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等によって例示される芳香族ジカルボン酸やそのエステル形成性誘導体、例えば、ジアルキルエステルを挙げることができる。また、本発明において、グリコールとしては、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、１，４−シクロヘキサンジメタノール等を例示することができる。 The method for producing a polyester according to the present invention comprises an esterification reaction or a transesterification reaction of dicarboxylic acid or an ester-forming derivative thereof and glycol in the presence of the polycondensation catalyst. In the present invention, examples of the dicarboxylic acid include aliphatic dicarboxylic acids exemplified by oxalic acid, glutaric acid, adipic acid, dodecanedicarboxylic acid and the like, and ester-forming derivatives thereof such as dialkyl esters, terephthalic acid, isophthalic acid, naphthalene. Aromatic dicarboxylic acids exemplified by dicarboxylic acids and the like and ester-forming derivatives thereof, for example, dialkyl esters can be mentioned. In the present invention, examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,4-cyclohexanedimethanol and the like.
上述したなかでは、例えば、ジカルボン酸としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸が好ましく用いられ、また、グリコールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール等のアルキレングリコールが好ましく用いられる。 Among the above, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid are preferably used as the dicarboxylic acid, and alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol are used as the glycol. Is preferably used.
従って、本発明において、ポリエステルの好ましい具体例として、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリプロピレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリプロピレンナフタレート、ポリ（１，４−シクロヘキサンジメチレンテレフタレート）等を挙げることができる。 Accordingly, in the present invention, preferred specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate) and the like. be able to.
しかし、本発明において、用いることができるジカルボン酸又はそのエステル形成性誘導体や、グリコール又はそのエステル形成性誘導体は、上記例示に限定されるものではなく、また、得られるポリエステルも、上記例示に限定されるものではない。 However, the dicarboxylic acid or ester-forming derivative thereof, glycol or ester-forming derivative thereof that can be used in the present invention is not limited to the above examples, and the polyester obtained is also limited to the above examples. Is not to be done.
本発明による好ましい第１の重縮合触媒は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で０．１〜５０重量部のチタン酸からなる被覆層を表面に有する水酸化マグネシウム粒子からなる。A preferable first polycondensation catalyst according to the present invention comprises magnesium hydroxide particles having a coating layer made of 0.1 to 50 parts by weight of titanic acid in terms of TiO 2 on the surface with respect to 100 parts by weight of magnesium hydroxide. .
従って、本発明によれば、第１の重縮合触媒、即ち、表面にチタン酸からなる被覆層を有する水酸化マグネシウム粒子は、水酸化マグネシウム粒子の存在下に前記チタン化合物を５〜１００℃の範囲の温度、好ましくは、２５〜４０℃の範囲の温度で加水分解して、水酸化マグネシウムの表面にチタン酸を析出させることによって得ることができる。 Therefore, according to the present invention, the first polycondensation catalyst, that is, magnesium hydroxide particles having a coating layer made of titanic acid on the surface, is obtained by converting the titanium compound to 5-100 ° C. in the presence of magnesium hydroxide particles. It can be obtained by hydrolysis at a temperature in the range, preferably a temperature in the range of 25-40 ° C., to deposit titanic acid on the surface of the magnesium hydroxide.
詳しくは、本発明によれば、水酸化マグネシウムの水性スラリーを上記温度に保持しつつ、これに水酸化マグネシウム１００重量部に対してＴｉＯ２換算にて０．１〜５０重量部の前記チタン化合物を加え、得られた混合物にアルカリを加えて、上記スラリーをｐＨ５〜１２、好ましくは、７〜１０で加水分解して、水酸化マグネシウムの表面にチタン酸からなる被覆層を形成し、このような被覆層を有する水酸化マグネシウム粒子を６０〜１８０℃の温度で乾燥し、粉砕することによって、本発明による第１の重縮合触媒を得ることができる。Specifically, according to the present invention, while maintaining an aqueous slurry of magnesium hydroxide at the above temperature, 0.1 to 50 parts by weight of the titanium compound in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide. Then, an alkali is added to the resulting mixture, and the slurry is hydrolyzed at pH 5 to 12, preferably 7 to 10 to form a coating layer made of titanic acid on the surface of magnesium hydroxide. The first polycondensation catalyst according to the present invention can be obtained by drying and pulverizing magnesium hydroxide particles having an appropriate coating layer at a temperature of 60 to 180 ° C.
本発明による第１の重縮合触媒は、別の方法によっても得ることができる。例えば、水酸化マグネシウム粒子の水性スラリーを５〜１００℃、好ましくは、２５〜４０℃に保持しつつ、これに水酸化マグネシウム１００重量部に対してＴｉＯ２換算にて０．１〜５０重量部の前記チタン化合物とアルカリとをほぼ当量比にて加えて、必要に応じて、更にアルカリを加えて、ｐＨ５〜１２、好ましくは、７〜１０で加水分解して、同様に水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成し、６０〜１８０℃の温度で乾燥し、粉砕することによって得ることができる。The first polycondensation catalyst according to the present invention can also be obtained by another method. For example, while maintaining an aqueous slurry of magnesium hydroxide particles at 5 to 100 ° C., preferably 25 to 40 ° C., 0.1 to 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide. The titanium compound and the alkali are added at an approximately equivalent ratio, and if necessary, an alkali is further added and hydrolyzed at a pH of 5 to 12, preferably 7 to 10. A coating layer made of titanic acid is formed on the surface, dried at a temperature of 60 to 180 ° C., and pulverized.
本発明において、水酸化マグネシウムのスラリーとは、水溶性マグネシウム塩（例えば、塩化マグネシウムや硝酸マグネシウム等）の水溶性液を水酸化ナトリウムやアンモニア等のアルカリで中和し、水酸化マグネシウムを沈殿させて得られる水性スラリーや、水酸化マグネシウム粒子を水性媒体中に分散して得られるスラリーをいう。上記水溶性マグネシウム塩としては、例えば、塩化マグネシウムや硝酸マグネシウム等が好ましく用いられる。このような水溶性マグネシウム塩の水性溶液をアルカリで中和して、水酸化マグネシウムの水性スラリーを得る場合、水溶性マグネシウム塩の水溶液とアルカリとを同時中和してもよく、また、一方を他方に加えて中和してもよい。 In the present invention, the magnesium hydroxide slurry is a water-soluble magnesium salt (for example, magnesium chloride or magnesium nitrate) neutralized with an alkali such as sodium hydroxide or ammonia to precipitate magnesium hydroxide. Or an aqueous slurry obtained by dispersing magnesium hydroxide particles in an aqueous medium. As the water-soluble magnesium salt, for example, magnesium chloride or magnesium nitrate is preferably used. When neutralizing such an aqueous solution of a water-soluble magnesium salt with an alkali to obtain an aqueous slurry of magnesium hydroxide, the aqueous solution of the water-soluble magnesium salt and the alkali may be simultaneously neutralized. You may neutralize in addition to the other.
また、本発明において、水性スラリーとは、スラリーの分散媒が水又は少量の水溶性有機溶剤を含む水溶液をいい、水性溶液とは、同様に、溶液の溶媒が水又は少量の水溶性有機溶剤を含む水溶液をいい、水性媒体とは、水又は少量の水溶性有機溶剤を含む水溶液をいう。 In the present invention, the aqueous slurry means an aqueous solution in which the slurry dispersion medium contains water or a small amount of a water-soluble organic solvent. Similarly, the aqueous solution means that the solvent of the solution is water or a small amount of a water-soluble organic solvent. An aqueous medium refers to an aqueous solution containing water or a small amount of a water-soluble organic solvent.
