CN101253215A - Method for producing polyester - Google Patents
Method for producing polyester Download PDFInfo
- Publication number
- CN101253215A CN101253215A CNA200680031678XA CN200680031678A CN101253215A CN 101253215 A CN101253215 A CN 101253215A CN A200680031678X A CNA200680031678X A CN A200680031678XA CN 200680031678 A CN200680031678 A CN 200680031678A CN 101253215 A CN101253215 A CN 101253215A
- Authority
- CN
- China
- Prior art keywords
- section
- polyester
- solid phase
- prepolymer
- phase polycondensation
- 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 428
- 238000004519 manufacturing process Methods 0.000 title claims description 190
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 508
- 239000007790 solid phase Substances 0.000 claims abstract description 309
- 239000002245 particle Substances 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims description 242
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 239
- 238000010438 heat treatment Methods 0.000 claims description 123
- 238000005886 esterification reaction Methods 0.000 claims description 114
- 238000007669 thermal treatment Methods 0.000 claims description 109
- 230000032050 esterification Effects 0.000 claims description 106
- 238000002425 crystallisation Methods 0.000 claims description 98
- 230000008025 crystallization Effects 0.000 claims description 98
- -1 polyethylene terephthalate Polymers 0.000 claims description 95
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 72
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 66
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 57
- 239000012071 phase Substances 0.000 claims description 47
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 39
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000155 melt Substances 0.000 claims description 27
- 230000006837 decompression Effects 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 19
- 230000000630 rising effect Effects 0.000 claims description 15
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 5
- 230000000699 topical effect Effects 0.000 claims description 5
- 150000003658 tungsten compounds Chemical class 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract 2
- 238000010924 continuous production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 172
- 239000000523 sample Substances 0.000 description 105
- 229910052757 nitrogen Inorganic materials 0.000 description 86
- 230000004927 fusion Effects 0.000 description 68
- 230000000052 comparative effect Effects 0.000 description 50
- 239000007789 gas Substances 0.000 description 45
- 230000000694 effects Effects 0.000 description 43
- 239000000243 solution Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 26
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 23
- 230000008859 change Effects 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 23
- 238000005809 transesterification reaction Methods 0.000 description 22
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 238000012546 transfer Methods 0.000 description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 239000000376 reactant Substances 0.000 description 18
- 230000033228 biological regulation Effects 0.000 description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- 238000012643 polycondensation polymerization Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 10
- 239000011654 magnesium acetate Substances 0.000 description 10
- 235000011285 magnesium acetate Nutrition 0.000 description 10
- 229940069446 magnesium acetate Drugs 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000004437 phosphorous atom Chemical group 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 9
- 229960004217 benzyl alcohol Drugs 0.000 description 9
- 235000019445 benzyl alcohol Nutrition 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000009849 deactivation Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 210000004899 c-terminal region Anatomy 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 229940095643 calcium hydroxide Drugs 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- 235000001055 magnesium Nutrition 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 229960001708 magnesium carbonate Drugs 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229940091250 magnesium supplement Drugs 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 229940093932 potassium hydroxide Drugs 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 229960004249 sodium acetate Drugs 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012611 container material Substances 0.000 description 3
- 230000000881 depressing effect Effects 0.000 description 3
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241001411320 Eriogonum inflatum Species 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003190 augmentative effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000002650 habitual effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-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
- KTFJPMPXSYUEIP-UHFFFAOYSA-N 3-benzoylphthalic acid Chemical compound OC(=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C(O)=O KTFJPMPXSYUEIP-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
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001149900 Fusconaia subrotunda Species 0.000 description 1
- PPTNAISLXZARAA-UHFFFAOYSA-N P(=O)(O)(O)O.C(C)C(CCCCC)SP(O)(O)=S Chemical compound P(=O)(O)(O)O.C(C)C(CCCCC)SP(O)(O)=S PPTNAISLXZARAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 230000000994 depressogenic effect Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
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- 239000006210 lotion Substances 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
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- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 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
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
A polyester having desired physical properties can be efficiently produced by producing polyester prepolymer particles having specific physical properties by a continuous process and performing the solid-phase polycondensation of the particles.
Description
Technical field
The present invention relates to a kind of manufacture method of polyester.It at length is the method that (1) relates to a kind of following manufacturing polyester, by making a kind of continuously in the melt phase polycondensation device of oversimplifying also is as the lower polyester prepolymer particle of the molecular weight ratio that is suitable for solid phase polycondensation of the intermediate in the polyester manufacturing, the polyester prepolymer particle that will obtain in this manufacture method carries out solid phase polycondensation, makes polyester.(2) relate to and a kind ofly low-molecular-weight polyester prepolymer is heat-treated under solid state and carry out the manufacture method of the polyester of solid phase polycondensation.
The invention still further relates to a kind of by low-molecular-weight polyethylene terephthalate is heat-treated the method for making the high-molecular weight polyethylene terephthalate under solid state.At length be that (1) relates to a kind of following method, by the solid phase polycondensation that carries out low-molecular-weight polyethylene terephthalate prepolymer being heat-treated, make the high-molecular weight polyethylene terephthalate at high speed on prescribed condition next stage property ground.At length be that (2) relate to a kind of following method, by interimly low-molecular-weight polyethylene terephthalate prepolymer being heat-treated under given conditions, carry out solid state polycondensation, with being shorter than the used time of usual method, make the high-molecular weight polyethylene terephthalate.
Background technology
The polyester of polyethylene terephthalate (the following PET that abbreviates as sometimes) representative is owing to mechanical properties, thermal properties, electrical property etc. are good, so be widely used on the molding of film, thin slice, bottle etc. of fiber and various uses, demand also enlarges.
Polyethylene terephthalate is also different according to the desired rerum natura of its purposes, the high-molecular weight polyester that uses as container material as bottle etc., usually form property derivative and glycol component through esterification and/or transesterification reaction by making as the dicarboxylic acid of dicarboxylic acid composition and/or its ester, generate low-molecular-weight oligomer, proceed melt polycondensation reaction, solid phase polycondensation, make.
Now, in the process for producing polyester that industrial circle is extensively implemented, the high-molecular weight polyester is by obtained the higher polyester prepolymer of molecular weight ratio by melt polycondensation reaction, make it carry out solid phase polycondensation, make, but in this case, in order to obtain the higher polyester prepolymer of molecular weight ratio, in the back segment of melt phase polycondensation, to use the horizontal reaction machine that possesses complicated agitating vane with plug flow.On the other hand, as the melt polycondensation reaction device, do not use reaction machine with such complex construction, and as the method for effectively making polyester, a kind of manufacture method of polyester is for example proposed in the patent documentation 1, obtain the lower polyester prepolymer of molecular weight ratio of the polymerization degree 5～35 by melt polycondensation reaction, make its crystallization under given conditions after, use for the solid phase polycondensation operation.Yet, the crystallization under the specified conditions in this method may not be applicable in the continuous life easily, and, on the long solid phase polycondensation time this point of needs, may not be can be satisfactory method.
In order to control the solid phase polycondensation speed in the polyester manufacturing, various trials are proposed again.For example, patent documentation 2 has been put down in writing the end carboxy concentration of solid phase polycondensation speed dependent in polycondensation catalyst amount and prepolymer, having put down in writing the feed rate ratio by changing terephthalic acid in the esterification and ethylene glycol or having added with respect to the initial stage inlet amount by the latter stage in reaction is the ethylene glycol of excess quantity, adjust the end carboxy concentration of prepolymer, further, by after the melt phase polycondensation operation becomes partial vacuum, adding catalyzer, adjust.Yet it is numerous and diverse that this method is applicable to that the successive manufacture method of polyester is accompanied by, and, aspect polycondensation speed, may not be can be satisfactory method.
When patent documentation 3 has been put down in writing low-molecular-weight polyethylene terephthalate carried out solid phase polycondensation, use the crystallization polyethylene terephthalate prepolymer of the ratio of C-terminal base unit weight and C-terminal base unit weight at specified range again.Yet the many conditions of this method regulation C-terminal base unit weight again, also are that the C-terminal base unit weight is at 165eq/10 in an embodiment
6More than the g (per 1 ton of polyester prepolymer is 165 equivalents), and do not put down in writing about the solid phase polycondensation in the little zone of the concentration of carboxyl endways as the application.
Again, for PET, according to the difference of its purposes, the molecular weight (intrinsic viscosity) that needs is also different, and for example, being defined as usually when being used for bottle is 0.70～0.95dL/g, is 0.95～1.20dL/g when being used for tyre cord.
Therefore, in order to have given play to necessary shaping processability, mechanical characteristics in the such use, molecular weight (intrinsic viscosity) need be brought up to the level of regulation, as this method, to carry out melt phase polycondensation and the PET prepolymer that obtains is proceeded solid phase polycondensation to the polyethylene terephthalate raw material, the method for carrying out high molecular is widely used industrial.Solid phase polycondensation is normally by under the inert atmosphere or under the decompression carrying out melt phase polycondensation resulting PET prepolymer to heat-treating, but need the long period owing to reach desirable molecular weight, therefore wish to have a kind of manufacture method outstanding aspect productivity.As this method, propose a kind ofly to obtain the lower PET prepolymer of the polymerization degree with melt phase polycondensation, at high temperature make this prepolymer carry out the method for solid phase polycondensation.
For example, patent documentation 4 discloses and has a kind ofly used mean polymerisation degree that melt phase polycondensation obtains to carry out crystallization from the about 5 lower molecular weight prepolymers to about 35 (intrinsic viscosity from about 0.10 to 0.36dL/g), make the appearance crystallite size more than 9nm, carry out the method for solid phase polycondensation then.Yet according to our research, in the method, the polymerization degree when beginning owing to solid phase polycondensation is low excessively, or because crystalline growth suppresses moving of molecule, therefore may not necessarily obtain the solid state polycondensation speed of satisfaction.
Again, patent documentation 5 has been put down in writing and has been made the particle of the PET prepolymer of intrinsic viscosity from 0.08 to 0.5dL/g carry out solid phase polycondensation than this glass transition temp under the high high temperature more than 140 ℃, but the median size of the prepolymer of this occasion is greatly more than 1mm, may not necessarily not obtain sufficient solid state polycondensation speed in the temperature range of fusion adhesion does not take place particle each other.Again, patent documentation 6 discloses a kind of polymeric solid phase polycondensation method of carrying out earlier before carrying out crystallization, promptly, lower molecular weight PET prepolymer particle is contacted with heat-conducting medium, use less than after the temperature that was warming up to about 205 ℃～240 ℃ scope in 10 minutes, in inert gas flow, carry out the method for solid phase polycondensation.Yet, in the method for the disclosure,, in the extremely short time, be warming up to the temperature of about 205 ℃～240 ℃ scope owing to give and thermal shocking, therefore particle fusion adhesion easily each other, in order to prevent this situation, need try every possible means special equipment is set, so that PET prepolymer particle does not contact each other, again, in the method, can not obtain shortening the solid state polycondensation effect of required time, may not be can gratifying method.
On the other hand, patent documentation 7 is disclosed to be relevant to making PET carry out the method that solid phase polycondensation improves molecular weight, in this solid phase polycondensation operation, use the heat treatment step of continuous moving-bed more than 2 sections, but this disclosed technology is when the PET prepolymer particle that makes intrinsic viscosity be roughly the moderate molecular weight of 0.5～0.65dL/g carries out solid phase polycondensation, heat up interimly, so that particle not fusion adhesion each other, condensation polymerization speed may not necessarily obtain improvement.Again, in order to obtain the prepolymer of this moderate molecular weight, this melt phase polycondensation equipment is than the equipment price height that obtains low-molecular-weight prepolymer, and therefore from comprehensive viewpoint, this may not be can gratifying method.
Patent documentation 1: the flat 10-512608 communique of Japanese Unexamined Patent Application Publication
Patent documentation 2: Japanese kokai publication sho 55-133421 communique
Patent documentation 3: TOHKEMY 2000-204145 communique
Patent documentation 4: No. 3626758 communique of Japanese Patent
Patent documentation 5: TOHKEMY 2004-67997 communique
Patent documentation 6: Japanese Unexamined Patent Application Publication 2004-537622 communique
Patent documentation 7: No. 5408035 communiques of United States Patent (USP)
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of method of making polyester, this method is the melt polycondensation reaction device of utilization structure complexity not, and it is make high molecular and the high-quality polyester that meets as the practicality of container material etc. with the relatively short solid phase polycondensation time, thereby cheap and make efficiently and obtain polyester.
The object of the present invention is to provide a kind of manufacture method of polyester, the manufacture method of this polyester is heat-treated low-molecular-weight polyester prepolymer particle, does not make its fusion adhesion and carries out solid phase polycondensation at high speed.
The object of the present invention is to provide a kind of manufacture method at industrial useful polyethylene terephthalate, this manufacture method is heat-treated low-molecular-weight polyethylene terephthalate prepolymer particle, particulate fusion adhesion not taking place and carry out solid phase polycondensation with big condensation polymerization speed, can make more high-molecular weight polyethylene terephthalate efficiently.
Solve the used means of problem
The inventor attentively inquires into research in view of above-mentioned problem, found that by have the polyester prepolymer particle of specific rerum natura with the successive processes manufacturing, make this particle carry out solid phase polycondensation, can make polyester efficiently, thereby reach first invention with desirable rerum natura.Just, the main points of first invention are as follows.
A kind of manufacture method of polyester; it is characterized in that; have: esterification step (a); in the presence of catalyst for esterification reaction; make with the terephthalic acid and be the dicarboxylic acid composition of main component and be that the glycol component of main component is carried out esterification with ethylene glycol; obtain oligopolymer, melt phase polycondensation operation (b) makes the oligopolymer that obtains carry out melt polycondensation reaction; obtain the polyester prepolymer; granulating operation (c), the polyester prepolymer granulating with obtaining obtains polyester prepolymer particle; heat treatment step (d); obtain polyester by making the polyester prepolymer particle that obtains carry out solid state polycondensation, described method satisfies following 1～3 prerequisite
1. each operation (a) and (b) and (c) be successive processes;
2. the polyester prepolymer particulate intrinsic viscosity that obtains in operation (c) is more than the 0.18dL/g, below the 0.40dL/g;
3. the polyester prepolymer particulate end carboxy concentration that in operation (c), obtains be per 1 ton of this particle have more than 1 equivalent, below 50 equivalents.
Again, we find to make solid state polycondensation speed at high temperature become big, thereby to reach second invention by at high temperature carrying out carrying out solid phase polycondensation than its solid phase polycondensation temperature in advance under the low temperature more than 15 ℃ before the solid phase polycondensation.
That is, the main points of second invention are as described below.