また、上記水酸化マグネシウム粒子は、その由来は、何ら制約されるものではなく、例えば、天然鉱石を粉砕して得られた粉末、マグネシウム塩水溶液をアルカリで中和して得られた粉末等であってもよい。 Further, the origin of the magnesium hydroxide particles is not limited, and for example, powder obtained by pulverizing natural ore, powder obtained by neutralizing magnesium salt aqueous solution with alkali, etc. There may be.
次に、本発明による第２の重縮合触媒は、ハイドロタルサイト１００重量部に対して、ＴｉＯ２換算で０．１〜５０重量部のチタン酸からなる被覆層を表面に有するハイドロタルサイト粒子からなる。Next, the second polycondensation catalyst according to the present invention has hydrotalcite particles having a coating layer composed of 0.1 to 50 parts by weight of titanic acid in terms of TiO 2 on the surface with respect to 100 parts by weight of hydrotalcite. Consists of.
本発明において、ハイドロタルサイトは、好ましくは、下記一般式（Ｉ）
Ｍ２＋１−ｘＭ３＋ ｘ（ＯＨ−）２Ａｎ− ｘ／ｎ・ｍＨ２Ｏ … （Ｉ）
（式中、Ｍ２＋はＭｇ２＋、Ｚｎ２＋及びＣｕ２＋から選ばれる少なくとも１種の２価金属イオンを示し、Ｍ３＋はＡｌ３＋、Ｆｅ３＋及びＴｉ３＋から選ばれる少なくとも１種の３価金属イオンを示し、Ａｎ−はＳＯ４ ２−、Ｃｌ−、ＣＯ３ ２−及びＯＨ−から選ばれる少なくとも１種のアニオンを示し、ｎは上記アニオンの価数を示し、ｘは０＜ｘ＜０．５を満足する数であり、ｍは０≦ｍ＜２を満足する数である。）
で表される。In the present invention, the hydrotalcite is preferably the following general formula (I):
M 2 + 1-x M 3+ x (OH -) 2 A n- x / n · mH 2 O ... (I)
( Wherein M 2+ represents at least one divalent metal ion selected from Mg 2+ , Zn 2+ and Cu 2+ , and M 3+ represents at least one trivalent metal selected from Al 3+ , Fe 3+ and Ti 3+. It indicates ion, a n-is SO 4 2-, Cl -, CO 3 2- and OH - represents at least one anion selected from, n represents indicates the valence of the anion, x is 0 <x < 0.5 is a number that satisfies 0.5, and m is a number that satisfies 0 ≦ m <2.)
It is represented by
特に、本発明においては、Ｍ２＋がＭｇ２＋であり、Ｍ３＋がＡｌ３＋であり、Ａｎ−がＣＯ３ ２−であるハイドロタルサイト、即ち、一般式（ＩＩ）
Ｍｇ２＋ １−ｘＡｌ３＋ ｘ（ＯＨ−）２（ＣＯ３ ２−）ｘ／２・ｍＨ２Ｏ…（ＩＩ）
（式中、ｘ及びｍは前記と同じである。）
で表されるものが好ましく用いられる。このようなハイドロタルサイトは市販品として容易に入手することができるが、必要に応じて、適宜の原料を用いて、従来より知られている方法、例えば、水熱法によって製造することもできる。Particularly, in the present invention, M 2+ is the Mg 2+, M 3+ is the Al 3+, hydrotalcite A n- is CO 3 is 2, i.e., the general formula (II)
Mg 2+ 1-x Al 3+ x (OH − ) 2 (CO 3 2− ) x / 2 · mH 2 O (II)
(Wherein x and m are the same as above)
What is represented by these is used preferably. Such hydrotalcite can be easily obtained as a commercial product, but if necessary, it can also be produced by a conventionally known method, for example, a hydrothermal method, using appropriate raw materials. .
本発明によれば、第２の重縮合触媒、即ち、表面にチタン酸からなる被覆層を有するハイドロタルサイト粒子は、ハイドロタルサイトの存在下に５〜１００℃の範囲の温度、好ましくは、２５〜４０℃の範囲の温度で前述したチタン化合物を加水分解して、ハイドロタルサイトの表面にチタン酸を析出させることによって得ることができる。 According to the invention, the second polycondensation catalyst, i.e. hydrotalcite particles having a coating layer of titanic acid on the surface, is in the presence of hydrotalcite at a temperature in the range of 5 to 100 ° C., preferably It can be obtained by hydrolyzing the titanium compound described above at a temperature in the range of 25 to 40 ° C. and precipitating titanic acid on the surface of the hydrotalcite.
詳しくは、ハイドロタルサイトの水性スラリーを５〜１００℃、好ましくは、２５〜４０℃に保持しつつ、これにハイドロタルサイト１００重量部に対してＴｉＯ２換算にて０．１〜５０重量部の前記チタン化合物を加え、得られた混合物に前記アルカリを加えて、上記スラリーをｐＨ５〜１２、好ましくは、７〜１０で加水分解することによって、ハイドロタルサイトの表面にチタン酸からなる被覆層を形成し、６０〜１８０℃の温度で乾燥し、粉砕することに寄って，第２の重縮合触媒を得ることができる。Specifically, while maintaining the aqueous slurry of hydrotalcite at 5 to 100 ° C., preferably 25 to 40 ° C., 0.1 to 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite. A coating layer made of titanic acid on the surface of hydrotalcite by adding the alkali to the obtained mixture and hydrolyzing the slurry at pH 5-12, preferably 7-10. The second polycondensation catalyst can be obtained by forming and drying at a temperature of 60 to 180 ° C. and pulverizing.
本発明による第２の重縮合触媒は、別の方法によっても得ることができる。例えば、ハイドロタルサイトの水性スラリーを５〜１００℃、好ましくは、２５〜４０℃に保持しつつ、これにハイドロタルサイト１００重量部に対して、ＴｉＯ２換算にて０．１〜５０重量部の前記チタン化合物とアルカリとをほぼ当量比にて加えて、必要に応じて、更にアルカリを加えて、ｐＨ５〜１２、好ましくは、７〜１０で加水分解することによって、同様にハイドロタルサイトの表面にチタン酸からなる被覆層を形成し、６０〜１８０℃の温度で乾燥し、粉砕することによって得ることができる。The second polycondensation catalyst according to the present invention can also be obtained by another method. For example, an aqueous slurry of hydrotalcite is maintained at 5 to 100 ° C., preferably 25 to 40 ° C., and 0.1 to 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite. The above-mentioned titanium compound and alkali are added at an approximately equivalent ratio, and if necessary, further alkali is added and hydrolyzed at a pH of 5 to 12, preferably 7 to 10. A coating layer made of titanic acid is formed on the surface, dried at a temperature of 60 to 180 ° C., and pulverized.
本発明において、ハイドロタルサイトの水性スラリーとは、前述したハイドロタルサイトを前述した水性媒体中に分散して得られるスラリーをいう。 In the present invention, the hydrotalcite aqueous slurry refers to a slurry obtained by dispersing the hydrotalcite described above in the aqueous medium described above.