A kind of manufacture method of polyester, it is characterized in that, comprise thermal treatment, this thermal treatment is that intrinsic viscosity is heat-treated at solid state at the polyester prepolymer more than the 0.18dL/g, below the 0.40dL/g, the intrinsic viscosity of this polyester prepolymer is increased more than the 0.50dL/g, obtain polyester, described thermal treatment is divided into the n stage, and satisfy following conditions
1) temperature of j section (Tj) is more than 190 ℃, below 230 ℃, and the intrinsic viscosity rising value of j section is more than 0.03dL/g;
2) have the temperature (Tj (℃) of 1 group of described heat treated j section at least) and the temperature of k section (Tk (℃)) satisfy the j section of following (formula 1a) and the combination of k section;
(formula 1a) Tj+15≤Tk≤245
3) in the combination of described j section, k section, the difference of the intrinsic viscosity when intrinsic viscosity when the j section finishes and k section begin is below 0.10dL/g;
4) n is the integer more than 2, and j and k are the integers that satisfies 1≤j＜k≤n.
Again, another main points of second invention are as described below.
A kind of manufacture method of polyester, it is characterized in that, comprise thermal treatment, this thermal treatment is that intrinsic viscosity is heat-treated at solid state at the polyester prepolymer more than the 0.18dL/g, below the 0.40dL/g, the intrinsic viscosity of this polyester prepolymer is increased more than the 0.50dL/g, obtain polyester, described thermal treatment all contains in order: temperature T 1a (℃) under, make the 1st section of described polyester prepolymer crystallization; The polyester prepolymer that makes crystallization temperature T 2a (℃) under carry out the 2nd section of solid phase polycondensation; Make the 2nd section product that obtains be warming up to temperature T 3a (℃) the 3rd section; Make the 3rd section product that obtains temperature T 4a (℃) under carry out the 4th section of solid phase polycondensation; Make described the 2nd section intrinsic viscosity rising value more than 0.03dL/g, the difference of the intrinsic viscosity when described the 2nd section intrinsic viscosity when finishing begins with the 4th section is below 0.10dL/g, described T1a, T2a, T3a, T4a (℃) satisfy following (formula 4a)～(formula 7a)
(formula 4a) 100≤T1a≤200
(formula 5a) 190≤T2a≤230
(formula 6a) T4a≤T3a≤250
(formula 7a) T2a+15≤T4a≤245.
Again, temperature in the solid phase polycondensation operation and the relation between the condensation polymerization speed have been carried out detailed research, found that if carry out the solid phase polycondensation operation interimly, leading portion operation in this operation, promptly the 1st section solid phase polycondensation operation be than back segment operation, promptly implement under the low temperature more than 15 ℃ of the temperature of the 2nd section solid phase polycondensation operation, the solid state polycondensation speed of the then whole the 1st and the 2nd section solid phase polycondensation operation all becomes greatly, thereby reaches the 3rd invention.
Promptly, the main points of the 3rd invention: a kind of manufacture method of polyethylene terephthalate, it is characterized in that, pass through intrinsic viscosity in the thermal treatment of polyethylene terephthalate prepolymer under solid state more than the 0.18dL/g, below the 0.40dL/g, making intrinsic viscosity is the above polyethylene terephthalate of 0.70dL/g, thermal treatment comprises following 1 in order) the 1st section solid phase polycondensation operation and 2) the 2nd section solid phase polycondensation operation
1) the 1st section solid phase polycondensation operation: in temperature (T1b) is more than 200 ℃ below 225 ℃, under the inert gas atmosphere or under the decompression, mean residence time is more than 0.5 hour below 10 hours, the polyethylene terephthalate prepolymer is heat-treated, and the rising value that makes the intrinsic viscosity of this prepolymer is the above operation of 0.03dL/g;
2) the 2nd section solid phase polycondensation operation: in temperature (T2b) is more than 215 ℃ below 240 ℃, under the inert gas atmosphere or under the decompression, mean residence time is under the condition more than 2 hours, to the operation of heat-treating through the prepolymer of the 1st section solid phase polycondensation operation;
Wherein, said temperature T1b (℃) and T2b (℃) satisfy following (formula 1b),
T1b+15≤T2b (formula 1b).
Further, we have carried out detailed research to the condition of solid phase polycondensation, discovery by contain " the 1st section solid phase polycondensation operation " in order, " heating process " reaches " the 2nd section solid phase polycondensation operation ", with the intensification condition enactment of heating process in specific scope, then the speed of response of the 2nd section solid phase polycondensation operation becomes big, can make the high-molecular weight polyethylene terephthalate in the short time than common method, thereby reach the 4th invention.Promptly the main points of the 4th invention are as follows.
A kind of manufacture method of polyethylene terephthalate, it is characterized in that, making intrinsic viscosity is that the polyethylene terephthalate prepolymer that 0.18dL/g is above, 0.40dL/g is following is heat-treated under solid state, making intrinsic viscosity is more than the 0.70dL/g, thermal treatment under the solid state contains the 1st section solid phase polycondensation operation, heating process and the 2nd section solid phase polycondensation operation in order, and each operation satisfies following 1)～3)
1) the 1st section solid phase polycondensation operation: under inert gas atmosphere or under the decompression, the polyethylene terephthalate prepolymer is heat-treated, and its heat treated temperature (T1c) is more than 190 ℃, below 225 ℃.
2) heating process: under inert gas atmosphere or under the decompression, to heat up through the polyethylene terephthalate prepolymer of the 1st section solid phase polycondensation operation heat treated temperature (T1c) or the temperature below it since the 1st section solid phase polycondensation operation, be warming up to temperature (T2c), 30 minutes with interior from temperature T 1c (℃) be warming up to (T1c+15) ℃, and temperature T 1c (℃) and T2c (℃) satisfy following (formula 1c) and (formula 2c)
T1c+15≤T2c (formula 1c)
205℃≤T2c≤240℃。
3) the 2nd section solid phase polycondensation operation: under inert gas atmosphere or under the decompression, to heat-treating through the polyethylene terephthalate prepolymer of the 1st section solid phase polycondensation operation and heating process, and its heat treated temperature (T3c) is more than 190 ℃, below 240 ℃.
The effect of invention
Manufacture method according to first polyester of inventing, can be manufactured in the time at short solid phase polycondensation in the practicality of container material etc. of bottle etc. and have the high molecular of needed rerum natura, high-quality polyester, and melt polycondensation reaction device that can the utilization structure complexity.As a result, can be cheap and make polyester efficiently, therefore the method for first invention industrial be exceedingly useful method.According to the manufacture method of second polyester of inventing, a kind of low-molecular-weight polyester prepolymer particle fusion adhesion that do not make can be provided, carry out the manufacture method of the polyester of solid phase polycondensation at a high speed.The polyester that obtains by this method can be used for the extensive use of beverage with bottle and industrial fibre etc.
According to the manufacture method of the 3rd polyethylene terephthalate of inventing, a kind of low-molecular-weight PET prepolymer fusion adhesion that can not make can be provided, carry out the manufacture method of the PET of solid phase polycondensation with big condensation polymerization speed.By the PET molecular weight height that this method obtains, can be used for the widely purposes of beverage with bottle and industrial fibre etc.Because can utilize low-molecular-weight PET prepolymer,, be in the very big method of economic aspect benefit so also can reduce the machine utilization in the melt phase polycondensation operation again.
Manufacture method according to the 4th polyethylene terephthalate of inventing, can not make the low-molecular-weight PET prepolymer particle fusion adhesion that obtains by melt phase polycondensation, carry out solid phase polycondensation with big condensation polymerization speed, can make high-molecular weight PET efficiently.
Promptly, the manufacture method of the PET of the 4th invention is by under inert gas atmosphere or under the decompression PET prepolymer particle that obtains by melt phase polycondensation being heat-treated, promptly under solid state, carry out polycondensation (solid phase polycondensation), make all-purpose desirable high-molecular weight PET efficiently, at this moment, prerequisite is to use low-molecular-weight material to carry out solid phase polycondensation under prescribed condition as the PET prepolymer.Because by being controlled at the solid phase polycondensation of this prescribed condition, with such condition in the former method, promptly the occasion of carrying out solid phase polycondensation in a section under 190 ℃ to 240 ℃ is compared, can obtain big condensation polymerization speed in the high molecular zone, therefore, can shorten the solid phase polycondensation time, reduce boosting productivity and saving energy of the required heat of polycondensation etc.
Description of drawings
Fig. 1 is a mode chart of representing thermal treatment unit used in embodiment and the comparative example.
Fig. 2 is a mode chart of representing fusion adherence test device used in embodiment and the comparative example.
Nomenclature
1: the thermal treatment pipe
2: gas meter
3: nitrogen ingress pipe
4: the nitrogen preheating tube
5: oil bath
6: breaker plate
7: the sample layer
8: strainer
9: the gas sweetening mouth
10: arm
11: thermopair
12: thermometer
21: the thermal treatment pipe
22: gas meter
23: nitrogen ingress pipe
24: the nitrogen preheating tube
25: oil bath
26: breaker plate
27: the sample layer
28: strainer
29: the gas sweetening mouth
30: wire cloth
31: pillar
32: pin
33: pedestal
Embodiment
The manufacture method of the polyester of first invention (below; also claim " manufacture method of first invention "); the manufacture method of this polyester has: make with the terephthalic acid to be the dicarboxylic acid composition of main component and to be that the glycol component of main component is carried out the esterification step (a) that esterification obtains oligopolymer with ethylene glycol in the presence of catalyst for esterification reaction; make the oligopolymer that obtains carry out melt polycondensation reaction and obtain the melt phase polycondensation operation (b) of polyester prepolymer; the polyester prepolymer that obtains is carried out granulating and obtains polyester prepolymer particulate granulating operation (c); by making the polyester prepolymer particle that obtains carry out the heat treatment step (d) that solid state polycondensation obtains polyester, must be each operation (a) at least; (b); (c) be a kind of successive processes.
Here, so-called successive processes is the term relative with interrupter method, comprises the situation that situation that the process among each operation (a) and (b), (c) implements separately continuously and operation (a) and (b), (c) implement as a series of continuous processing.
Manufacture method according to first invention, because by operation (a) and (b), (c) are respectively successive processess at least, obtain at aspects such as intrinsic viscosity and end carboxy concentration stay-in-grade polyester prepolymer particle, the quality of the polyester that obtains so pass through operation (d) thus also can be stablized.In the manufacture method of first invention, it is desirable to further, operation (d) also is a successive processes.
Carry out without successive processes at operation (a) and (b), (c); and carry out esterification under the situation of carrying out with for example interrupter method; it is proceeded after the melt polycondensation reaction; with the polyester prepolymer spheroidizing that obtains thus; but because when this prepolymer particle changed into particle; along with granulating elapsed time intrinsic viscosity descends, end carboxy concentration increases, so be difficult to obtain the polyester prepolymer particle of quality homogeneous.
In the manufacture method of first invention, the polyester prepolymer particulate intrinsic viscosity that operation (c) obtains is more than the 0.18dL/g, below the 0.40dL/g.Lower value it is desirable to 0.19dL/g, and that better is 0.20dL/g, and higher limit it is desirable to 0.35dL/g, and that better is 0.32dL/g.If this prepolymer particulate intrinsic viscosity is less than lower value, then unsatisfactory as the required elongated this respect of time of the reaction in the heat treatment step (d) of the back operation of operation (c), on the other hand, the occasion that surpasses higher limit, then must use horizontal reacting machine to use equipment complicated and high price as needs such as the polycondensation machines in the melt phase polycondensation operation with plug flow, and undesirable.
Again, the polyester prepolymer particulate end carboxy concentration that operation (c) obtains is to be below 50 equivalents in this prepolymer particle per ton, it is desirable at 30 equivalents/below the ton, and better is at 20 equivalents/below the ton.End carboxy concentration is if surpass this value and too high, and then often solid phase polycondensation speed diminishes, and undesirable.Lower value is more little unreasonablely to be thought, but is actually 1 equivalent/ton usually.
In the manufacture method of first invention, be that the dicarboxylic acid composition of main component is meant that 85 moles of accounting for whole dicarboxylic acid compositions of using when making polyester are the dicarboxylic acid composition as the terephthalic acid composition more than the % with the terephthalic acid, it is desirable to account for 90 moles more than the %, better is to account for 95 moles more than the %.The content of terephthalic acid composition is less than above-mentioned scope, and is then when the polyester that will obtain makes molding, often bad as the thermotolerance of the molding of heat-resisting bottle etc.
Again, be that the glycol component of main component is meant that glycol component accounts for 85 moles of whole glycol component of using when making polyester more than the % with ethylene glycol, it is desirable to account for 90 moles more than the %, better is to account for 95 moles more than the %.
As the dicarboxylic acid composition except that terephthalic acid that can in manufacture method of the present invention, use, for example phthalic acid can be arranged for example, m-phthalic acid, two bromo m-phthalic acids, sulfoisophthalic acid sodium, phenylene dihydroxyl dicarboxylic acid, 4,4 '-diphenyldicarboxylic acid, 4,4 '-the phenyl ether dicarboxylic acid, 4,4 '-the benzophenone dicarboxylic acid, 4,4 '-the biphenoxyl ethane dicarboxylic acid, 4,4 '-phenylbenzene sulfo group dicarboxylic acid, 2, the aromatic dicarboxylic acid of 6-naphthalene dicarboxylic acids etc., hexahydroterephthalic acid, the ester ring type dicarboxylic acid of hexahydro-m-phthalic acid etc., and Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, the aliphatic dicarboxylic acid of dodecanedicarboxylic acid etc. etc. and these ester formation property derivative.
Again, as the glycol component except that ethylene glycol, except that Diethylene Glycol, for example propylene glycol, pentanediol, hexylene glycol, ethohexadiol, decanediol, neopentyl glycol, 2-ethyl-2-butyl-1 can be arranged for example, the aliphatic dihydroxy alcohol of ammediol, polyoxyethylene glycol, polytetramethylene ether diol (polytetramethylene ether glycol, Port リ テ ト ラ メ チ レ Application エ one テ Le グ リ コ one Le) etc.; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-hexanaphthene dimethyl alcohol, 1,4-hexanaphthene dimethyl alcohol, 2, the ester ring type dibasic alcohol and the xylyl alcohol, 4 of 5-norbornane dimethyl alcohol etc., 4 '-dihydroxybiphenyl, 2,2 '-two (4 '-hydroxy phenyl) propane, 2, the aromatic diol and 2 of 2-two (4 '-beta-hydroxy ethoxyl phenenyl) propane, two (4-hydroxy phenyl) sulfone, two (4-beta-hydroxy ethoxyl phenenyl) sulfonic acid etc., the ethylene oxide adduct of 2-two (4 '-hydroxy phenyl) propane or propylene oxide adduct etc.
Further, the purpose of the desirable rerum natura of the polyester that obtains according to adjustment, as required, also can be with functional group's number at the compound more than 3, for example, one or more of hydroxycarboxylic acid of the polyalcohols of the poly carboxylic acid of trimellitic acid, pyromellitic acid etc. and these acid anhydrides and Pehanorm, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, glycerol, hexanetriol etc. and oxysuccinic acid, citric acid etc. etc. are used as copolymer composition.