一般に、ポリエチレンテレフタレートにて代表されるポリエステルは、次のいずれかの方法によって製造されている。即ち、テレフタル酸に代表されるジカルボン酸とエチレングリコールに代表されるグリコールとの直接エステル化反応によって、前記ＢＨＥＴを含む低分子量のオリゴマーを得、更に、このオリゴマーを重縮合触媒の存在下に高真空、高温下に溶融重縮合させて、所要の分子量を有するポリエステルを得る方法か、又はジメチルテレフタレートに代表されるテレフタル酸ジアルキルエステルとエチレングリコールに代表されるグリコールとのエステル交換反応によって、同様に、前記ＢＨＥＴを含む低分子量のオリゴマーを得、更に、このオリゴマーを重縮合触媒の存在下に高真空、高温下に溶融重縮合させて、所要の分子量を有するポリエステルを得る方法である。 In general, a polyester represented by polyethylene terephthalate is produced by one of the following methods. That is, a low molecular weight oligomer containing BHET is obtained by a direct esterification reaction between a dicarboxylic acid typified by terephthalic acid and a glycol typified by ethylene glycol, and this oligomer is further increased in the presence of a polycondensation catalyst. Similarly, a method of obtaining a polyester having a required molecular weight by melt polycondensation under vacuum or high temperature, or a transesterification reaction between a dialkyl ester of terephthalic acid represented by dimethyl terephthalate and a glycol represented by ethylene glycol. In this method, a low molecular weight oligomer containing BHET is obtained, and this oligomer is melt polycondensed in the presence of a polycondensation catalyst in a high vacuum and at a high temperature to obtain a polyester having a required molecular weight.
本発明においても、上述した第１又は第２の重縮合触媒を用いる以外は、従来より知られているように、前述した直接エステル化反応又はエステル交換反応によって前記ＢＨＥＴを含む低分子量のオリゴマーを得、次いで、このオリゴマーを上記重縮合触媒の存在下に高真空、高温下に溶融重縮合させることによって、所要の分子量を有するポリエステルを得ることができる。 Also in the present invention, the low molecular weight oligomer containing BHET is obtained by the direct esterification reaction or transesterification reaction described above, as is conventionally known except that the first or second polycondensation catalyst described above is used. Then, the oligomer having the required molecular weight can be obtained by subjecting the oligomer to melt polycondensation in the presence of the polycondensation catalyst under high vacuum and high temperature.
ポリエチレンテレフタレートの製造を例にとって説明すれば、常法に従って、知られているように、ジメチルテレフタレートとエチレングリコールを触媒、例えば、酢酸カルシウムと共に反応槽に仕込み、常圧下に加熱し、エチレングリコールの還流温度で、メタノールを反応系外に留去しつつ、反応させることによって、ＢＨＥＴを含む低分子量のオリゴマーを得ることができる。オリゴマーの重合度は、通常、１０程度までである。必要に応じて、加圧下に反応を行ってもよい。留出したメタノールの量にて反応を追跡することができ、通常、エステル化率は９５％程度である。 The production of polyethylene terephthalate will be described as an example. According to a conventional method, as is known, dimethyl terephthalate and ethylene glycol are charged into a reaction vessel together with a catalyst, for example, calcium acetate, heated under normal pressure, and reflux of ethylene glycol. A low molecular weight oligomer containing BHET can be obtained by reacting while distilling methanol out of the reaction system at a temperature. The degree of polymerization of the oligomer is usually up to about 10. If necessary, the reaction may be performed under pressure. The reaction can be followed by the amount of methanol distilled, and the esterification rate is usually about 95%.
また、直接エステル化反応によるときは、テレフタル酸とエチレングリコールを反応槽に仕込み、生成する水を留去しながら、必要に応じて、加圧下に加熱すれば、同様に、ＢＨＥＴを含む低分子量のオリゴマーを得ることができる。このような直接エステル化反応によるときは、予め、製造したＢＨＥＴを含む低分子量のオリゴマーを原料と共に反応槽に加え、この低分子量のオリゴマーの共存下に直接エステル化反応を行うことが好ましい。 In the case of direct esterification reaction, terephthalic acid and ethylene glycol are charged into a reaction vessel, and if necessary, heated under pressure while distilling off generated water, similarly, low molecular weight containing BHET. Can be obtained. In the case of such direct esterification reaction, it is preferable to add the low molecular weight oligomer containing BHET produced together with the raw material to the reaction vessel in advance and perform the direct esterification reaction in the presence of the low molecular weight oligomer.
次いで、このようにして得られた低分子量のオリゴマーは、重合槽に移送し、ポリエチレンテレフタレートの融点（通常、２４０〜２８０℃である。）以上の温度に減圧下に加熱し、未反応のエチレングリコールと反応によって生成したエチレングリコールを反応系外に留去しつつ、同時に、溶融反応物の粘度をモニタリングしながら、上記オリゴマーを溶融重縮合させる。この重縮合反応は、必要に応じて、複数の反応槽を用いて、それぞれの反応槽において、反応温度と圧力を最適に変更させながら行ってもよい。反応混合物の粘度が所要値に達すれば、減圧を止め、例えば、窒素ガスにて重合槽内を常圧に戻して、得られたポリエステルを反応槽から、例えば、ストランド状に吐出させ、水冷し、切断して、ペレットとする。本発明によれば、このようにして、通常、固有粘度〔η〕が０．４〜１．０ｄＬ／ｇのポリエステルを得ることができる。 Next, the low molecular weight oligomer thus obtained is transferred to a polymerization tank and heated under a reduced pressure to a temperature equal to or higher than the melting point of polyethylene terephthalate (usually 240 to 280 ° C.). While the ethylene glycol produced by the reaction with glycol is distilled out of the reaction system, the oligomer is melt polycondensed while simultaneously monitoring the viscosity of the molten reactant. This polycondensation reaction may be performed using a plurality of reaction vessels as necessary, while optimally changing the reaction temperature and pressure in each reaction vessel. When the viscosity of the reaction mixture reaches the required value, the decompression is stopped, for example, the inside of the polymerization tank is returned to normal pressure with nitrogen gas, and the obtained polyester is discharged from the reaction tank, for example, in the form of a strand and cooled with water. Cut into pellets. According to the present invention, a polyester having an intrinsic viscosity [η] of 0.4 to 1.0 dL / g can be usually obtained in this manner.
本発明によるポリエステル製造用重縮合触媒は、前記ＢＨＥＴを含むオリゴマーの製造のための直接エステル化反応やエステル交換反応時に反応系に加えてもよく、また、低分子量のオリゴマーを得た後、これを更に重縮合させる際に反応系に加えてもよい。また、本発明による重縮合触媒は、そのまま、粉末状で反応系に加えてもよく、また、原料として用いるグリコールに分散させて、反応系に加えてもよい。しかし、本発明による重縮合触媒は、グリコール、特に、エチレングリコールに容易に分散させることができるので、好ましくは、前記ＢＨＥＴを含むオリゴマーの製造のための直接エステル化反応やエステル交換反応に際して、反応系に加えて用いられる。 The polycondensation catalyst for polyester production according to the present invention may be added to the reaction system during the direct esterification reaction or transesterification reaction for the production of the oligomer containing BHET, and after obtaining a low molecular weight oligomer, May be added to the reaction system when further polycondensation. In addition, the polycondensation catalyst according to the present invention may be added to the reaction system as it is in the form of a powder, or may be dispersed in glycol used as a raw material and added to the reaction system. However, since the polycondensation catalyst according to the present invention can be easily dispersed in glycol, particularly ethylene glycol, the reaction is preferably performed during direct esterification or transesterification for the production of the oligomer containing BHET. Used in addition to the system.
本発明による重縮合触媒は、用いるジカルボン酸又はそのエステル形成性誘導体１００モル部に対して、通常、１×１０−５〜１×１０−１モル部の範囲で用いられる。用いるジカルボン酸又はそのエステル形成性誘導体１００モル部に対して、本発明による重縮合触媒の割合が１×１０−５モル部よりも少ないときは、触媒活性が十分でなく、目的とする高分子量のポリエステルを得ることができないおそれがあり、他方、１×１０−１モル部よりも多いときは、得られるポリエステルが熱安定性に劣るおそれがある。The polycondensation catalyst according to the present invention is usually used in the range of 1 × 10 −5 to 1 × 10 −1 mol part with respect to 100 mol part of the dicarboxylic acid or ester-forming derivative thereof used. When the proportion of the polycondensation catalyst according to the present invention is less than 1 × 10 −5 mol parts relative to 100 mol parts of the dicarboxylic acid or ester-forming derivative thereof used, the catalytic activity is not sufficient and the intended high molecular weight On the other hand, when it is more than 1 × 10 −1 mol part, the obtained polyester may be inferior in thermal stability.
本発明による重縮合触媒はいずれも、溶融重合のみならず、固相重合や溶液重合においても、触媒活性を有しており、いずれの場合にも、ポリエステルの製造に用いることができる。 Any of the polycondensation catalysts according to the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization, and in any case, it can be used for production of polyester.
本発明による重縮合触媒は、成分として、アンチモンを含まないので、得られるポリエステルに黒ずみを与えたり、得られるポリエステル中に異物として混入することがなく、しかも、アンチモンを成分として含む触媒と同等又はそれ以上の触媒活性を有し、すぐれた色調と透明性を有するポリエステルを得ることができる。しかも、本発明による重縮合触媒は、毒性がなく、安全である。 Since the polycondensation catalyst according to the present invention does not contain antimony as a component, the resulting polyester is not darkened or mixed as a foreign substance in the obtained polyester, and is equivalent to a catalyst containing antimony as a component or A polyester having a catalytic activity higher than that and having excellent color and transparency can be obtained. Moreover, the polycondensation catalyst according to the present invention is non-toxic and safe.
ジカルボン酸又はそのエステル形成性誘導体とグリコールとのエステル化反応又はエステル交換反応によるポリエステルの製造において、チタン酸の酸触媒作用は、ジカルボン酸又はそのエステル形成性誘導体のカルボニル基にルイス酸として配位して、グリコールの上記カルボニル炭素への攻撃を容易にすると同時に、グリコールの解離をも促進して、その求核性を大きくすることであると推測される。しかし、この酸触媒作用が強すぎるときは、望ましくない副反応が起こって、ポリエステルの分解反応や着色を招くとみられる。ここに、本発明による重縮合触媒によれば、チタン酸からなる被覆層を固体塩基である水酸化マグネシウムやハイドロタルサイトの粒子の表面に形成することによって、チタン酸の酸触媒作用が適度になる結果、すぐれた色調と透明性を有する高分子量ポリエステルを与えるものとみられる。 In the production of polyester by esterification or transesterification of dicarboxylic acid or its ester-forming derivative and glycol, the acid catalysis of titanic acid is coordinated as a Lewis acid to the carbonyl group of dicarboxylic acid or its ester-forming derivative. Thus, it is presumed that the attack of the glycol on the carbonyl carbon is facilitated, and at the same time, the dissociation of the glycol is promoted to increase its nucleophilicity. However, when this acid catalysis is too strong, an undesirable side reaction may occur, leading to a polyester degradation reaction or coloring. Here, according to the polycondensation catalyst of the present invention, by forming a coating layer made of titanic acid on the surface of particles of magnesium hydroxide or hydrotalcite, which are solid bases, the acid catalytic action of titanic acid is moderately increased. As a result, it is considered to give a high molecular weight polyester having excellent color tone and transparency.
しかし、本発明によれば、ポリエステルの製造において、本発明による重縮合触媒を用いる利点を損なわない範囲において、従来より知られている重縮合触媒、例えば、アンチモン、ゲルマニウム、チタン、スズ、アルミニウム等の化合物からなる重縮合触媒を併用してもよい。更に、必要に応じてアルカリ金属化合物、熱安定性向上のため、リン酸化合物を併用してもよい。 However, according to the present invention, conventionally known polycondensation catalysts, such as antimony, germanium, titanium, tin, aluminum, etc., are used in the production of polyesters, as long as the advantages of using the polycondensation catalyst according to the present invention are not impaired. You may use together the polycondensation catalyst which consists of these compounds. Further, if necessary, an alkali metal compound and a phosphoric acid compound may be used in combination for improving thermal stability.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。以下の実施例及び比較例において、得られたポリエステルの固有粘度は、ＩＳＯ１６２８−１によって測定し、色調は、４５°拡散方式色差計（スガ試験機（株）製ＳＣ２−ＣＨ型）を用いて測定した。また、得られたポリエステルのヘイズ値は、ポリエステルを２８０℃で加熱溶融し、段付き角板を成形して、ＪＩＳ Ｋ−７１３６による５ｍｍ厚さの各板について測定したものである。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the intrinsic viscosity of the obtained polyester was measured by ISO1628-1, and the color tone was measured using a 45 ° diffusion type color difference meter (SC2-CH type manufactured by Suga Test Instruments Co., Ltd.). It was measured. Further, the haze value of the obtained polyester is measured for each plate having a thickness of 5 mm according to JIS K-7136 by melting the polyester at 280 ° C. to form a stepped square plate.
参考例１
（水酸化マグネシウムの水スラリーの調製）
水５Ｌを反応器に仕込み、これに４モル／Ｌの塩化マグネシウム水溶液１６．７Ｌと１４．３モル／Ｌの水酸化ナトリウム水溶液８．４Ｌとを撹拌下に同時に加えた後、１７０℃で０．５時間水熱反応を行った。このようにして得られた水酸化マグネシウムを濾過、水洗し、得られたケーキを水に再び懸濁させて、水酸化マグネシウムの水スラリー（１２３ｇ／Ｌ）を得た。Reference example 1
(Preparation of water slurry of magnesium hydroxide)
5 L of water was charged into the reactor, and 16.7 L of a 4 mol / L magnesium chloride aqueous solution and 8.4 L of a 14.3 mol / L sodium hydroxide aqueous solution were simultaneously added to the reactor while stirring. The hydrothermal reaction was performed for 5 hours. The magnesium hydroxide thus obtained was filtered and washed with water, and the resulting cake was resuspended in water to obtain an aqueous magnesium hydroxide slurry (123 g / L).
参考例２
（ハイドロタルサイトの水スラリーの調製）
３．８モル／Ｌ濃度の硫酸マグネシウム水溶液２．６Ｌと０．８５モル／Ｌ濃度の硫酸アルミニウム水溶液２．６Ｌとの混合溶液と９．３モル／Ｌ濃度の水酸化ナトリウム水溶液２．８Ｌと２．５４モル／Ｌ濃度の炭酸ナトリウム水溶液２．６Ｌとの混合溶液を攪拌下に同時に反応器に加えた後、１８０℃で２時間水熱反応を行った。反応終了後、得られたスラリーを濾過、洗浄した後、乾燥、粉砕して、Ｍｇ０．７Ａｌ０．３（ＯＨ）２（ＣＯ３）０．１５・０．４８Ｈ２Ｏなる組成を有するハイドロタルサイトを得た。このハイドロタルサイトを水に懸濁させて、ハイドロタルサイトの水スラリー（１００ｇ／Ｌ）を得た。Reference example 2
(Preparation of hydrotalcite water slurry)
A mixed solution of 2.6 L of a 3.8 mol / L aqueous magnesium sulfate solution and 2.6 L of a 0.85 mol / L aqueous aluminum sulfate solution, and 2.8 L of a 9.3 mol / L aqueous sodium hydroxide solution A mixed solution of 2.64 mol / L sodium carbonate aqueous solution with a concentration of 2.54 mol / L was simultaneously added to the reactor with stirring, and then hydrothermal reaction was performed at 180 ° C. for 2 hours. After completion of the reaction, the obtained slurry is filtered, washed, dried and pulverized to have a composition of Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 · 0.48H 2 O. Hydrotalcite was obtained. This hydrotalcite was suspended in water to obtain a hydrotalcite water slurry (100 g / L).