The manufacture method of first invention is except being undertaken by the aforesaid (a) and (b) of operation at least, (c) each personal successive processes, and by adjusting the reaction conditions in catalysts, temperature of reaction, reaction pressure and reaction times etc. in its process aptly, making polyester prepolymer particulate intrinsic viscosity that operation (c) obtains and end carboxy concentration is that other can carry out according to the manufacture method of known polyester outside the above-mentioned prescribed value.
Below, creating conditions in the manufacture method of first invention described.
In the manufacture method of first invention, usually dicarboxylic acid composition and glycol component are mixed the brewable material slip.The modulation of raw material slip, to be with the terephthalic acid dicarboxylic acid composition of main component and with ethylene glycol be the glycol component of main component and use as required be copolymerized into to grade and modulate, the mol ratio of glycol component and dicarboxylic acid composition is 1.0～2.0.This mol ratio it is desirable to 1.05～1.8, and better is 1.1～1.6.
Then, synthetic raw material slip is delivered to the esterification step with one or more esterification grooves continuously, under normal pressure～add is depressed, heated, makes it carry out esterification, make oligopolymer (esterification step (a)).
In the manufacture method of first invention, in esterification, use catalyst for esterification reaction, and by using catalyst for esterification reaction, not only can make speed of response become big, and the end carboxy concentration at the polyester prepolymer that obtains in melt phase polycondensation that generates oligopolymer is diminished, therefore desirable.
As catalyst for esterification reaction, do not limit especially, can from known catalyzer, select aptly, but, for example tungsten compound, titanium compound can be arranged for example as object lesson.As tungsten compound, for example para-tungstic acid, metatungstic acid, wolframic acid, silicotungstic acid, phospho-wolframic acid and their salt can be arranged for example, wherein it is desirable to ammonium metawolframate, ammonium paratungstate, sodium wolframate, wolframic acid, it is desirable to ammonium metawolframate, ammonium paratungstate especially.
As titanium compound; metatitanic acid four alcoxyl esters, acetic acid titanium, titanous oxalate, titanium chloride of metatitanic acid four n-propyls, titanium isopropylate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, metatitanic acid four tert-butyl esters, metatitanic acid ethanoyl-three isopropyl ester etc. etc. for example can be arranged for example; wherein; it is desirable to titanium isopropylate, tetra-n-butyl titanate, it is desirable to tetra-n-butyl titanate especially.
In the occasion of single esterification groove, the reaction conditions in the above-mentioned esterification normally temperature is approximately 204 ~ 290 ℃, and pressure is approximately 0 ~ 400kPaG (0 ~ 4kg/cm
2G), stirring the following reaction times (residence time) is approximately 1～10 hour.Again, in the occasion of a plurality of esterification grooves, the temperature of reaction in the 1st section the esterification groove is generally 240～270 ℃, it is desirable to 245～265 ℃, and pressure is generally 5～300kPaG (0.05～3kg/cm
2G), it is desirable to 10～200kPaG (0.1～2kg/cm
2G), the temperature of reaction in the final stage is generally 250～290 ℃, it is desirable to 255～280 ℃, and pressure is generally 0～150kPaG (0～1.5kg/cm
2G), it is desirable to 0～130kPaG (0～1.3kg/cm
2G).Here, kPaG is with respect to atmospheric relative pressure with the kPa unit representation.
In the manufacture method of first invention, as the esterification yield of the oligopolymer of esterification reaction product (in whole carboxyls of raw material dicarboxylic acid composition, react the components in proportions of carrying out esterification with glycol component) it is desirable to more than 90%, better is more than 94%.
The oligopolymer that will obtain with esterification step (a) continues be delivered to continuously the melt phase polycondensation operation with polycondensation groove, under reduced pressure, heating down, make it carry out melt polycondensation reaction (melt phase polycondensation operation (b)).Melt polycondensation reaction can carry out with 1 section or multistage by successive processes, uses 1 section or 2 sections usually, according to circumstances, and with 1 section prepolymer that can obtain having desirable rerum natura.
In the manufacture method of first invention; because the intrinsic viscosity of the polyester prepolymer that obtains with melt polycondensation reaction is adjusted to lower; make this prepolymer carry out particulate intrinsic viscosity after the granulating below 0.40dL/g; it is desirable to below 0.35dL/g; so in order to obtain the polymer prepolymer; widely used the 2nd section before may not needing with high viscosity with the horizontal plug flow type of agitating vane; the 3rd section polycondensation groove; the melt phase polycondensation operation also can be oversimplified; the cost of reduction equipment; also can in the single reactive tank of the complete mixed type that possesses agitating vane, carry out again.
Catalyzer as in the melt polycondensation reaction does not limit especially, can use known catalyzer.Specifically, for example, the germanium compound of germanium dioxide, four germanium oxides, hydroxide germanium, oxalic acid germanium, tetraethoxy germanium, four n-butoxy germanium etc. can be arranged for example; The antimony compounds of ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, antimony acetate, methoxyl group antimony etc.; The titanium compounds of metatitanic acid four n-propyls, titanium isopropylate, tetra-n-butyl titanate, titanous oxalate, titanium potassium oxalate(T.P.O.) etc. etc., these can be used singly or in combination.Wherein, titanium compound is owing to active high being suitable for of polycondensation used.The catalyzer usage quantity with respect to the resulting polyester prepolymer, is generally 1～400 quality ppm.
Also usefulness as stablizer, can be used the phosphorus compound of ortho-phosphoric acid, ortho-phosphoric acid alkyl ester, acid phosphate ester (ethyl acidphosphate), acid tricresyl phosphate glycol ester, phosphorous acid, alkyl phosphite etc.Its usage quantity with respect to the resulting polyester prepolymer, it is desirable to 1～1000 quality ppm, it is desirable to 2～200 quality ppm especially.
Further, also the basic metal of Lithium Acetate, sodium-acetate, Potassium ethanoate, magnesium acetate, magnesium hydroxide, alkoxide magnesium, magnesiumcarbonate, potassium hydroxide, calcium hydroxide, calcium acetate, lime carbonate etc., the compound of alkaline-earth metal can be used with above-mentioned polycondensation catalyst.Its usage quantity with respect to the resulting polyester prepolymer, is generally 1～100 quality ppm.
Reaction conditions in the melt polycondensation reaction that is undertaken by successive processes normally temperature is 260～290 ℃, it is desirable to 270～280 ℃, and pressure is 100～0.1kPaA, it is desirable to 50～0.1kPaA.Reaction times (residence time) depends on temperature and pressure; but as long as polyester prepolymer particulate intrinsic viscosity is adjusted in the afore mentioned rules scope; be typically about 0.5～3 hour, this polyester prepolymer particle is meant by carrying out the particle that spheroidizing obtains at the polyester prepolymer that the melt phase polycondensation operation obtains in granulating operation described later.Here, kPaA is with kPa unit representation absolute pressure.
For example with 2 sections occasions of carrying out, about reaction conditions, the 1st section temperature is 260～280 ℃ to melt polycondensation reaction with multistage, and pressure is 100～1kPaA, and the 2nd section temperature is 270～290 ℃, and pressure is 10～0.1kPaA, carries out under above-mentioned reaction conditions.In order to carry out polyreaction fully, the temperature that it is desirable to when the 2nd section reaction is last is carried out under the condition more than 270 ℃ at least.
To continue at the polyester prepolymer that melt phase polycondensation operation (b) obtains in granulating operation (c), to carry out granulating continuously, and become particle.The lower value of the polyester prepolymer particulate intrinsic viscosity after the granulating is 0.18dL/g, it is desirable to 0.19dL/g, and that better is 0.20dL/g, and higher limit is 0.40dL/g, it is desirable to 0.35dL/g, and that better is 0.32dL/g.
Again, polyester prepolymer particulate end carboxy concentration is that per 1 ton of this prepolymer particle has below 50 equivalents, it is desirable to 30 equivalents/below the ton, better is 20 equivalents/and below the ton.Lower value is more little unreasonablely to be thought, but is actually 1 equivalent/ton usually.
Above-mentioned prepolymer particulate intrinsic viscosity and end carboxy concentration are identical with the prepolymer that obtains in the melt phase polycondensation operation (b) in essence.
In the manufacture method of first invention, the miniaturation method in the granulating operation (c) can adopt topical application and strand cutting method aptly.So-called topical application is a kind of method as described below; be to make the polyester prepolymer of the molten state that obtains by melt polycondensation reaction from the injector head towards vertical lower is the strand form drippage gas after; utilize universal gravity constant to carry out granulating; simultaneously by and environmental gas between heat exchange make its curing, make particle.Usually with intrinsic viscosity be below the 0.25dL/g, when it is desirable to prepolymer below the 0.20dL/g and making particle, can adopt this method ideally.In topical application, especially can adopt the method (for example with reference to Japanese Unexamined Patent Application Publication 2003-531259 communique) of vibration polyester prepolymer ideally.By giving and shaking, owing to shortening the dropping distance that makes the strand granulating required, so can reduce the size of whole device.
In topical application, solidify required decline length (distance) in order to shorten, also can water-bath etc. be set at the drop point of prepolymer, the liquid of water etc. makes it cooling curing.When water-bath is set,, it is desirable to make the glassware for drinking water in the water-bath that flow velocity is arranged in order to prevent the fusion adhesion each other of solidified particle.The method that makes it to have flow velocity is not limited especially, but it is desirable to for example when the proportion as polyethylene terephthalate surpasses 1 polyester, its structure is to flow through water from the top of the water-bath of whole ロ one ト shape, from discharging the slip that constitutes by water and prepolymer particle near the center of bottom, or its structure is to flow through water from the top on scarp, reclaims the slip that is made of water and prepolymer particle in the bottom.Also can adopt the method that makes it cooling curing on the ribbon that rotates the metal manufacturing moving etc. that drops in again.By adopting such method, can obtain polyester prepolymer particle efficiently.
On the other hand, the strand cutting method is a method as described below, by toothed gear pump etc., the polyester prepolymer of the molten state that generates by melt polycondensation reaction is discharged gas phase from the punch die fishplate bar with a plurality of pores (nib) become strand form, then, with the water-cooled while or after, with the turning gear and the fixed teeth that have with the rotation axis of discharging direction approximate vertical direction it is cut off, thereby make particle with water cooling.Usually, when with intrinsic viscosity being more than the 0.18dL/g, it is desirable to prepolymer more than 0.20dL/g and make particle, can adopt this method ideally.
In the strand cutting method, the linear velocity that fused polyester prepolymer is the polyester of strand form ground when nib is discharged it is desirable at 0.1m/ more than second, 3m/ below second.Again, the strand form polyester that is directed in turning gear and the fixed teeth must be solidified into the degree that can cut off.Here, the so-called degree that can cut off that is cured to is to instigate the surface temperature of strand to be cooled to below the second-order transition temperature of this polyester, it is desirable to be cooled to than below the temperature of low 5 ℃ of second-order transition temperature and the solidified state.For example, when this polyester is polyethylene terephthalate, make the surface temperature of strand be cooled to get final product below 75 ℃, it is desirable to be cooled to get final product below 70 ℃.Therefore, the temperature of the water of use is usually in the scope more than 5 ℃, below 90 ℃, and thickness of temperature, fusing point, softening temperature, second-order transition temperature or strand during according to the fusion of polyester etc. is selected aptly.When especially polyester was polyethylene terephthalate, the lower limit of the temperature of water that better is was 10 ℃, and the upper limit is 65 ℃.
In the manufacture method of first invention, it is desirable to the particulate median size is 0.1～3.0mm.That the lower value of median size is better is 0.5mm, it is desirable to 0.65mm especially, and on the other hand, that higher limit is better is 2.0mm, and that better is 1.8mm, it is desirable to 1.6mm especially.If median size is less than 0.1mm, then fine powder becomes many during granulating, breaks down easily in the conveying of thereafter operation.If median size, is then made the required solid phase polycondensation time of high-molecular weight polyester with desirable intrinsic viscosity above 3.0mm and is often become very big, and undesirable.Here, the particulate median size is that the dry screen separating tests legal system of putting down in writing according to JISK0069 is made the cumulative distribution curve, is that 50% o'clock value is as median size with the accumulative total percentage.
In the manufacture method of first invention, do not make limit especially as the concrete grammar of heat treatment step (d), carry out according to known method.For example; can pass through as required; for example in 120～180 ℃ inert gas flow, made the polyester prepolymer particle flow that in granulating operation (c), obtains 0.5～12 hour; carry out after crystallization and the drying treatment; usually more than 180 ℃, below temperature, in the moving-bed that rare gas element is circulating, implement solid phase polycondensation continuously than low 5 ℃ of the fusing point of polyester.The solid phase polycondensation time gets final product according to the desirable intrinsic viscosity setting that generates polyester, is typically about 1～50 hour.The common lower limit of intrinsic viscosity behind the solid phase polycondensation it is desirable to 0.70dL/g, and that better is 0.72dL/g, and that better is 0.74dL/g, and the upper limit is generally 1.50dL/g, it is desirable to 1.45dL/g, and that better is 1.40dL/g.Intrinsic viscosity behind the solid phase polycondensation of the polyester that obtains of manufacture method by first invention is when this scope, and the physical strength and the melt-shaping of the molding that this polyester is shaped form are good, thereby further desirable.Above-mentioned heat treatment step (d) also can by second, third or the 4th the invention in thermal treatment carry out.
After the polyester that obtains of manufacture method by first invention can be shaped by injection molding forming and extrusion molding preplasticizing parison,, make the bottle that is used for drink pack etc., again, also can make bottle by direct blow molding by draw blow molding.
Again, can also do film forming, thin slice, be used for the various uses of wrapping material etc. by extrusion molding and stretch forming.Can also be shaped by extrusion stretching, make fiber.
The manufacture method of the polyester of second invention (below, be also referred to as " manufacture method of second invention "), it is characterized in that, under inert gas atmosphere or under the decompression, the polyester prepolymer that obtains by melt phase polycondensation is heat-treated under solid state, carry out polycondensation (solid phase polycondensation), when making the polyester that is suitable for being shaped efficiently, use low-molecular-weight material as prepolymer, compare the solid phase polycondensation under the low temperature, heat up afterwards more than 15 ℃, under than higher temperature, carry out solid phase polycondensation, up to the polyester of the molecular weight that obtains stipulating.By doing like this, compare with the situation of just carrying out solid phase polycondensation from beginning under than higher temperature, can in the high molecular zone, obtain big condensation polymerization speed.Its reason is also unclear, following deduction.Just, be inferred as: during owing to crystallization under lower molecular weight, because of forming crystalline texture the mobility of polyester molecule chain is reduced, the terminal group deactivation of a part, especially under lower molecular weight during crystallization, it is big that the absolute value of the terminal radix of deactivation becomes, so diminish at the latter half condensation polymerization speed of solid phase polycondensation.To this, by bestowing the temperature difference on the way is that such heat hot more than 15 ℃ is handled, though maintenance solid state, but owing to the crystalline fusion taking place and recrystallizing, form the non-crystalline areas that has many terminal group once more, so the part of the terminal group of deactivation obtains activity again, condensation polymerization speed is increased.