実施例１
（重縮合触媒Ａの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．２ｇ／Ｌ）０．０１６Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で９９．６ｇ／Ｌ）０．０１６Ｌを調製した。参考例１で得られた水酸化マグネシウムの水スラリー（１２３ｇ／Ｌ）９．０Ｌを２５Ｌ容量の反応器に仕込んだ後、この水酸化マグネシウムの水スラリーにそのｐＨが１０．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に０．０２時間かけて滴下した。滴下終了後、１時間熟成して、水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成した。このようにして得られた表面にチタン酸からなる被覆層を有する水酸化マグネシウム粒子の水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ａを得た。この重縮合触媒におけるチタン酸被覆の割合は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で、０．１重量部であった。Example 1
(Preparation of polycondensation catalyst A)
0.016 L of titanium tetrachloride aqueous solution (69.2 g / L in terms of TiO 2 ) and 0.016 L of aqueous sodium hydroxide solution (99.6 g / L in terms of NaOH) were prepared. After charging 9.0 L of the magnesium hydroxide aqueous slurry (123 g / L) obtained in Reference Example 1 into a 25 L reactor, the pH of the magnesium hydroxide aqueous slurry was adjusted to 10.0. The titanium tetrachloride aqueous solution and the sodium hydroxide aqueous solution were simultaneously added dropwise over 0.02 hours. After completion of the dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the magnesium hydroxide particles. A water slurry of magnesium hydroxide particles having a coating layer made of titanic acid on the surface thus obtained was filtered, washed with water, dried and pulverized to obtain a polycondensation catalyst A according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 0.1 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルａの製造）
側管を取付けたガラス製反応槽にテレフタル酸ジメチル１３．６ｇ（０．０７０モル）、エチレングリコール１０．０ｇ（０．１６モル）、酢酸カルシウム二水和物０．０２２ｇ及び重縮合触媒Ａ０．００１２ｇ（２．１×１０−５モル、テレフタル酸ジメチル１００モル部に対して０．０３モル部）を仕込み、この反応槽の一部を温度１９７℃の油浴に入れ、テレフタル酸ジメチルをエチレングリコールに溶解させた。反応槽の底部に届くように、キャピラリーを反応管内に挿入し、このキャピラリーを利用して、反応槽内に１時間窒素を吹き込んで、生成したメタノールの大部分を留出させながら、２時間加熱を続けて、ＢＨＥＴを含むオリゴマーを得た。(Production of polyester a)
In a glass reaction vessel equipped with a side tube, 13.6 g (0.070 mol) of dimethyl terephthalate, 10.0 g (0.16 mol) of ethylene glycol, 0.022 g of calcium acetate dihydrate and polycondensation catalyst A0. 0012 g (2.1 × 10 −5 mol, 0.03 mol part with respect to 100 mol parts of dimethyl terephthalate) was charged, and a part of this reaction vessel was placed in an oil bath at a temperature of 197 ° C. Dissolved in glycol. A capillary is inserted into the reaction tube so that it reaches the bottom of the reaction vessel. Using this capillary, nitrogen is blown into the reaction vessel for 1 hour, and most of the produced methanol is distilled for 2 hours. Then, an oligomer containing BHET was obtained.
次いで、２２２℃で１５分間加熱すると、エチレングリコールが留出して、重縮合が開始した。この後、２８３℃に昇温し、この温度に保持すると、エチレングリコールが更に留出し、重縮合が進行した。１０分後、減圧を開始し、１５分間かけて、２７Ｐａ以下まで圧力を低減した。その後、３時間で重縮合を終了した。重縮合反応の終了後、反応槽内を窒素ガスで常圧に戻し、得られたポリエステルを反応槽の底部の抜出し口からストランド状に吐出させ、冷却し、切断して、ポリエステルのペレットを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。 Subsequently, when heated at 222 ° C. for 15 minutes, ethylene glycol was distilled off and polycondensation started. Thereafter, when the temperature was raised to 283 ° C. and kept at this temperature, ethylene glycol further distilled and polycondensation proceeded. After 10 minutes, pressure reduction was started, and the pressure was reduced to 27 Pa or less over 15 minutes. Thereafter, polycondensation was completed in 3 hours. After completion of the polycondensation reaction, the inside of the reaction vessel is returned to normal pressure with nitrogen gas, and the obtained polyester is discharged in a strand form from the outlet at the bottom of the reaction vessel, cooled and cut to obtain polyester pellets. It was. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例２
（ポリエステルｂの製造）
テレフタル酸４３ｇ（０．２６モル）とエチレングリコール１９ｇ（０．３１モル）を反応槽に仕込み、窒素ガス雰囲気下に攪拌して、スラリーとした。この反応槽の温度を２５０℃、大気圧に対する相対圧力を１．２×１０５Ｐａに保ちながら、４時間かけてエステル化反応を行った。このようにして得られた低分子量オリゴマーのうち、５０ｇを窒素ガス雰囲気下、温度２５０℃、常圧に保持した重縮合反応槽に移した。Example 2
(Production of polyester b)
43 g (0.26 mol) of terephthalic acid and 19 g (0.31 mol) of ethylene glycol were charged into a reaction vessel and stirred in a nitrogen gas atmosphere to obtain a slurry. The esterification reaction was carried out over 4 hours while maintaining the temperature of this reaction vessel at 250 ° C. and the relative pressure to atmospheric pressure at 1.2 × 10 5 Pa. 50 g of the low molecular weight oligomer thus obtained was transferred to a polycondensation reaction tank maintained at a temperature of 250 ° C. and normal pressure in a nitrogen gas atmosphere.
重縮合触媒Ａ０．００２２ｇ（３．９×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０１５モル部）を予めエチレングリコールに分散させてスラリーとし、このスラリーを上記重縮合反応槽に加えた。この後、反応槽内を３時間かけて２５０℃から２８０℃まで昇温し、この温度を保持すると同時に、１時間かけて常圧から絶対圧力４０Ｐａに減圧して、この圧力を維持しながら、更に、２時間加熱を続けて、重縮合反応を行った。重縮合反応の終了後、反応槽内を窒素ガスで常圧に戻し、得られたポリエステルを反応槽の底部の抜出し口からストランド状に吐出させ、冷却し、切断して、ポリエステルのペレットを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。0.0022 g of polycondensation catalyst A (3.9 × 10 −5 mol, 0.015 mol part with respect to 100 mol parts of terephthalic acid component subjected to polycondensation) was previously dispersed in ethylene glycol to form a slurry. Added to the polycondensation reactor. Thereafter, the temperature in the reaction vessel was raised from 250 ° C. to 280 ° C. over 3 hours, and this temperature was maintained, and at the same time, the pressure was reduced from normal pressure to absolute pressure 40 Pa over 1 hour. Further, heating was continued for 2 hours to carry out a polycondensation reaction. After completion of the polycondensation reaction, the inside of the reaction vessel is returned to normal pressure with nitrogen gas, and the obtained polyester is discharged in a strand form from the outlet at the bottom of the reaction vessel, cooled and cut to obtain polyester pellets. It was. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例３
（重縮合触媒Ｂの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．２ｇ／Ｌ）０．１６Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で９９．６ｇ／Ｌ）０．１６Ｌを調製した。参考例１で得られた水酸化マグネシウムの水スラリー（１２３ｇ／Ｌ）９．０Ｌを２５Ｌ容量の反応器に仕込んだ後、この水酸化マグネシウムのスラリーにそのｐＨが１０．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に０．２時間かけて滴下した。滴下終了後、１時間熟成して、水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成した。このようにして得られた表面にチタン酸からなる被覆層を有する水酸化マグネシウムの水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｂを得た。この重縮合触媒におけるチタン酸被覆の割合は、水酸化マグネシウム１００重量部に対して、チタン酸換算で、１．０重量部であった。Example 3
(Preparation of polycondensation catalyst B)
0.16 L of titanium tetrachloride aqueous solution (69.2 g / L in terms of TiO 2 ) and 0.16 L of aqueous sodium hydroxide solution (99.6 g / L in terms of NaOH) were prepared. After charging 9.0 L of the magnesium hydroxide aqueous slurry (123 g / L) obtained in Reference Example 1 into a 25 L reactor, the pH of the magnesium hydroxide slurry was adjusted to 10.0. The titanium tetrachloride aqueous solution and the sodium hydroxide aqueous solution were added dropwise simultaneously over 0.2 hours. After completion of the dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the magnesium hydroxide particles. The aqueous slurry of magnesium hydroxide having a coating layer made of titanic acid on the surface thus obtained was filtered, washed with water, dried and then pulverized to obtain a polycondensation catalyst B according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 1.0 part by weight in terms of titanic acid with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルｃの製造）
上記重縮合触媒Ｂを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。(Production of polyester c)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst B was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例４
（ポリエステルｄの製造）
上記重縮合触媒Ｂを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。Example 4
(Production of polyester d)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst B was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例５
（重縮合触媒Ｃの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．２ｇ／Ｌ）１．６Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で９９．６ｇ／Ｌ）１．６Ｌを調製した。参考例１で得られた水酸化マグネシウムの水スラリー（１２３ｇ／Ｌ）９．０Ｌを２５Ｌの反応器に仕込んだ後、この水酸化マグネシウムのスラリーにそのｐＨが１０．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に２時間かけて滴下した。滴下終了後、１時間熟成して、水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成した。このようにして得られた表面にチタン酸からなる被覆層を有する水酸化マグネシウムの水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｃを得た。この重縮合触媒におけるチタン酸被覆の割合は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で、１０重量部であった。Example 5
(Preparation of polycondensation catalyst C)
1.6 L of titanium tetrachloride aqueous solution (69.2 g / L in terms of TiO 2 ) and 1.6 L of aqueous sodium hydroxide solution (99.6 g / L in terms of NaOH) were prepared. After charging 9.0 L of the magnesium hydroxide aqueous slurry (123 g / L) obtained in Reference Example 1 into a 25 L reactor, the magnesium hydroxide slurry was adjusted so that its pH was 10.0. An aqueous titanium tetrachloride solution and an aqueous sodium hydroxide solution were added dropwise simultaneously over 2 hours. After completion of the dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the magnesium hydroxide particles. The aqueous slurry of magnesium hydroxide having a coating layer made of titanic acid on the surface thus obtained was filtered, washed with water, dried and then pulverized to obtain a polycondensation catalyst C according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 10 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルｅの製造）
上記重縮合触媒Ｃを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。(Manufacture of polyester e)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst C was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例６
（ポリエステルｆの製造）
上記重縮合触媒Ｃを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。Example 6
(Production of polyester f)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst C was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例７
（重縮合触媒Ｄの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．２ｇ／Ｌ）３．２Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で９９．６ｇ／Ｌ）３．２Ｌを調製した。参考例１で得られた水酸化マグネシウムの水スラリー（１２３ｇ／Ｌ）９．０Ｌを２５Ｌ容量の反応器に仕込んだ後、この水酸化マグネシウムのスラリーにそのｐＨが１０．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に４時間かけて滴下した。滴下終了後、１時間熟成して、水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成した。このようにして得られた表面にチタン酸からなる被覆層を有する水酸化マグネシウムの水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｄを得た。この重縮合触媒におけるチタン酸被覆の割合は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で、２０重量部であった。Example 7
(Preparation of polycondensation catalyst D)
A titanium tetrachloride aqueous solution (69.2 g / L in terms of TiO 2 ) and 3.2 L of a sodium hydroxide aqueous solution (99.6 g / L in terms of NaOH) were prepared. After charging 9.0 L of the magnesium hydroxide aqueous slurry (123 g / L) obtained in Reference Example 1 into a 25 L reactor, the pH of the magnesium hydroxide slurry was adjusted to 10.0. The titanium tetrachloride aqueous solution and the sodium hydroxide aqueous solution were added dropwise simultaneously over 4 hours. After completion of the dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the magnesium hydroxide particles. The aqueous slurry of magnesium hydroxide having a coating layer made of titanic acid on the surface thus obtained was filtered, washed with water, dried and pulverized to obtain a polycondensation catalyst D according to the present invention. The ratio of the titanic acid coating in this polycondensation catalyst was 20 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルｇの製造）
上記重縮合触媒Ｄを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。(Manufacture of polyester g)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst D was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例８
（ポリエステルｈの製造）
上記重縮合触媒Ｄを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。Example 8
(Manufacture of polyester h)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst D was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例９
（重縮合触媒Ｅの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．２ｇ／Ｌ）８．０Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で９９．６ｇ／Ｌ）８．０Ｌを調製した。参考例１で得られた水酸化マグネシウムのスラリー（１２３ｇ／Ｌ）９．０Ｌを４０Ｌ容量の反応器に仕込んだ後、この水酸化マグネシウムのスラリーにそのｐＨが１０．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に１０時間かけて滴下した。滴下終了後、１時間熟成して、水酸化マグネシウム粒子の表面にチタン酸からなる被覆層を形成した。このようにして、表面にチタン酸からなる被覆層を有する水酸化マグネシウムの水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｅを得た。この重縮合触媒におけるチタン酸被覆の割合は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で、５０重量部であった。Example 9
(Preparation of polycondensation catalyst E)
8.0 L of titanium tetrachloride aqueous solution (69.2 g / L in terms of TiO 2 ) and 8.0 L of sodium hydroxide aqueous solution (99.6 g / L in terms of NaOH) were prepared. After charging 9.0 L of the magnesium hydroxide slurry (123 g / L) obtained in Reference Example 1 into a 40 L reactor, the magnesium hydroxide slurry was adjusted so that its pH was 10.0. A titanium tetrachloride aqueous solution and a sodium hydroxide aqueous solution were added dropwise simultaneously over 10 hours. After completion of the dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the magnesium hydroxide particles. Thus, a magnesium hydroxide aqueous slurry having a coating layer made of titanic acid on the surface was filtered, washed with water, dried and then pulverized to obtain a polycondensation catalyst E according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルｉの製造）
上記重縮合触媒Ｅを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。(Production of polyester i)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst E was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例１０
（ポリエステルｊの製造）
上記重縮合触媒Ｅを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。Example 10
(Manufacture of polyester j)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst E was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例１１
（重縮合触媒Ｆの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．４ｇ／Ｌ）０．０７Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で１００ｇ／Ｌ）０．０７Ｌを調製した。参考例２で得られたハイドロタルサイトの水スラリー（１００ｇ／Ｌ）５．０Ｌを２５Ｌ容量の反応器に仕込んだ後、このハイドロタルサイトのスラリーにそのｐＨが９．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に０．２時間かけて滴下した。滴下終了後、１時間熟成して、ハイドロタルサイト粒子の表面にチタン酸からなる被覆層を形成した。このようにして、表面にチタン酸からなる被覆層を有するハイドロタルサイト粒子の水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｆを得た。この重縮合触媒におけるチタン酸被覆の割合は、ハイドロタルサイト１００重量部に対して、ＴｉＯ２換算で、１．０重量部であった。Example 11
(Preparation of polycondensation catalyst F)
0.07 L of titanium tetrachloride aqueous solution (69.4 g / L in terms of TiO 2 ) and 0.07 L of aqueous sodium hydroxide solution (100 g / L in terms of NaOH) were prepared. After charging 5.0 L of the hydrotalcite water slurry (100 g / L) obtained in Reference Example 2 to a 25 L reactor, the pH of the hydrotalcite slurry is 9.0. The titanium tetrachloride aqueous solution and the sodium hydroxide aqueous solution were added dropwise simultaneously over 0.2 hours. After completion of dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the hydrotalcite particles. In this way, a water slurry of hydrotalcite particles having a coating layer made of titanic acid on the surface was filtered, washed with water, dried and then pulverized to obtain a polycondensation catalyst F according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 1.0 part by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite.