The manufacture method of second invention, it is characterized in that, it is a kind of method that comprises heat treated manufacturing polyester, this thermal treatment is that intrinsic viscosity is heat-treated under solid state at the polyester prepolymer more than the 0.18dL/g, below the 0.40dL/g, the intrinsic viscosity of this polyester prepolymer is increased more than the 0.50dL/g, obtain polyester, thermal treatment is divided into the n stage, and satisfies certain conditions.
In the manufacture method of second invention, so-called thermal treatment is meant and comprises drying process, heating process, crystallization step, solid phase polycondensation operation etc., surpassing under the temperature condition of normal temperature, handles the operation of the polyester prepolymer of solid state.
Also have, in the manufacture method of second invention, use intrinsic viscosity as the index of molecular weight.
Below, second invention is described in detail.
The used polyester prepolymer of manufacture method of second invention can for example use in the manufacturing of polyester prepolymer institute's customary way to make.Specifically, generally can use polycondensation catalyst to carry out melt phase polycondensation, make by making dicarboxylic acid and/or its ester formation property derivative and dibasic alcohol through esterification and/or transesterification reaction.In detail, for example, dicarboxylic acid and dibasic alcohol are thrown in the slip preparation vessel, mix and make the raw material slip, distillation is removed in the esterification groove by the water that reaction is produced under depressing, heating at normal pressure～add etc., and after esterification, resulting polyester lower molecular weight body (oligopolymer) as reactant of esterification is delivered to the polycondensation groove, under reduced pressure, heating down, use polycondensation catalyst to make its melt phase polycondensation, obtain polyester.
As the catalyzer that is used for above-mentioned esterification or transesterification reaction and be used for the catalyzer of polycondensation, do not limit especially, can select aptly to use from known catalyzer.Specifically, illustrative catalyzer in the manufacture method of above-mentioned first invention can be arranged for example.The usage quantity of above-mentioned catalyzer with respect to the resulting polyester prepolymer, is generally 1～400 quality ppm.In addition,,, consider its usage quantity, it is desirable to make it in this scope so be used in these whens reaction because titanium compound also has the effect as esterification and/or transesterification catalyst.
Also have,, can use the phosphorus compound of ortho-phosphoric acid, ortho-phosphoric acid alkyl ester, acid phosphate ester, acid tricresyl phosphate glycol ester, phosphorous acid, alkyl phosphite etc. as stablizer.。Its usage quantity with respect to the resulting polyester prepolymer, it is desirable to 1～1000 quality ppm, it is desirable to 2～200 quality ppm especially.
Further, also the basic metal of Lithium Acetate, sodium-acetate, Potassium ethanoate, magnesium acetate, magnesium hydroxide, alkoxide magnesium, magnesiumcarbonate, potassium hydroxide, calcium hydroxide, calcium acetate, lime carbonate etc., the compound of alkaline-earth metal can be used with above-mentioned polycondensation catalyst.Its usage quantity with respect to the resulting polyester prepolymer, is generally 1～100 quality ppm.
In addition, the dicarboxylic acid composition is that the ester of dicarboxylic acid forms the property derivative, when for example being the material of the fusing point with appropriateness of dimethyl terephthalate (DMT) etc., also can not make slip with dibasic alcohol, after the fusion for the transesterification reaction use of dibasic alcohol.
In addition, these are made by any one method in continous way, intermittent type, the semibatch, and again, esterification groove (or transesterification reaction groove), melt polycondensation reaction groove can be made one section respectively, also can make multistage.
In the manufacture method of second invention, as the polyester prepolymer that can be suitable for especially ideally, polyethylene terephthalate prepolymer and/or polybutylene terephthalate prepolymer can be arranged for example, these are terephthalic acid and/or dimethyl terephthalate (DMT) and the main component of dibasic alcohol is ethylene glycol and/or 1 by the main component of dicarboxylic acid normally, 4-butyleneglycol and make the polyester prepolymer that forms.
Here, the meaning of above-mentioned " main component " is that terephthalic acid accounts for 85 moles of whole dicarboxylic acid compositions more than the %, it is desirable to account for 90 moles more than the %, better is to account for 95 moles more than the %, ethylene glycol and/or 1, the 4-butyleneglycol accounts for 85 moles of whole glycol component more than the %, it is desirable to account for 90 moles more than the %, and better is to account for 95 moles more than the %.
As the dicarboxylic acid composition except that above-mentioned terephthalic acid, with used the same in the manufacture method of above-mentioned first invention.
As removing above-mentioned ethylene glycol, 1, the glycol component beyond the 4-butyleneglycol is with used the same in the manufacture method of above-mentioned first invention.
The above-mentioned polyester that is obtained by melt polycondensation reaction is supplied with to the die head that is connected on the melt polycondensation reaction groove by pipeline and/or toothed gear pump and/or strainer, discharged, be strand form or drip shape from a plurality of nibs of the front end that is arranged on mould.The polyester that is discharged from granulatings such as for example strand cutters, can be made the polyester prepolymer of the manufacture method that is used for second invention.
The median size that is used for the above-mentioned polyester prepolymer of second manufacture method of inventing it is desirable to usually more than the 0.5mm, below the 3.0mm, better is more than the 0.6mm, it is desirable to more than the 0.65mm especially, on the other hand, better is below the 2.0mm, further it is desirable to it is desirable to below the 1.6mm especially below the 1.8mm.If median size is less than 0.5mm, then fine powder becomes many during granulating, breaks down easily in the conveying of thereafter operation.If median size surpasses 3.0mm, though can not influence the effect of second invention, the solid phase polycondensation time that needs becomes very long.
Polyester prepolymer with median size of above-mentioned scope when for example carrying out granulating with the strand cutter, can obtain by the speed of pulling of mould wheel diameter or prepolymer output and strand is regulated.
Above-mentioned median size is the dry screen separating tests method of putting down in writing according to JISK0069, makes the cumulative distribution curve, is that 50% o'clock value is as median size with the accumulative total percentage.
The intrinsic viscosity that is used for the polyester prepolymer of second manufacture method of inventing is more than the 0.18dL/g, below the 0.40dL/g.Lower value it is desirable to more than the 0.20dL/g.On the other hand, higher limit it is desirable to it is desirable to below the 0.35dL/g especially below 0.38dL/g.Intrinsic viscosity is easy to generate fine powder during less than 0.18dL/g during granulating, again, though help to bring into play the effect of second invention, because the solid phase polycondensation time of needs becomes very long and undesirable.When intrinsic viscosity surpasses 0.40dL/g, then in the melt phase polycondensation operation, need weaken the effect of second invention in order to carry out the high price equipment that high viscosity liquid stirs, high vacuum is reacted.
Polyester prepolymer with intrinsic viscosity of above-mentioned scope can be by controlling and obtain polycondensation temperature, time, decompression degree.
The end carboxy concentration of polyester prepolymer that is used for the manufacture method of second invention it is desirable at 100 equivalents/below the ton.Better is 70 equivalents/below the ton further it is desirable to 40 equivalents/below the ton, it is desirable to 20 equivalents/below the ton especially.If surpass 100 equivalent/tons, then in operation solid phase polycondensation thereafter, polycondensation speed tends to diminish.
Again, above-mentioned end carboxyl concentration (AV) can be passed through sample dissolution to measure with the sodium hydroxide titration behind solvent.
In addition, above-mentioned end carboxyl concentration (AV) can be controlled according to temperature, pressure, the admixture of esterification operation and/or polycondensation operation or the method for adding catalyzer and ethylene glycol again.
According to the manufacture method of second invention,, carry out polycondensation up to the intrinsic viscosity that reaches regulation under solid state, heat-treating by the above-mentioned polyester prepolymer that obtains like this.The operation of the multistage (n section) that the thermal treatment of manufacture method of second invention is divided into intensification, crystallization, solid phase polycondensation, heat up etc. again.Thermal treatment in the manufacture method of second invention also can be carried out with interrupter method, but considers from the production efficiency aspect, it is desirable to carry out continuously.
Again, the manufacture method of second invention is a kind of method that comprises heat treated manufacturing polyester, and this thermal treatment is a kind of above-mentioned polyester prepolymer to be heat-treated under solid state, and intrinsic viscosity is increased more than the 0.50dL/g, thereby obtains the operation of polyester.The increasing amount that it is desirable to the intrinsic viscosity in above-mentioned thermal treatment is more than the 0.53dL/g, and better is more than the 0.55dL/g, it is desirable to more than the 0.58dL/g especially.On the other hand, the increasing amount of above-mentioned intrinsic viscosity is usually below 2.00dL/g.
The increasing amount of above-mentioned intrinsic viscosity is during less than 0.50gL/g, and the such effect of the improved solid state polycondensation speed of second invention is not got in touch with boosting productivity.
Above-mentioned heat treated solid phase polycondensation operation has the j section at least, these 2 sections of the k sections in j section downstream, have the temperature (Tj (℃) of 1 group of j section at least) and the temperature of k section (Tk (℃)) satisfy the j section of (formula 1a) Tj+15≤Tk≤245 and the combination of k section.And above-mentioned j and k are the integers that satisfies 1≤j＜k≤n, and n is the integer more than 2.
The temperature T j of above-mentioned j section is more than 190 ℃ below 230 ℃, and lower limit it is desirable to 200 ℃.On the other hand, the upper limit it is desirable to 220 ℃, better be 215 ℃.If above-mentioned lower limit is less than 190 ℃, then the solid phase polycondensation speed in the j section diminishes, becomes big as the load of the k section of back operation.If the above-mentioned upper limit surpasses 230 ℃, then the temperature T k of k section surpasses 245 ℃, the bad situation that causes that polyester granulate fusion adhesion each other takes place easily etc.And for example the above, the scope of Tk shows (formula 1a) Tj+15 ℃≤Tk≤245 ℃, but if Tk, then can not obtain the effect of the raising solid phase polycondensation speed of second invention less than Tj+15 ℃.
The rising of the intrinsic viscosity in the above-mentioned j section it is desirable to more than 0.05dL/g more than 0.03dL/g.If less than 0.03dL/g, then be not enough to obtain the effect of the raising solid phase polycondensation speed of k section.As long as it is minimum for the shortest and/or input heat that the upper limit of the ascensional range of the intrinsic viscosity in the j section is set whole heat treatment period for, usually greatly below 0.30dL/g, it is desirable to greatly below 0.25dL/g, better is greatly below 0.20dL/g.
Again, the difference of the intrinsic viscosity of the polyester the when intrinsic viscosity of the polyester when above-mentioned j section finishes and k section begin it is desirable to below 0.05dL/g below 0.10dL/g.When surpassing 0.10dL/g, the heat treatment time when the j section finishes during to the k section is elongated, and the effect of second invention that the result obtains by heating up at short notice from the j section to the k section does not obtain bringing into play, and undesirable.
Also have, above-mentioned j section and/or k section it is desirable to moving-bed, especially implement with the continous way moving-bed.
For from above-mentioned j section to the transition reposefully of k section, it is desirable between j section and k section, h section (heating process) is set.It is desirable to its temperature T ha (℃) satisfy (formula 3a) Tk≤Tha≤250 ℃.More than Tk, can make the polyester granulate of k section be difficult for taking place the fusion adhesion each other by Tha.Again, Tj, Tha, Tk are naturally below the fusing point of second polyester of inventing.As long as the difference of the intrinsic viscosity of the polyester the when intrinsic viscosity of the polyester the when residence time of h section is arranged to the j section is finished and k section begin is below the 0.10dL/g, usually in 90 minutes, it is desirable in 60 minutes, better is in 40 minutes.The residence time of above-mentioned heating process then shortens solid state polycondensation time effective according to the manufacture method of second invention when above-mentioned scope.The equipment that h section so long as can heat heats up polyester granulate just has no particular limits, and uses the fluidized-bed of rare gas element to carry out if adopt, and then particle fusion adhesion each other etc. is less, thereby desirable.
It is desirable to, in above-mentioned thermal treatment, before j section solid phase polycondensation operation, have the c section (crystallization step) of at least a portion crystallization of the polyester prepolymer that in fact makes noncrystalline state.At least a portion crystallization of the polyester prepolymer by making noncrystalline state, the polyester granulate fusion adhesion each other that can alleviate thereafter j section, k section etc.It is desirable to, the temperature T ca of above-mentioned c section (℃) satisfied 100≤Tca≤200 ℃.At Tca during less than 100 ℃, for making its crystallization, need long time to the polyester prepolymer particle degree of not fusion adhesion each other, reduced the effect of second invention.If Tca surpasses 200 ℃, then the polyester prepolymer particle of c section often is easy to generate the fusion adhesion each other.The c section uses the fluidized-bed of rare gas element to carry out so long as the equipment that can heat polyester prepolymer particle just has no particular limits if adopt, and then particle fusion adhesion each other etc. is less, thereby desirable.
Again, can before the c section, have the operation that is warming up to Tca, also can heat up and crystallization in the c section.Also can carry out polyester prepolymer particulate drying in the c section again.Polyester prepolymer particulate drying also can be carried out at the initial stage of solid phase polycondensation.
The heat treated better dividing method in the manufacture method of second invention and the example of temperature condition thereof are described.Just, it is desirable to above-mentioned thermal treatment and all contain according to following order: temperature T 1a (℃) under, in fact make the 1st section of at least a portion crystallization of the polyester prepolymer of noncrystalline state; Temperature T 2a (℃) under, make the polyester prepolymer of crystallization carry out the 2nd section of solid phase polycondensation; Make the 2nd section resulting product be warming up to temperature T 3a (℃) the 3rd section; Temperature T 4a (℃) under, make at the 3rd section resulting product and carry out the 4th section of solid phase polycondensation, intrinsic viscosity rising value in the 2nd section is more than 0.03dL/g, the difference of the intrinsic viscosity when the 2nd section intrinsic viscosity when finishing begins with the 4th section below 0.10dL/g, T1a, T2a, T3a, T4a (℃) satisfy following (formula 4a)～(formula 7a).
(formula 4a) 100≤T1a≤200
(formula 5a) 190≤T2a≤230
(formula 6a) T4a≤T3a≤250
(formula 7a) T2a+15≤T4a≤245
Can be used in the shaping raw material of fiber, film, bottle etc. suitably by the polyester that obtains of manufacture method of second invention.Especially, can be by injection molding forming and extrusion molding, preplasticizing parison is shaped after, by draw blow molding, make the bottle that is used for drink pack etc.Can also make bottle by direct blow molding.
Can also do film forming, thin slice by extrusion molding and stretch forming, be used for the various uses of wrapping material etc.Can also be shaped by extrusion stretching, make fiber.