（ポリエステルｋの製造）
上記重縮合触媒Ｆを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。(Manufacture of polyester k)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst F was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例１２
（ポリエステルｌの製造）
上記重縮合触媒Ｆを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表１に示す。Example 12
(Manufacture of polyester l)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst F was used. The intrinsic viscosity, color tone and haze value of the polyester thus obtained are shown in Table 1.
実施例１３
（重縮合触媒Ｇの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．４ｇ／Ｌ）０．７２Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で１００ｇ／Ｌ）０．７２Ｌを調製した。参考例２で得られたハイドロタルサイトの水スラリー（１００ｇ／Ｌ）５．０Ｌを２５Ｌの反応器に仕込んだ後、このハイドロタルサイトのスラリーにそのｐＨが９．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に２時間かけて滴下した。滴下終了後、１時間熟成し、ハイドロタルサイト粒子の表面にチタン酸からなる被覆層を形成した。このような水スラリーからハイドロタルサイトを濾過し、水洗、乾燥した後、粉砕して本発明による重縮合触媒Ｇを得た。この重縮合触媒におけるチタン酸被覆の割合は、ハイドロタルサイト１００重量部に対して、ＴｉＯ２換算で、１０重量部であった。Example 13
(Preparation of polycondensation catalyst G)
0.72 L of titanium tetrachloride aqueous solution (69.4 g / L in terms of TiO 2 ) and 0.72 L of sodium hydroxide aqueous solution (100 g / L in terms of NaOH) were prepared. After charging 5.0 L of the hydrotalcite water slurry (100 g / L) obtained in Reference Example 2 into a 25 L reactor, the pH of the hydrotalcite slurry was adjusted to 9.0. An aqueous titanium tetrachloride solution and an aqueous sodium hydroxide solution were added dropwise simultaneously over 2 hours. After completion of dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the hydrotalcite particles. Hydrotalcite was filtered from such water slurry, washed with water, dried, and then pulverized to obtain a polycondensation catalyst G according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 10 parts by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite.
（ポリエステルｍの製造）
上記重縮合触媒Ｇを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。(Manufacture of polyester m)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst G was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
実施例１４
（ポリエステルｎの製造）
上記重縮合触媒Ｇを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Example 14
(Manufacture of polyester n)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst G was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
実施例１５
（重縮合触媒Ｈの調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．４ｇ／Ｌ）３．６Ｌと水酸化ナトリウム水溶液（ＮａＯＨ換算で１００ｇ／Ｌ）３．６Ｌを調製した。参考例２で得られたハイドロタルサイトの水スラリー（１００ｇ／Ｌ）５．０Ｌを２５Ｌの反応器に仕込んだ後、このハイドロタルサイトの水スラリーにそのｐＨが９．０になるように、上記四塩化チタン水溶液と水酸化ナトリウム水溶液とを同時に１０時間かけて滴下した。滴下終了後、１時間熟成して、ハイドロタルサイト粒子の表面にチタン酸からなる被覆層を形成した。このようにして得られた表面にチタン酸からなる被覆層を有するハイドロタルサイトの水スラリーを濾過し、水洗、乾燥した後、粉砕して、本発明による重縮合触媒Ｈを得た。この重縮合触媒におけるチタン酸被覆の割合は、ハイドロタルサイト１００重量部に対して、ＴｉＯ２換算で、５０重量部であった。Example 15
(Preparation of polycondensation catalyst H)
3.6 L of titanium tetrachloride aqueous solution (69.4 g / L in terms of TiO 2 ) and 3.6 L of sodium hydroxide aqueous solution (100 g / L in terms of NaOH) were prepared. After charging 5.0 L of the hydrotalcite water slurry (100 g / L) obtained in Reference Example 2 into a 25 L reactor, the pH of the hydrotalcite water slurry is 9.0. The titanium tetrachloride aqueous solution and the sodium hydroxide aqueous solution were added dropwise simultaneously over 10 hours. After completion of dropping, the mixture was aged for 1 hour to form a coating layer made of titanic acid on the surface of the hydrotalcite particles. The hydrotalcite water slurry having a coating layer made of titanic acid on the surface thus obtained was filtered, washed with water, dried and then pulverized to obtain a polycondensation catalyst H according to the present invention. The ratio of titanic acid coating in this polycondensation catalyst was 50 parts by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite.
（ポリエステルｏの製造）
上記重縮合触媒Ｈを用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。(Production of polyester o)
A polyester was obtained in the same manner as in Example 1 except that the polycondensation catalyst H was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
実施例１６
（ポリエステルｐの製造）
上記重縮合触媒Ｈを用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Example 16
(Manufacture of polyester p)
A polyester was obtained in the same manner as in Example 2 except that the polycondensation catalyst H was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例１
（ポリエステルｑの製造）
実施例１において、重縮合触媒Ａに代えて、三酸化アンチモン０．００６１ｇ（２．１×１０−５モル、テレフタル酸ジメチル１００モル部に対して０．０３モル部）を用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Comparative Example 1
(Production of polyester q)
In Example 1, instead of the polycondensation catalyst A, 0.0061 g of antimony trioxide (2.1 × 10 −5 mol, 0.03 mol part relative to 100 mol parts of dimethyl terephthalate) was used. In the same manner as in Example 1, a polyester was obtained. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例２
（ポリエステルｒの製造）
実施例２において、重縮合触媒Ａに代えて、三酸化アンチモン０．０１１４ｇ（３．９×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０１５モル部）を用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Comparative Example 2
(Manufacture of polyester r)
In Example 2, instead of polycondensation catalyst A, 0.0114 g of antimony trioxide (3.9 × 10 −5 mol, 0.015 mol part relative to 100 mol parts of terephthalic acid component subjected to polycondensation) was used. A polyester was obtained in the same manner as in Example 2 except that it was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例３
（チタン酸の調製）
四塩化チタン水溶液（ＴｉＯ２換算で６９．４ｇ／Ｌ）７．２Ｌを調製した。 上記四塩化チタン水溶液を２５Ｌ容量の反応器に仕込んだ後、この四塩化チタン水溶液に攪拌しながらそのｐＨが７．０になるように滴下した。滴下終了後、スラリーからチタン酸を濾過し、水洗した後、再濾過して、チタン酸のケーキ（ＴｉＯ２換算で３３重量％）を得た。Comparative Example 3
(Preparation of titanic acid)
7.2 L of titanium tetrachloride aqueous solution (69.4 g / L in terms of TiO 2 ) was prepared. The titanium tetrachloride aqueous solution was charged into a 25 L reactor, and the titanium tetrachloride aqueous solution was added dropwise with stirring to a pH of 7.0. After completion of the dropping, titanic acid was filtered from the slurry, washed with water, and then refiltered to obtain a titanic acid cake (33% by weight in terms of TiO 2 ).