The manufacture method of the PET of the 3rd invention (below, be also referred to as " manufacture method of the 3rd invention "), relate in a kind of and pass through under the inert gas atmosphere or under the decompression, the PET prepolymer particle that obtains by melt phase polycondensation is heat-treated, promptly under solid state, carry out polycondensation (solid phase polycondensation), make efficiently be suitable for being shaped, have the method for desirable high-molecular weight PET, at this moment, prerequisite is to use low-molecular-weight material as the PET prepolymer, under the afore mentioned rules condition, carry out solid phase polycondensation interimly.Because by being controlled in the method for this prescribed condition, with in the former method from the beginning at high temperature, promptly carry out the solid phase polycondensation occasion under the temperature of the 2nd section solid phase polycondensation operation of the manufacture method of the 3rd invention and compare, can in the high molecular zone, obtain big condensation polymerization speed, the raising of the productivity of the heat of therefore can shorten the solid phase polycondensation time, the reduction polycondensation is required etc.
Thermal treatment in the manufacture method of the 3rd invention is meant and comprises drying process, heating process, crystallization step, solid phase polycondensation operation etc., surpassing under the temperature condition of normal temperature, handles the operation of the PET prepolymer of solid state.In the 3rd invention, use intrinsic viscosity as the index of the molecular weight of PET again.
Below, the 3rd invention is described in detail.
To not special qualification of method of the used PET prepolymer of manufacture method that obtains the 3rd invention, usually so long as the manufacture method of habitual PET just.Specifically, usually, if the words that need, in the presence of esterification or transesterification catalyst, make that to form the property derivative be the dicarboxylic acid composition of main component and be that the glycol component of main component is carried out esterification and/or transesterification reaction with ethylene glycol with terephthalic acid and/or its ester, then, use polycondensation catalyst that its melt phase polycondensation is made.In detail, for example, raw material dicarboxylic acid composition and glycol component are thrown in the slip preparation vessel, mixed, make the raw material slip, distillation is removed and is passed through at normal pressure～the add water that reaction is produced under depressing, heating etc. in the esterification groove, and after esterification, resulting PET lower molecular weight body (oligopolymer) as reactant of esterification is delivered to the polycondensation groove, under reduced pressure, heating uses polycondensation catalyst to make its melt phase polycondensation down, obtains PET.
In the manufacture method of the 3rd invention, be that main component is meant and accounts for be used in whole dicarboxylic acid compositions of making PET 90 moles more than the % with the terephthalic acid, it is desirable to account for 95 moles of % above be that phthalic acid and/or its ester form the property derivative, again, with ethylene glycol is that main component is meant that ethylene glycol accounts for more than 90% of whole glycol component that is used in manufacturing PET, it is desirable to account for 95 moles more than the %.
Here, as the dicarboxylic acid composition except that above-mentioned terephthalic acid, with used the same in the manufacture method of above-mentioned first invention.
Again, as the glycol component except that above-mentioned ethylene glycol, with used the same in the manufacture method of above-mentioned first invention.
As the catalyzer that is used for above-mentioned esterification or transesterification reaction and be used for the catalyzer of polycondensation, do not limit especially, can select aptly to use from known catalyzer.Specifically, illustrative catalyzer in the manufacture method of above-mentioned first invention can be arranged for example.The usage quantity of above-mentioned catalyzer with respect to resulting PET prepolymer, is generally 1～400 quality ppm.In addition,,, consider its usage quantity, use in this scope so it is desirable to be used in these whens reaction because titanium compound also has the effect as esterification and/or transesterification catalyst.
Also have,, can use the phosphorus compound of ortho-phosphoric acid, ortho-phosphoric acid alkyl ester, acid phosphate ester, acid tricresyl phosphate glycol ester, phosphorous acid, alkyl phosphite etc. as stablizer.。Its usage quantity with respect to resulting PET prepolymer, it is desirable to 1～1000 quality ppm, it is desirable to 2～200 quality ppm especially.
Further, also the basic metal of Lithium Acetate, sodium-acetate, Potassium ethanoate, magnesium acetate, magnesium hydroxide, alkoxide magnesium, magnesiumcarbonate, potassium hydroxide, calcium hydroxide, calcium acetate, lime carbonate etc., the compound of alkaline-earth metal can be used with above-mentioned polycondensation catalyst.Its usage quantity with respect to resulting PET prepolymer, is generally 1～100 quality ppm.
Concrete the creating conditions of the used PET prepolymer of manufacture method of the 3rd invention can be made in order to method down etc.For example, use with terephthalic acid as the dicarboxylic acid of main component and/or its ester forms the property derivative and with the dibasic alcohol of ethylene glycol as main component, usually, the dicarboxylic acid composition: glycol component is 1: 1～1: 2 (mol ratio), the words that need are in the presence of esterifying catalyst, usually greatly about 240～280 ℃ temperature, usually depress about normal pressure to adding of 0.4MPa greatly, in the esterification groove, carry out about 1～10 hour esterification, perhaps in the presence of transesterification catalyst, carry out transesterification reaction, resulting resultant (PET lower molecular weight body) is delivered to the polycondensation groove, then, carries out melt phase polycondensation.Melt phase polycondensation is, uses polycondensation catalyst, is being approximately under 250～290 ℃ the temperature usually, reduce pressure gradually from normal pressure, final common under the decompression that is approximately 10～0.1kPa, under agitation, making it carry out melt phase polycondensation to intrinsic viscosity becomes 0.18dL/g～0.40L/g.
In addition, the dicarboxylic acid composition is that the ester of dicarboxylic acid forms the property derivative, when for example being the material of the fusing point with appropriateness of dimethyl terephthalate (DMT) etc., also can not make slip with dibasic alcohol, supplies with the transesterification reaction of dibasic alcohol after the fusion and uses.
In addition, above-mentioned reaction can be undertaken by any one method in continous way, intermittent type, the semibatch, and again, esterification groove (or transesterification reaction groove), melt polycondensation reaction groove can be made one section respectively, also can make multistage.
The PET prepolymer that will be obtained by melt polycondensation reaction is supplied with to the die head that is connected on the melt polycondensation reaction groove by pipeline and/or toothed gear pump and/or strainer, discharges from a plurality of nibs of the front end that is arranged on mould, is strand form or drips shape.The PET that will be discharged by strand form ground is with cut-outs such as for example strand cutter, granulating glomeration.
The particulate median size of the PET prepolymer that is obtained by melt polycondensation reaction that is used for the manufacture method of the 3rd invention is generally 0.5～3.0mm, be limited to 0.6mm under better being, it is desirable to 0.65mm especially, on the other hand, be limited to 2.0mm on better is, further it is desirable to 1.8mm, it is desirable to 1.6mm especially.If median size is less than 0.5mm, then fine powder becomes many during granulating, breaks down easily in the conveying of thereafter operation.Median size is left having or not of the 3rd invention effect aside for the moment if surpass 3.0mm, and it is elongated to reach the required solid state polycondensation time of desirable molecular weight.
Here, the particulate median size is the dry screen separating tests method of putting down in writing according to JISK0069, makes the cumulative distribution curve, and the accumulative total percentage is reached 50% o'clock value as median size.
The intrinsic viscosity that is used for the PET prepolymer of the 3rd manufacture method of inventing is 0.18～0.40dL/g.The lower value of intrinsic viscosity it is desirable to 0.20dL/g, and higher limit it is desirable to 0.38dL/g, it is desirable to 0.35dL/g especially.The intrinsic viscosity of this prepolymer is easy to generate fine powder during less than lower value during granulating, again, though help to bring into play the effect of the 3rd invention, become very long and undesirable because of reaching the required solid state polycondensation time of desirable high molecular.On the other hand, if surpass higher limit, even intrinsic viscosity is than higher prepolymer, can not obtain shortening the effect in the reaction times that obtains high-molecular weight PET, and, need carry out the equipment of the high price that high viscosity liquid stirs, high vacuum is reacted in the melt phase polycondensation operation, as whole manufacturing process, the effect of the 3rd invention is weakened.
The end carboxy concentration of PET prepolymer that is used for the manufacture method of the 3rd invention it is desirable at 100 equivalents/below the ton.Better is 70 equivalents/below the ton further it is desirable to 40 equivalents/below the ton, it is desirable to 20 equivalents/below the ton especially.If surpass 100 equivalent/tons, then in operation solid phase polycondensation thereafter, condensation polymerization speed tends to diminish.
Under solid state, heat-treat according to the manufacture method of the 3rd invention by the above-mentioned PET prepolymer particle that obtains like this, carry out solid phase polycondensation up to the intrinsic viscosity that reaches regulation.The thermal treatment of the 3rd invention mainly comprises interim solid phase polycondensation operation and heating process, and these operations also can be carried out with interrupter method, but considers from the production efficiency this respect, it is desirable to carry out continuously.The intrinsic viscosity of the PET that the manufacture method of the 3rd invention obtains is more than the 0.70dL/g.Manufacturing is during less than the PET of 0.70gL/g, then with former method relatively, do not give full play to the effect that can make solid state polycondensation speed become big such the 3rd invention, therefore undesirable.
The thermal treatment of the 3rd invention contains following the 1st section solid phase polycondensation operation and the 2nd section these two operations of solid phase polycondensation operation at least in order.
1) the 1st section solid phase polycondensation operation:
This operation is to be more than 200 ℃, below 225 ℃ in temperature (T1b), under the inert gas atmosphere or under the decompression, mean residence time is more than 0.5 hour, below 10 hours, the PET prepolymer is heat-treated, and the rising value that makes the intrinsic viscosity of this prepolymer is the above operation of 0.03dL/g;
2) the 2nd section solid phase polycondensation operation:
This operation is to be more than 215 ℃, below 240 ℃ in temperature (T2b), inert gas atmosphere down or decompression down, mean residence time is under the condition more than 2 hours, to the operation of heat-treating through the prepolymer of the 1st section solid phase polycondensation operation;
Wherein, said temperature T1b (℃) and T2b (℃) satisfy following (formula 1b).
T1b+15≤T2b (formula 1b)
These the 1st section and the 2nd section solid phase polycondensation operation are carried out under inert gas atmosphere or under the decompression, and here, " rare gas element " is meant oxygen concn below 0.1 volume %, ideal below 0.05 volume %, and in fact not with the gas of polyester (PET) reaction.As in fact not with the gas of pet reaction, specifically, can enumerate nitrogen, helium, neon, argon gas, xenon, carbonic acid gas etc., mainly, it is desirable to use nitrogen from the viewpoint of economy.Also have, " decompression down " is meant and is in the following pressure status of absolute pressure 2kPa.
The temperature (T1b) of the 1st section solid phase polycondensation operation is more than 200 ℃, below 225 ℃, and lower value it is desirable to 205 ℃.Higher limit it is desirable to 222 ℃, better be 220 ℃.If 200 ℃ of less thaies, then the solid state polycondensation speed in the 1st section operation diminishes, the load of the 2nd section operation thereafter becomes big.If surpass 225 ℃, then the temperature (T2b) of the 2nd section solid phase polycondensation operation surpasses 240 ℃ of higher limits, the bad situation that causes that the fusion adhesion each other of PET particle takes place easily etc.
Again, T1b and T2b must satisfy T1b+15 ℃≤T2b (formula 1b), if T2b, then can not obtain the effect of the raising solid state polycondensation speed of the 3rd invention sometimes less than T1b+15 ℃.
The mean residence time of the 1st section solid phase polycondensation operation is also according to its temperature, and more than 0.5 hour, below 10 hours, lower value it is desirable to 1.0 hours usually.Higher limit it is desirable to 9 hours, and better is 8 hours.If less than 0.5 hour, then the intrinsic viscosity rising value in the 1st section operation diminishes, the load of the 2nd section operation becomes big.If surpass 5 hours, then the solid state polycondensation speed of the latter half in the 1st section operation diminishes, not efficient.
The rising of the intrinsic viscosity in the 1st section solid phase polycondensation operation it is desirable to more than 0.05dL/g more than 0.03dL/g.If less than 0.03dL/g, then can not fully obtain the effect of the 2nd section raising solid state polycondensation speed in the operation.Satisfy whole heat treatment period for the shortest and/or to drop into heat be minimum as long as the upper limit of the ascensional range of the intrinsic viscosity in the 1st section operation is set for, be typically about 0.30dL/g.
The temperature (T2b) of the 2nd section solid phase polycondensation operation is more than 215 ℃, below 240 ℃, and lower value it is desirable to 220 ℃.Higher limit it is desirable to 237 ℃, better be 235 ℃.If less than 215 ℃, the polymerization degree that then arrives target needs for a long time and undesirable.If surpass 240 ℃, the bad situation that causes that then the fusion adhesion each other of PET particle takes place easily etc.
The mean residence time of the 2nd section solid phase polycondensation operation it is desirable to more than 4 hours more than 2 hours, usually below 36 hours.If less than 2 hours, then the intrinsic viscosity rising value in the 2nd section operation diminish, in order to obtain having the PET of the desirable polymerization degree, it is big that the load of the 1st section operation becomes.
Above-mentioned the 1st section solid phase polycondensation operation and the 2nd section solid phase polycondensation operation of the manufacture method of the 3rd invention it is desirable to carry out continuously, it is desirable to use the continous way moving-bed especially.
In the manufacture method of the 3rd invention, in order to prevent to it is desirable between the 1st section operation and the 2nd section operation, heating process is set from of the PE particle fusion adhesion each other of the 1st section solid phase polycondensation operation to the 2nd section solid phase polycondensation operation transit time.Temperature in the heating process (Thb) condition it is desirable to more than the T1b, below 250 ℃, and better is more than the T2b, below 250 ℃.By making Thb, the fusion adhesion each other of the 2nd section polymer beads in the solid phase polycondensation operation is become be difficult to take place in this scope.Again, we infer, compare when temperature being increased progressively handle, by temperature is changed in the 1st section and the 2nd section operation interimly, especially be under the temperature more than the T2b the heat treated PET particle in through the 1st section to be carried out the thermal treatment of short period of time at Thb therebetween, make rise some and crystalline texture of the intrinsic viscosity of PET that some variations take place, it is to the speed of response that makes the solid phase polycondensation in the 2nd section operation bigger desirable influence that has that becomes, again, to preventing that the 2nd section fusion adhesion in the solid phase polycondensation operation from being effective.
The residence time in the heating process it is desirable to below 25 minutes usually below 30 minutes, and better is below 20 minutes.The residence time of heating process is when this scope, owing to be used for the equipment Miniaturizable of heating process, thereby desirable.Be used for the equipment of heating process so long as can make the equipment of PET particle heat temperature raising, just have no particular limits, use the fluidized-bed of rare gas element desirable less because of particle fusion adhesion each other.
It is desirable to, before heat treated the 1st section solid phase polycondensation operation of the 3rd invention, the crystallization step of at least a portion crystallization of the PET prepolymer that in fact makes noncrystalline state is set.By making at least a portion crystallization of PET prepolymer, can alleviate the PET particle fusion adhesion each other of thereafter the 1st section, the 2nd section solid phase polycondensation operation etc.Crystallization is undertaken by the PET prepolymer is heat-treated, and the temperature (Tc) that it is desirable to its crystallization step is more than 140 ℃, below 200 ℃.Less than 140 ℃ the time, arrive this prepolymer particle degree of not fusion adhesion each other for making its crystallization, need long time, reduced the effect of the 3rd invention.If surpass 200 ℃, then the prepolymer particle often is easy to generate the fusion adhesion each other.The residence time it is desirable to below 60 minutes usually below 90 minutes.