（ポリエステルｓの製造）
実施例１において、重縮合触媒Ａに代えて、上記チタン酸のケーキ０．００５１ｇ（ＴｉＯ２として２．１×１０−５モル、テレフタル酸ジメチル１００モル部に対して０．０３モル部）を用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。(Manufacture of polyester s)
In Example 1, instead of the polycondensation catalyst A, 0.0051 g of the titanic acid cake (2.1 × 10 −5 mol as TiO 2 , 0.03 mol part relative to 100 mol parts of dimethyl terephthalate) A polyester was obtained in the same manner as in Example 1 except that it was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例４
（ポリエステルｔの製造）
実施例２において、重縮合触媒Ａに代えて、比較例３で得られたチタン酸のケーキ０．００９３ｇ（ＴｉＯ２として３．９×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０１５モル部）を用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Comparative Example 4
(Manufacture of polyester t)
In Example 2, instead of the polycondensation catalyst A, 0.0093 g of the titanic acid cake obtained in Comparative Example 3 (3.9 × 10 −5 mol as TiO 2 , 100 mol of the terephthalic acid component used for polycondensation) A polyester was obtained in the same manner as in Example 2 except that 0.015 mol part) was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例５
（チタン酸と水酸化マグネシウムの混合物の調製）
参考例１で得られた水酸化マグネシウムのスラリー（１２３ｇ／Ｌ）９．０Ｌを２５Ｌ容量の反応器に仕込んだ後、比較例３で得られたチタン酸のケーキ（ＴｉＯ２換算で３３重量％）３３５ｇを加えて、２時間撹拌し、撹拌終了後、１時間熟成した。このようなスラリーから混合物を濾過し、水洗、乾燥した後、粉砕して、チタン酸と水酸化マグネシウムの混合物を得た。この混合物におけるチタン酸の割合は、水酸化マグネシウム１００重量部に対して、ＴｉＯ２換算で１０重量部であった。Comparative Example 5
(Preparation of a mixture of titanic acid and magnesium hydroxide)
After charging 9.0 L of the magnesium hydroxide slurry (123 g / L) obtained in Reference Example 1 into a 25 L reactor, the titanic acid cake obtained in Comparative Example 3 (33 wt% in terms of TiO 2) ) 335 g was added and stirred for 2 hours, and after completion of stirring, aged for 1 hour. The mixture was filtered from such a slurry, washed with water, dried and then pulverized to obtain a mixture of titanic acid and magnesium hydroxide. The ratio of titanic acid in this mixture was 10 parts by weight in terms of TiO 2 with respect to 100 parts by weight of magnesium hydroxide.
（ポリエステルｕの製造）
実施例１において、重縮合触媒Ａに代えて、上記チタン酸と水酸化マグネシウムの混合物０．００１３ｇ（２．１×１０−５モル、テレフタル酸ジメチル１００モル部に対して０．０３モル部）を用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。(Manufacture of polyester u)
In Example 1, in place of the polycondensation catalyst A, 0.0013 g of the above mixture of titanic acid and magnesium hydroxide (2.1 × 10 −5 mol, 0.03 mol part relative to 100 mol parts of dimethyl terephthalate) A polyester was obtained in the same manner as in Example 1 except that was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例６
（ポリエステルｖの製造）
実施例２において、重縮合触媒Ａに代えて、比較例５で得られたチタン酸と水酸化マグネシウムの混合物 ０．００２４ｇ（３．９×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０１５モル部）を用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Comparative Example 6
(Production of polyester v)
In Example 2, instead of polycondensation catalyst A, a mixture of titanic acid and magnesium hydroxide obtained in Comparative Example 5 0.0024 g (3.9 × 10 −5 mol, terephthalic acid component 100 subjected to polycondensation 100 A polyester was obtained in the same manner as in Example 2 except that 0.015 mol part) was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例７
（チタン酸とハイドロタルサイトの混合物の調製）
参考例２で得られたハイドロタルサイトのスラリー（１００ｇ／Ｌ）１１．０Ｌを２５Ｌ容量の反応器に仕込んだ後、比較例３で得られたチタン酸のケーキ（ＴｉＯ２換算で３３重量％）３３４ｇを加えて、２時間撹拌し、撹拌終了後、１時間熟成した。このようなスラリーから混合物を濾過し、水洗、乾燥した後、粉砕して、チタン酸とハイドロタルサイトの混合物を得た。この混合物におけるチタン酸の割合は、ハイドロタルサイト１００重量部に対して、ＴｉＯ２換算で１０重量部であった。Comparative Example 7
(Preparation of a mixture of titanic acid and hydrotalcite)
After 11.0 L of the hydrotalcite slurry (100 g / L) obtained in Reference Example 2 was charged into a 25 L reactor, the titanic acid cake obtained in Comparative Example 3 (33 wt% in terms of TiO 2) 334 g was added and stirred for 2 hours. After completion of stirring, the mixture was aged for 1 hour. The mixture was filtered from such a slurry, washed with water, dried and then pulverized to obtain a mixture of titanic acid and hydrotalcite. The ratio of titanic acid in this mixture was 10 parts by weight in terms of TiO 2 with respect to 100 parts by weight of hydrotalcite.
（ポリエステルｗの製造）
実施例１において、重縮合触媒Ａに代えて、上記チタン酸とハイドロタルサイトの混合物 ０．０１２ｇ（２．１×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０３０モル部）を用いた以外は、実施例１と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。(Manufacture of polyester w)
In Example 1, instead of the polycondensation catalyst A, 0.012 g (2.1 × 10 −5 mol, mixture of titanic acid and hydrotalcite, 0 with respect to 100 mol parts of the terephthalic acid component subjected to polycondensation 0.030 mol part) was used in the same manner as in Example 1 to obtain a polyester. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
比較例８
（ポリエステルｘの製造）
実施例２において、重縮合触媒Ａに代えて、比較例７で得られたチタン酸とハイドロタルサイトの混合物０．０２２ｇ（３．９×１０−５モル、重縮合に供したテレフタル酸成分１００モル部に対して０．０１５モル部）を用いた以外は、実施例２と同様にして、ポリエステルを得た。このようにして得られたポリエステルの固有粘度、色調及びヘイズ値を表２に示す。Comparative Example 8
(Manufacture of polyester x)
In Example 2, instead of the polycondensation catalyst A, 0.022 g (3.9 × 10 −5 mol of a mixture of titanic acid and hydrotalcite obtained in Comparative Example 7 was used for polycondensation 100 A polyester was obtained in the same manner as in Example 2 except that 0.015 mol part) was used. Table 2 shows the intrinsic viscosity, color tone and haze value of the polyester thus obtained.
表１と表２に示す結果から明らかなように、本発明によれば、三酸化アンチモンを重縮合触媒として用いる場合とほぼ同等の固有粘度と色調とヘイズ値を有するポリエステルを得ることができる。これに対して、チタン酸を単独で重縮合触媒として用いるときは、固有粘度が低く、色相、ヘイズ値においても劣るポリエステルを得ることができるにすぎない。また、チタン酸を水酸化マグネシウムやハイドロタルサイトと混合して、重縮合触媒として用いても、同様に、得られるポリエステルは、固有粘度が低く、色相、ヘイズ値も満足できるものではない。 As is apparent from the results shown in Tables 1 and 2, according to the present invention, it is possible to obtain a polyester having an intrinsic viscosity, a color tone and a haze value almost equal to those when antimony trioxide is used as a polycondensation catalyst. On the other hand, when titanic acid is used alone as a polycondensation catalyst, it is only possible to obtain a polyester having a low intrinsic viscosity and inferior in hue and haze value. Further, even when titanic acid is mixed with magnesium hydroxide or hydrotalcite and used as a polycondensation catalyst, the resulting polyester has a low intrinsic viscosity and does not satisfy the hue and haze value.
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