In crystallization step, carry out the crystallization of PET prepolymer, it arrives the crystallization degree approximately is 30～60 weight % usually.Crystallization step is so long as the equipment that can heat the PET particle just has no particular limits, if undertaken by the fluidized-bed that uses rare gas element, then particle fusion adhesion each other less and desirable.The operation that is warming up to Tcb can be set before crystallization step, also can in crystallization step, heat up and crystallization.Also can in crystallization step, carry out the drying of prepolymer again.Again, the drying of prepolymer also can be carried out at the initial stage of the 1st section solid phase polycondensation operation.
Can be used in the shaping raw material of fiber, film, bottle etc. suitably by the PET that obtains of manufacture method of the 3rd invention.Especially, can be by injection molding forming and extrusion molding, preplasticizing parison is shaped after, by draw blow molding, make the bottle that is used for drink pack etc.Can also make bottle by direct blow molding.
Can also do film forming, thin slice by extrusion molding and stretch forming, be used for the various uses of wrapping material etc.Can also be shaped by extrusion stretching, make fiber.
Embodiment to the manufacture method of the PET of the 4th invention (following, be also referred to as " the 4th invention manufacture method ") is described in detail.
Thermal treatment in the 4th invention is meant and comprises drying process, heating process, crystallization step, solid phase polycondensation operation etc., surpassing under the temperature condition of normal temperature, handles the operation of the PET prepolymer of solid state.
In addition, in the 4th invention,, use intrinsic viscosity as the index of the molecular weight of PET.
Method to the PET prepolymer of the manufacture method that obtains being used for the 4th invention does not limit especially, for example, can make with the manufacture method of habitual PET.Specifically, usually, if the words that need, in the presence of esterification or transesterification catalyst, make that to form the property derivative be the dicarboxylic acid composition of main component and be that the glycol component of main component is carried out esterification and/or transesterification reaction with ethylene glycol with terephthalic acid and/or its ester, then, use polycondensation catalyst that its melt phase polycondensation is made.In detail, following method can be arranged for example, for example, raw material dicarboxylic acid composition and glycol component are thrown in the slip preparation vessel, mix, make the raw material slip, distillation is removed and is passed through at normal pressure～the add water that reaction is produced under depressing, heating etc. in the esterification groove, and after esterification, resulting PET lower molecular weight body (oligopolymer) as reactant of esterification is delivered to the polycondensation groove, and under reduced pressure, heating down, use polycondensation catalyst to make its melt phase polycondensation, obtain the PET prepolymer.
In the manufacture method of the 4th invention, be that main component is meant and accounts for be used in whole dicarboxylic acid compositions of making PET 90 moles more than the % with the terephthalic acid, it is desirable to account for 95 moles of % above be that terephthalic acid and/or its ester form the property derivative, again, with ethylene glycol is that main component is meant that ethylene glycol accounts for more than 90% of whole glycol component that is used in manufacturing PET, it is desirable to account for 95 moles more than the %.
Here, as the dicarboxylic acid composition except that above-mentioned terephthalic acid, with used the same in the manufacture method of above-mentioned first invention.
Again, as the glycol component except that above-mentioned ethylene glycol, with used the same in the manufacture method of above-mentioned first invention.
As the catalyzer that is used for above-mentioned esterification or transesterification reaction and be used for the catalyzer of polycondensation, do not limit especially, can select aptly to use from known catalyzer.Specifically, illustrative catalyzer in the manufacture method of above-mentioned first invention can be arranged for example.The usage quantity of above-mentioned catalyzer with respect to resulting PET prepolymer, is generally 1～400 quality ppm.In addition,,, consider its usage quantity, it is desirable to use in this scope so be used in these whens reaction because titanium compound also has the effect as esterification and/or transesterification catalyst.
Also have,, can use the phosphorus compound of ortho-phosphoric acid, ortho-phosphoric acid alkyl ester, etherophosphoric acid, tricresyl phosphate glycol ester, phosphorous acid, alkyl phosphite etc. as stablizer.。Its usage quantity with respect to resulting PET prepolymer, it is desirable to 1～1000 quality ppm, it is desirable to 2～200 quality ppm especially.
Further, also the basic metal of Lithium Acetate, sodium-acetate, Potassium ethanoate, magnesium acetate, magnesium hydroxide, alkoxide magnesium, magnesiumcarbonate, potassium hydroxide, calcium hydroxide, calcium acetate, lime carbonate etc., the compound of alkaline-earth metal can be used with above-mentioned polycondensation catalyst.Its usage quantity with respect to resulting PET prepolymer, is generally 1～100 quality ppm.
The representation example of manufacture method more specifically as the PET prepolymer of the manufacture method that is used for the 4th invention has following method for example.
Use with terephthalic acid as the dicarboxylic acid of main component and/or its ester forms the property derivative and with the dibasic alcohol of ethylene glycol as main component, usually, the dicarboxylic acid composition: glycol component is 1: 1～1: 2 (mol ratio), the words that need are in the presence of esterifying catalyst, usually greatly about 240～280 ℃ temperature, usually be to depress adding of 0.4MPa extremely about normal pressure greatly with respect to atmospheric relative pressure, in the esterification groove, carry out about 1～10 hour esterification, perhaps in the presence of transesterification catalyst, carry out transesterification reaction, resulting resultant (PET lower molecular weight body) is delivered to the polycondensation groove, then, carry out melt phase polycondensation.Melt phase polycondensation is, use polycondensation catalyst, usually be approximately under 250～290 ℃ the temperature, reduce pressure gradually from normal pressure, finally be approximately under the decompression of 10～0.1kPa in absolute pressure usually, under agitation, making it carry out melt phase polycondensation, is 0.18dL/g～0.40L/g as described below up to intrinsic viscosity.
In addition, the dicarboxylic acid composition is that the ester of dicarboxylic acid forms the property derivative, when for example being the material of the fusing point with appropriateness of dimethyl terephthalate (DMT) etc., also can not make slip with dibasic alcohol, after the fusion, for the transesterification reaction use of dibasic alcohol.In addition, above-mentioned reaction can be undertaken by any one method in continous way, intermittent type, the semibatch, and again, esterification groove (or transesterification reaction groove), melt polycondensation reaction groove can be made one section respectively, also can make multistage.
The PET prepolymer that will be obtained by melt polycondensation reaction is supplied with to the die head that is connected on the melt polycondensation reaction groove by pipeline and/or toothed gear pump and/or strainer, discharges from a plurality of nibs of the front end that is arranged on mould, is strand form or drips shape.The PET prepolymer that to be discharged by strand form ground is with cut-outs such as for example strand cutter, granulating glomeration.
It is 0.1～30mg/ grain that the particulate average quality of the PET prepolymer that is obtained by melt polycondensation reaction that is used for the manufacture method of the 4th invention it is desirable to, better is that lower value is the 0.5mg/ grain, it is desirable to the 0.8mg/ grain especially, on the other hand, better is that higher limit is the 10mg/ grain, further it is desirable to the 5mg/ grain, it is desirable to the 3mg/ grain especially.The used PET prepolymer of the manufacture method particulate average quality of the 4th invention is when above-mentioned lower value is above, when thereafter operation and strength transportation, be difficult for breaking down, therefore further desirable, again, when above-mentioned higher limit is following, can shorten the time that reaches the required solid state polycondensation of desirable molecular weight, therefore further desirable.In addition, be meant in the average quality of the so-called PET prepolymer of this specification sheets and use precision balance, measure 30 PET prepolymer particulate total mass, be accurate to the figure place of 0.1mg, the value that measured value is calculated divided by 30.
The intrinsic viscosity that is used for the PET prepolymer of the 4th manufacture method of inventing is 0.18～0.40dL/g.The lower value of intrinsic viscosity it is desirable to 0.20dL/g, and higher limit it is desirable to 0.38dL/g, it is desirable to 0.35dL/g especially.The intrinsic viscosity of this prepolymer during granulating, is easy to generate fine powder during less than above-mentioned lower value, again, becomes very long and undesirable because reach the desired required solid state polycondensation time of high molecular.On the other hand, if surpass above-mentioned higher limit, can not obtain as the feature of the manufacture method of the 4th invention, shorten and to obtain the high-molecular weight PET effect in required reaction times, and, in the melt phase polycondensation operation, need to carry out the equipment of the high price that high viscosity liquid stirs, high vacuum is reacted, as whole manufacturing process, the effect of the 4th invention is weakened.
The end carboxy concentration of PET prepolymer that is used for the manufacture method of the 4th invention it is desirable at 100 equivalents/below the ton.End carboxy concentration is better is 70 equivalents/below the ton, further it is desirable to 40 equivalents/below the ton, it is desirable to 20 equivalents/below the ton especially.If the end carboxy concentration of PET prepolymer surpasses 100 equivalent/tons, then in operation solid phase polycondensation thereafter, condensation polymerization speed tends to diminish.
Under solid state, heat-treat by the manufacture method of the 4th invention by the above-mentioned PET prepolymer particle that obtains like this, carry out solid phase polycondensation up to the intrinsic viscosity that reaches regulation.The thermal treatment of the manufacture method of the 4th invention mainly comprises interim solid phase polycondensation operation and heating process.These operations also can be carried out with interrupter method, but consider from the production efficiency aspect, it is desirable to carry out continuously.The intrinsic viscosity of the PET that the manufacture method of the 4th invention obtains is more than the 0.70dL/g.Manufacturing is during less than the PET of 0.70gL/g, then with former method relatively, do not give full play to the effect that can make solid state polycondensation speed become big such the 4th invention, therefore undesirable.
The thermal treatment of the manufacture method of the 4th invention contains the 1st section following solid phase polycondensation operation, heating process at least in order, reaches the 2nd section solid phase polycondensation operation.
1) the 1st section solid phase polycondensation operation:
This operation is under inert gas atmosphere or the operation of under the decompression PET prepolymer being heat-treated, and is that its heat treated temperature (T1c) is the operation more than 190 ℃, below 225 ℃.
2) heating process;
This operation is under inert gas atmosphere or under the decompression, to heat up through the PET prepolymer of the 1st section solid phase polycondensation operation heat treated temperature (T1c) or the temperature below it since the 1st section solid phase polycondensation operation, be warming up to the operation of temperature (T2c), be in 30 minutes, from temperature T 1c (℃) be warming up to (T1c+15) ℃, and temperature T 1c (℃) and T2c (℃) satisfy the operation of following (formula 1c) and (formula 2c).
T1c+15≤T2c (formula 1c)
205 ℃≤T2c≤240 ℃ (formula 2c)
3) the 2nd section solid phase polycondensation operation:
This operation is under inert gas atmosphere or under the decompression, to the operation of heat-treating through the PET prepolymer of the 1st section solid phase polycondensation operation and heating process, and is that its heat treated temperature (T3c) is in the operation more than 190 ℃, below 240 ℃.
These heating process, the 1st section and the 2nd section solid phase polycondensation operation are carried out under inert gas atmosphere or under the decompression, here, " rare gas element " is meant oxygen concn below 0.1 volume %, ideal below 0.05 volume %, and in fact not with the gas of polyester (PET) reaction.As in fact not with the gas of pet reaction, specifically, can enumerate nitrogen, helium, neon, argon gas, xenon, carbonic acid gas etc., mainly, it is desirable to use nitrogen from the viewpoint of economy.Again, " under reducing pressure " is meant and is in the following pressure status of absolute pressure 2kPa.
The temperature (T1c) of the 1st section solid phase polycondensation operation is more than 190 ℃, below 225 ℃, and lower value it is desirable to 200 ℃, and better is 205 ℃.The higher limit of T1c it is desirable to 220 ℃.If 190 ℃ of T1c less thaies, then the condensation polymerization speed in the 1st section operation diminishes, the load of the 2nd section operation thereafter becomes big and undesirable.If T1c surpasses 225 ℃, then as described later, the temperature of heating process (T2c) surpasses 240 ℃ of higher limits, the bad situation that causes that the fusion adhesion each other of PET particle takes place easily etc.
Again, in the heating process behind first section solid phase polycondensation of manufacture method of the 4th invention, T1c and T2c must satisfy T1c+15 ℃≤T2c (formula 1c), and no matter how long the time is, also must be at 30 minutes with interior intensification more than at least 15 ℃.Just, T1c is more than 190 ℃, below 225 ℃, because T1c and T2c satisfy (formula 1c), as a result of, T2c will satisfy following (formula 2c).
205 ℃≤T2c≤240 ℃ (formula 2c)
Thus, can obtain the effect of big such the 4th invention of the speed of the solid phase polycondensation behind the heating process.
By such heating process, the reason that obtains the 4th effect of inventing is also unclear, and we are presumed as follows.
Just, during owing to crystallization under lower molecular weight, because of forming crystalline texture the mobility of polyester molecule chain is reduced, the terminal group deactivation of a part, especially under lower molecular weight during crystallization, it is big that the absolute value of the terminal radix of deactivation becomes, so diminish at the latter half condensation polymerization speed of solid phase polycondensation.To this, by bestowing the temperature difference on the way at short notice is such heat treated more than 15 ℃, though maintenance solid state, but owing to the crystalline fusion taking place and recrystallizing, form the non-crystalline areas that has many terminal group once more, so the part of the terminal group of deactivation obtains activity again, condensation polymerization speed is increased.
If the intensification amplitude surpasses 30 minutes less than 15 ℃ or intensification required time, then can not obtain the effect of raising solid state polycondensation speed of the manufacture method of the 4th invention sometimes, especially can not obtain the effect in the 2nd section solid phase polycondensation operation.
The temperature (T3c) of the 2nd section solid phase polycondensation operation is more than 190 ℃, below 240 ℃, and the lower value of T3c it is desirable to 210 ℃, and better is 220 ℃.The higher limit of T3c it is desirable to 237 ℃, better be 235 ℃.If, then arriving the polymerization degree of target less than 190 ℃, T3c needs for a long time.Again, if T3c surpasses 240 ℃, the bad situation that causes that then the fusion adhesion each other of PET particle takes place easily etc.In addition, even when the temperature of T3c is hanged down than the temperature (T2c) of heating process, also can bring into play the big such effect of solid phase polycondensation speed of the 4th invention.
The mean residence time of the 1st section solid phase polycondensation operation is also according to its temperature T 1c, and more than 0.5 hour, below 10 hours, lower value it is desirable to 1.0 hours usually.Higher limit it is desirable to 9 hours, and better is 8 hours.If the mean residence time of the 1st section solid phase polycondensation operation is more than 0.5 hour, then the intrinsic viscosity rising value of the 1st section solid phase polycondensation operation becomes big, alleviates the load of the 2nd section solid phase polycondensation operation.Again, if the mean residence time of the 1st section solid phase polycondensation operation is below 10 hours, then the decline of the solid state polycondensation speed of the latter half in the 1st section solid phase polycondensation operation is slight, is respectively efficient, thereby better.
The rising of the intrinsic viscosity in the 1st section solid phase polycondensation operation, promptly the difference of the intrinsic viscosity of the PET before and after the 1st section solid phase polycondensation operation more than 0.03dL/g, it is desirable to more than 0.05dL/g usually.It is better if this value more than 0.03dL/g, then obtains the effect of the 2nd section raising solid state polycondensation speed in the solid phase polycondensation operation easily.Again, satisfy whole heat treatment period for the shortest and/or to drop into heat be minimum, be typically about 0.30dL/g as long as the upper limit of the ascensional range of the intrinsic viscosity in the 1st section solid phase polycondensation operation is set for.
The residence time in the heating process it is desirable to below 40 minutes usually below 60 minutes, and better is below 30 minutes.The residence time of heating process except the effect with the so greatly heating process of above-mentioned solid phase polycondensation speed, can also be used in the device miniaturization of heating process when this scope, thereby better.Be used for the equipment of heating process so long as can make the equipment of PET particle heat temperature raising, just have no particular limits, it is desirable to usually adopt the fluidized-bed that uses rare gas element, because use this fluidized-bed, particle fusion adhesion and particulate each other is broken few.
Through behind the heating process, the intrinsic viscosity that is supplied to the prepolymer of the 2nd section solid phase polycondensation operation it is desirable to more than 0.35dL/g, better is more than 0.40dL/g, further it is desirable to it is desirable to more than 0.45dL/g especially more than 0.43dL/g.The intrinsic viscosity of process heating process is when this scope, solid state polycondensation speed in the 2nd section solid phase polycondensation operation of the manufacture method of the 4th invention is big, simultaneously, and especially under load, often can suppress to have the heat fusing adhesion of the PET of copolymer composition, therefore better.The difference of the intrinsic viscosity of the intrinsic viscosity of the prepolymer of supplying with to the 2nd section solid phase polycondensation operation behind the process heating process and the polyester that obtains through the 2nd section solid phase polycondensation operation more than 0.10dL/g, it is desirable to more than 0.20dL/g usually.
The mean residence time of the 2nd section solid phase polycondensation operation is also according to its temperature, and more than 2 hours, below 50 hours, lower limit it is desirable to more than 4 hours usually.Mean residence time is when this scope, and it is big that the intrinsic viscosity rising value in the 2nd section solid phase polycondensation operation becomes, and the PET that can obtain having the desirable polymerization degree efficiently is therefore better.
Above-mentioned the 1st section solid phase polycondensation operation and the 2nd section solid phase polycondensation operation of the 4th invention it is desirable to carry out continuously, consider from aspects such as production efficiency, reaction control and operability, it is desirable to use the continous way moving-bed especially.
It is desirable to, before heat treated the 1st section solid phase polycondensation operation of the 4th invention, the crystallization step of at least a portion crystallization of the PET prepolymer that in fact makes noncrystalline state is set.By making at least a portion crystallization of PET prepolymer, can alleviate the PET particle fusion adhesion each other of thereafter the 1st section, the 2nd section solid phase polycondensation operation etc.Crystallization is undertaken by the PET prepolymer is heat-treated, and the temperature of its crystallization step (Tx) it is desirable to lower limit more than 140 ℃ usually more than 110 ℃, below 200 ℃, and better is that lower limit is more than 160 ℃.During in this scope, this prepolymer particle is difficult for the fusion adhesion each other, and is reaching sufficient crystallization degree than the short period, and is therefore better in the temperature (Tx) of crystallization step.Again, after next operation, also often be difficult for the fusion adhesion takes place, therefore better.
In crystallization step, it is desirable to carry out the crystallization of PET prepolymer, obtain the PET prepolymer that the crystallization degree is approximately 30～60 quality %.Crystallization step is so long as the equipment that can heat the PET particle just has no particular limits, but if undertaken by the fluidized-bed that uses rare gas element, then particle fusion adhesion each other etc. less and desirable.
In addition, can before this crystallization step, be provided with and make the PET prepolymer be warming up to the operation of Tx, also can in crystallization step, heat up and crystallization.Also can in crystallization step, carry out the drying of prepolymer again.Again, the drying of prepolymer also can be carried out at the initial stage of the 1st section solid phase polycondensation operation.
After heat treated the 2nd section solid phase polycondensation operation of the present invention, the 2nd section solid phase polycondensation operation, the 3rd section solid phase polycondensation operation can also be set.This occasion, it is desirable to respectively, the temperature (T3c) of the 2nd section solid phase polycondensation operation is more than 190 ℃, below 225 ℃, the temperature (T4c) of the 2nd section heating process than T3c (℃) high more than 15 ℃, below 240 ℃, the temperature (T5c) of the 3rd section solid phase polycondensation operation is more than 205 ℃, below 240 ℃.Here, the 2nd section heating process be from T3c (℃) or temperature below it begin to heat up, be warming up to the operation of temperature (T4c), it is desirable in 30 minutes, from temperature T 2c (℃) be warming up to (T2c+15) ℃.Equally, also can alternate repetition carry out solid phase polycondensation operation and heating process more than 3 times.
Aforesaid more cryogenic solid phase polycondensation operation be warming up to the method that comparison pyritous heating process alternate repetition carries out at short notice, especially when the PET prepolymer of fusion adhesion carries out solid phase polycondensation how and easily with the copolymerization amount, fusion adhesion in the time of often can suppressing with moving-bed enforcement solid phase polycondensation operation, again owing to often suppressing along with the deactivation of implementing a part of terminal group that solid phase polycondensation produces for a long time, therefore often can shorten whole heat treatment time, therefore better.
Below, by embodiment, the present invention will be described in more detail, but the present invention only limits to not exceed its main points, is not limited in the following examples.
The measuring method of the various rerum naturas in embodiment and the comparative example is as described below.
＜intrinsic viscosity (IV) 〉
Will about 0.25g sample dissolution in the mixed solvent of about 25mL phenol/sym.-tetrachloroethane (mass ratio 1/1), making its concentration is 1.00 * 10
-2Kg/L, the polyester or the PET of noncrystalline state are dissolved under 110 ℃, 30 minutes condition, polyester behind the solid phase polycondensation or PET dissolve under 140 ℃, 30 minutes condition, be cooled to 30 ℃ then, measuring concentration with full-automatic soltion viscosity meter (" 2CH type DJ504 " that Sentec company makes) is 1.00 * 10
-2The sample solution of kg/L and decline number second when having only solvent are calculated the result according to following formula.In addition, the measuring principle of above-mentioned full-automatic soltion viscosity meter is the fall time that descends in kapillary (tubule) of the solution of comparative unit volume and the fall time when having only solvent.
IV＝[(1+4K
H·η
sp)
0.5-1]/(200K
H·C)
Here, η
Sp=η/η
0-1, η is decline number second of sample solution, η
0Be decline number second of solvent, C is polymer solution concentration (kg/L), K
HIt is the He Jin constant.K
HAdopt 0.33.
＜polyester and PET prepolymer particulate average quality 〉
Use precision balance, measure 30 PET prepolymer particulate total mass, be accurate to the figure place of 0.1mg, observed value is calculated per 1 particulate average quality divided by 30.
＜polyester and PET prepolymer particulate median size 〉
The dry screen separating tests method of being put down in writing according to JIS K0069 is made the cumulative distribution curve, and the accumulative total percentage is reached 50% o'clock value as median size.
＜end carboxy concentration (AV) 〉
After the sample pulverizing, following dry 15 minutes with hot air dryer at 140 ℃, at the moisture eliminator internal cooling to room temperature, accurately take by weighing 0.1g and put into test tube from cooled sample, add the 3mL phenylcarbinol, the limit is blown into drying nitrogen, the limit makes it dissolve 3 minutes down at 195 ℃, then, gently add the 5mL chloroform, be cooled to room temperature.Add 1～2 phenol red indicator in this solution, the limit is blown into the drying nitrogen limit and stirs, and carries out titration with the benzyl alcohol solution of 0.1 sodium hydroxide of stipulating, stops when yellow becomes redness.Again,, do not use the vibrin sample, implement same operation, according to following formula, calculate end carboxy concentration with these results as blank.
AV (equivalent/ton)=(A-B) * 0.1 * f/W
(here, the amount (μ L) of the benzyl alcohol solution of the sodium hydroxide of 0.1 regulation that the titration when A is to use sample is required, B is the amount (μ L) of the benzyl alcohol solution of the 0.1 required sodium hydroxide of stipulating of the titration in blank, W is the amount (g) of vibrin sample, and f is the titre of the phenylcarbinol of 0.1 sodium hydroxide of stipulating.)
In addition, getting 5mL methyl alcohol puts in vitro, add 1～2 phenol red ethanolic soln as indicator, the benzyl alcohol solution of sodium hydroxide with 0.1 regulation of 0.4mL is carried out titration, to color transition point, then, get 0.2mL and add the hydrochloric acid of stipulating as the titre of reference liquid known 0.1, benzyl alcohol solution with 0.1 sodium hydroxide of stipulating is titrated to color transition point (above operation limit is blown into the drying nitrogen limit and carries out) again, by following formula, calculate the titre (f) of the benzyl alcohol solution of 0.1 sodium hydroxide of stipulating.
The titer (μ L) of the benzyl alcohol solution of the sodium hydroxide of the amount of taking (μ L)/0.1 regulation of the hydrochloric acid of the titre of the hydrochloric acid of titre (f)=0.1 regulation * 0.1 regulation
＜crystallization degree (X
c)
Crystallization degree (X
c) mensuration, as the density d of complete amorphous
a=1335kg/m
3, complete crystalline density d
c=1455kg/m
3, by the density d (kg/m of sample
3) calculate by following formula.
X
c＝(d-d
a)d
c/(d
c-d
a)d×100(％)
Again, the sample that takes by weighing 6～8g is put into the mensuration groove, and measuring temperature is 23 ℃, uses dry type automatic density determinator (the system Accupyc 1330 of Shimadzu Seisakusho Ltd.), measures the density d of sample.
＜Diethylene Glycol (DEG) copolymerization mole % 〉
Add 50mL4 regulation-potassium hydroxide/methanol solution at 5.00g in as the PET particle of sample, reflux cooler be set, at the hot plate (200 ℃ of surface temperatures) of band magnetic stirring apparatus Yi Bian on stir, Yi Bian reflux was hydrolyzed in 2 hours.After placing cooling, add about 20g high purity terephthalic acid, fully vibration, making it neutralization, is after slip 9 below filters with glass filter (11G-4) with this pH, usefulness 2ml washed with methanol 2 times, filtrate and washing lotion are lumped together, as the test liquid of air feed phase chromatography use.With microsyringe 1 μ l test liquid is injected the gas chromatographic column (form GC-14APF) that Shimadzu Seisakusho Ltd. makes, account for the mole % of whole glycol component according to following formula by the calculated by peak area Diethylene Glycol composition of ethylene glycol (EG) and Diethylene Glycol composition.
The copolymerization mole %=(A of DEG
DEG* C
FDEG)/(∑ (A * C
f)) * 100
A
DEG: the area of Diethylene Glycol composition (μ V second)
C
FDEG: the augmenting factor of its glycol component
A: the area of each glycol component (μ V second)
C
f: the augmenting factor of each glycol component
(embodiment 1)
Can use the apparatus for continously production of following polyester prepolymer to make polyester prepolymer particle, this apparatus for continously production possesses: the slip preparation vessel with stirrer, ethylene glycol feeding pipe and terephthalic acid feeding pipe; Slip is delivered to the pipeline of esterification first groove; First and second esterification groove of complete mixed type with stirrer, knockout tower, raw material receiving port, catalyst feed pipeline, reactant gas delivery path road; Reactant of esterification (oligopolymer) is delivered to the pipeline (still, possessing catalyst feed pipeline) of melt polycondensation reaction groove; Complete mixed type melt polycondensation reaction groove with stirrer, knockout tower, oligopolymer receiving port, catalyst feed pipeline; Will be by taking out pipeline, toothed gear pump being polyester prepolymer that strand form discharges from the punch die fishplate bar current cuts off and makes particulate strand cutter (Fitz chilsonator (P-USG100) that リ one one aumatic company makes).Whole reactions is all carried out under nitrogen atmosphere.
At first, two-(beta-hydroxy ethyl) terephthalate of 450 mass parts is thrown into the first esterification groove, in groove, carry out nitrogen replacement after, in 262 ℃ of following fusions of temperature.Again, is 1.5 to throw in the slip preparation vessel terephthalic acid and ethylene glycol with the mol ratio of ethylene glycol and terephthalic acid, stir and make slip, with this slip with 135 mass parts/hour speed to throw into pressure continuously be that 96kPaG, temperature are that making mean residence time is 4.5 hours (slip conveying operation) in 262 ℃ the first esterification groove.Simultaneously, add the ethylene glycol solution (concentration: as tungsten atom is 1.1 quality %) of ammonium metawolframate from the gas phase partial continuous ground of the first esterification groove, the amount of ammonium metawolframate is with respect to the resulting polyester prepolymer, as tungsten is 80 quality ppm, remove the water of generation from the knockout tower distillation, and carry out esterification (esterification step), take out reaction solution continuously, be delivered to the second esterification groove.In the second esterification groove, be that 260 ℃, pressure are 5kPaG, the residence time to be under 1.5 hours the condition in temperature, carry out esterification (esterification step).
The oligopolymer that obtains from the second esterification groove is delivered to the melt polycondensation reaction groove continuously by transfer line.Upstream side from the place of the interpolation antimonous oxide of this transfer line, add ortho-phosphoric ethylene glycol solution (concentration: as phosphorus atom is 1.6 quality %) continuously, ortho-phosphoric amount is for being the such amounts of 12 quality ppm with respect to the resulting polyester prepolymer as phosphorus, and, adding the ethylene glycol solution (concentration: as antimony atoms is 1.8 quality %) of antimonous oxide continuously supplies with to the melt polycondensation reaction groove, the amount of antimonous oxide is for being the such amounts of 209 quality ppm with respect to the resulting polyester prepolymer as antimony.
In the melt polycondensation reaction groove, at pressure is that 2.5kPaA, temperature are that 273 ℃, the residence time are to react (melt phase polycondensation operation) under 1.0 hours the condition, by taking out pipeline, toothed gear pump, make the resulting polyester prepolymer be strand form and discharge from the punch die fishplate bar.In the current of strand cutter (Fitz chilsonator (P-USG100) that リ one one aumatic company makes), make the polyester prepolymer cooling curing of this strand form, cut off with turning gear and fixed teeth simultaneously, make particle.To begin through 15 hours later particles as the sample that uses for solid phase polycondensation from melt polycondensation reaction.
The intrinsic viscosity (IV) of polyester prepolymer particle (sample) is 0.211dL/g, and end carboxy concentration (AV) is 16 equivalent/tons, and median size is 1.0mm.
This prepolymer particle of 18g is placed on the square that the bottom surface is 130mm * 170mm, the stainless steel vessel (vat) that the degree of depth is 30mm, under this state, put the gas inside temperature into and be 180 ℃ thermostat container (inert oven) (the IPHH-201m type that Tabaiespec company makes), making the flow of the nitrogen that the inside of thermostat container circulates is the 50NL/ branch, temperature is 180 ℃, and the crystallization that carried out 2 hours is handled.Here, NL is the volume (L) of the gas in 0 ℃, 101.3kPa.
The polyester prepolymer particle that 2g was carried out the crystallization of crystallization processing is placed in the described stainless steel vessel equably, put the gas inside temperature into and be 50 ℃ described thermostat container, the flow of the nitrogen that circulates in the inside of thermostat container is the 50NL/ branch, made temperature be warming up to 210 ℃ with 30 minutes from 50 ℃, 210 ℃ keep 20 minutes after, be warming up to 230 ℃ with 0.5 ℃/minute heat-up rate, keep the specified time, carry out solid phase polycondensation (solid phase polycondensation operation) thus at 230 ℃.
With the hold-time after arriving 230 ℃ as the solid phase polycondensation time, the intrinsic viscosity of resulting polyester was 0.760dL/g when the solid phase polycondensation time was 16 hours.Putting its result in order is shown in the table 1.
(comparative example 1)
Adding the ethylene glycol solution of ammonium metawolframate in the first esterification groove in omitting embodiment 1, other carry out similarly to Example 1.Its result is shown in the table 1.
(embodiment 2)
Omit and to add the ethylene glycol solution of ammonium metawolframate and the ethylene glycol solution that adds ortho-phosphoric acid and antimonous oxide to transfer line to the first esterification groove among the embodiment 1 from the second esterification groove to the melt polycondensation reaction groove, and add the ethylene glycol solution (concentration: as titanium atom is 0.075 quality %) of tetrabutyl titanate from the gas phase portion of slip preparation vessel, the amount of tetrabutyl titanate is for being 8 quality ppm with respect to the resulting polyester prepolymer as titanium, and in the reaction liquid phase, add the ethylene glycol solution (concentration: as magnesium atom is 0.040 quality %) of magnesium acetate 4 water salt and the ethylene glycol solution (concentration: as phosphorus atom is 0.030 quality %) of acid phosphate ester continuously, the amount of magnesium acetate 4 water salt is for being 8 quality ppm with respect to the resulting polyester prepolymer as magnesium, the amount of acid phosphate ester is for being 8 quality ppm with respect to the resulting polyester prepolymer as phosphorus, in addition, other and embodiment 1 carry out in the same manner.The result is shown in the table 1.
Table 1
| The prepolymer rerum natura | Behind the solid phase polycondensation | |||
| IV (dl/g) | AV (equivalent/ton) | Particle diameter (mm) | IV (dL/g) | |
| Embodiment 1 | 0.211 | 16 | 1.0 | 0.760 |
| Comparative example 1 | 0.209 | 143 | 1.0 | 0.567 |
| |
0.216 | 45 | 0.9 | 0.712 |
IV: intrinsic viscosity AV: end carboxy concentration
The result is with respect to embodiment 1,2, and comparative example 1 is because the end carboxy concentration of prepolymer is big, so the intrinsic viscosity behind the solid phase polycondensation little (solid phase polycondensation speed is little).
(embodiment 3)
Can use the apparatus for continously production of following PET prepolymer to make polyester prepolymer particle, this apparatus for continously production possesses: the slip preparation vessel with stirrer, ethylene glycol feeding pipe and terephthalic acid feeding pipe; Slip and reactant of esterification are delivered to each pipeline of each esterification groove; First and second esterification groove of complete mixed type with stirrer, knockout tower, raw material receiving port, catalyst feed pipeline, reactant gas delivery path road; Reactant of esterification (oligopolymer) is delivered to the pipeline of melt polycondensation reaction groove; The complete mixed type first melt polycondensation reaction groove with stirrer, knockout tower, oligopolymer receiving port, catalyst feed pipeline; Second and third melt polycondensation reaction groove of plug flow type that possesses stirrer, knockout tower, polymkeric substance receiving port, polymkeric substance conveying end; By conveying end prepolymer is strand form ground from the punch die fishplate bar by toothed gear pump and takes out, and at the granulation device (the strand cutter is the Fitz chilsonator (P-USG100) that リ one one automatic company makes) with the disconnected strand of water cooling incision.Whole reactions is all carried out under nitrogen atmosphere.
In the slip preparation vessel, terephthalic acid, m-phthalic acid, ethylene glycol are mixed, add the EG solution of tetra-n-butyl titanate simultaneously, modulation contains terephthalic acid/isophthalic acid/ethylene glycol (mol ratio 0.97: 0.03: 1.5) slip of tetra-n-butyl titanate, and the amount of tetra-n-butyl titanate is for being 8 quality ppm with respect to resulting polyester as titanium atom.Then, two-(beta-hydroxy ethyl) terephthalate of 400 mass parts is thrown into esterification first reactive tank, fusion under nitrogen atmosphere, remaining on temperature and be 262 ℃, pressure is 96kPaG, to wherein with 135 mass parts/hour speed drop into continuously described in the slip preparation vessel synthetic slip, making the mean residence time as polyester is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, esterification is carried out on the limit, and reaction solution is delivered to esterification second reactive tank continuously.
In the second esterification groove, be that 260 ℃, pressure are 5kPaG, the residence time to be to carry out esterification under 1.5 hours the condition in temperature, by transfer line, carry to the complete mixed type first melt polycondensation reaction groove continuously.
In the first melt polycondensation reaction groove, be that 270 ℃, pressure are 3.8kPaG, the residence time to be to react under 1.0 hours the condition in temperature, by transfer line, carry to the second melt polycondensation reaction groove continuously.In the second melt polycondensation reaction groove, be that 275 ℃, pressure are 3.8kPaG, the residence time to be under 1.0 hours the condition in temperature, carry out melt polycondensation reaction, by transfer line, carry to the 3rd melt polycondensation reaction groove.In the 3rd melt polycondensation reaction groove, be that 275 ℃, pressure are 3.8kPaA, the residence time to be under 1.2 hours the condition in temperature, carry out melt polycondensation reaction.
The molten polyester prepolymer that obtains is like this imported to die head by toothed gear pump and taking-up pipeline like this, be strand form ground from nib and discharge.In the current of strand cutter (Fitz chilsonator (P-USG100) that リ one one automatic company makes), make the polyester prepolymer cooling curing of this strand form, cut off with turning gear and fixed teeth simultaneously, make particle.To begin through 15 hours later particles as the sample that uses for solid phase polycondensation from melt polycondensation reaction.
The intrinsic viscosity (IV) of polyester prepolymer particle (sample) is 0.323dL/g, and end carboxy concentration (AV) is 26 equivalent/tons, and the copolymerization amount of m-phthalic acid, Diethylene Glycol is respectively 2.9 moles of %, 2.2 moles of %, and median size is 1.1mm.
It is the stainless steel vessel of 30mm that the particle of this prepolymer of 30g A is launched to be positioned over square, the degree of depth that the bottom surface is 130mm * 170mm, put the gas inside temperature into and be 180 ℃ thermostat container (the IPHH-201M type that Tabaiespec company makes), flow at the nitrogen of thermostat container internal circulation is that 50NL/ branch, temperature are 180 ℃, and the crystallization that carried out 1 hour is handled.Here, NL is the volume (L) in 0 ℃, 101.3kPa.
Heat-treat with the prepolymer particle that glass thermal treatment unit shown in Figure 1 was handled above-mentioned crystallization.
Below, this thermal treatment unit is described.
In thermal treatment unit shown in Figure 1, the internal diameter that sample is filled in the sample filling part is in the glass thermal treatment pipe (1) of 45mm.Through gas meter (2), nitrogen ingress pipe (3), nitrogen preheating tube (4), the nitrogen after heating by the oil that is filled in oil bath (5) again is directed to thermal treatment pipe (1).By the breaker plate (6) that is in thermal treatment pipe (1) bottom the nitrogen that imports is disperseed, have the roughly upwelling of the linear velocity of homogeneous inner formation of thermal treatment pipe (1), by sample layer (7).Nitrogen by sample layer (7) passes through the strainer (8) that is in thermal treatment pipe (1) top, is discharged to the outside of thermal treatment pipe (1) from gas sweetening mouth (9).Thermal treatment pipe (1) has arm (10), can be toward peristome (clogging with the glass bottle stopper usually) the input sample that is positioned at its top or from this peristome sample thief.Again, the temperature of the sample of thermal treatment pipe (1) inside can be measured with the thermometer that possesses thermopair (11) (12).In the temperature of the scope of present embodiment, superficial linear velocity, because the internal temperature of thermal treatment pipe (1) is than low 2 ℃ of the temperature of the oil in the oil bath, so the temperature regulation of oil bath is the high 2 ℃ of such temperature of solid phase polycondensation temperature that liken to target.
The prepolymer particle after crystallization is handled that 30g is above-mentioned is thrown into thermal treatment pipe (1) from the peristome of arm (10), makes the nitrogen circulation, and inside is replaced into nitrogen.Then, set the flow of nitrogen with gas meter (2), make thermal treatment pipe (1) nitrogen superficial linear velocity (here, the meaning of " superficial linear velocity " is the superficial linear velocity (following identical) of sample layer) under 210 ℃ 0.30m/ second, first oil bath (5) that is adjusted to 212 ℃ is flooded thermal treatment unit 2 hours.
Continue the flow of change nitrogen, make the superficial linear velocity of nitrogen be 1.0m/ second down at 235 ℃, the temperature regulation that thermal treatment unit is moved to oil is 237 ℃ second oil bath (5), floods 10 minutes.
Continue the flow of change nitrogen, make the superficial linear velocity of nitrogen be 0.30m/ second down at 230 ℃, the temperature regulation that thermal treatment unit is moved to oil is 232 ℃ the 3rd oil bath (5), floods 24 hours.
The intrinsic viscosity of the polyester that obtains like this is 0.850dL/g.Put its result in order, be shown in the table 2.
(comparative example 2)
Except the point of addition of the EG solution of the tetra-n-butyl titanate among the embodiment 3 was changed to transfer line between the second esterification groove and the first melt polycondensation reaction groove from the slip preparation vessel, other were identical with embodiment 3.Its result is shown in the table 2.
Table 2
| The prepolymer rerum natura | Behind the solid phase polycondensation | |||
| IV (dl/g) | AV (equivalent/ton) | Particle diameter (mm) | IV (dL/g) | |
| |
0.323 | 26 | 1.1 | 0.850 |
| Comparative example 2 | 0.330 | 60 | 1.1 | 0.723 |
IV: intrinsic viscosity, AV: end carboxy concentration
With respect to embodiment 3, comparative example 2 is because the end carboxy concentration of prepolymer is big, as a result the intrinsic viscosity behind the solid phase polycondensation little (solid phase polycondensation speed is little).
(Production Example of polyester prepolymer)
The manufacturing of＜polyester prepolymer A 〉
Use possesses the polyester apparatus for continously production with lower device, promptly possesses: the slip preparation vessel with stirrer, ethylene glycol feeding pipe and terephthalic acid feeding pipe; Slip is transported to the pipeline of the first esterification groove; First and second esterification groove of complete mixed type with stirrer, knockout tower, raw material receiving port, catalyst feed pipeline, reactant gas delivery path road; Reactant of esterification (oligopolymer) is transported to the pipeline of melt polycondensation reaction groove; The complete mixed type first melt polycondensation reaction groove with stirrer, knockout tower, oligopolymer receiving port, catalyst feed pipeline; Second and third melt polycondensation reaction groove of plug flow type with stirrer, knockout tower, polymkeric substance receiving port, polymkeric substance conveying end; From the punch die fishplate bar polymkeric substance is strand form ground by conveying end by toothed gear pump and takes out, with under the water cooling, cut off strand granulation device (the strand cutter be リ one one automatic company make Fitz chilsonator (P-USG100)).
At first, modulation is added with terephthalic acid/ethylene glycol (mol ratio 1: 1.5) slip of ortho-phosphoric ethylene glycol solution (concentration: as phosphorus atom is 0.50 quality %) in the slip preparation vessel, this ortho-phosphoric amount is the concentration that makes the phosphorus in the resulting polyester, calculating with phosphorus atom, is the such amounts of 22 quality ppm.Again, two-(beta-hydroxyethyl) terephthalate of 400 mass parts is put into the first esterification groove, fusion under nitrogen atmosphere, remain on temperature and be 262 ℃, pressure and be 96kPaG (below, G represents with respect to atmospheric relative pressure), to wherein with 135 mass parts/hour speed put into continuously described in the slip preparation vessel synthetic slip, making the mean residence time as polyester is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, esterification is carried out on the limit, and reaction solution is delivered to the second esterification groove continuously.
In the second esterification groove, in temperature is that 260 ℃, pressure are 5kPaG, the residence time to be under 1.5 hours the condition, the ethylene glycol solution (concentration: the concentration of antimony atoms is 1.8 quality %) of antimonous oxide is added on the limit continuously, esterification is carried out on the limit, by transfer line, to carry to the complete mixed type first melt polycondensation reaction groove, the amount of this antimonous oxide is the concentration that makes the antimony in the resulting polyester prepolymer, calculating with antimony atoms, is the such amounts of 183 quality ppm.In the first melt polycondensation reaction groove, the pressure of polycondensation groove be 2.0kPaA (below, A represents absolute pressure), temperature is that 278 ℃, the residence time are to react under 1.0 hours the condition, make the polyester prepolymer that obtains by the second melt polycondensation reaction groove, the 3rd melt polycondensation reaction groove, being strand form ground from the punch die fishplate bar by toothed gear pump continuously by the polymkeric substance conveying end takes out, under current, cut off strand, obtain the particle (median size is 1.2mm) of the polyester prepolymer A of 4000 mass parts.
The intrinsic viscosity of the polyester prepolymer A that obtains is 0.247dL/g, and end carboxy concentration is 55 equivalent/tons.
The manufacturing of＜polyester prepolymer B 〉
Use and be used to make the identical polyester apparatus for continously production of polyester prepolymer A, carry out the manufacturing of polyester prepolymer B.
At first, in the slip preparation vessel, modulation is added with terephthalic acid/ethylene glycol (mol ratio 1: 1.5) slip of the ethylene glycol solution (concentration: titanium atom is 0.075 quality %) of tetrabutyl titanate, the amount of tetrabutyl titanate is the concentration that makes the titanium in the polyester prepolymer that obtains, calculating with titanium atom, is the such amounts of 8 quality ppm.Again, two-(beta-hydroxy ethyl) terephthalate of 400 mass parts is put into the first esterification groove, fusion under nitrogen atmosphere, remaining on temperature and be 262 ℃, pressure is 96kPaG, to wherein, with 135 mass parts/hour speed drop into continuously described in the slip preparation vessel synthetic slip, making the mean residence time as polyester is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, and esterification is carried out on the limit, and reaction solution is delivered to the second esterification groove continuously.
In the second esterification groove, be that 260 ℃, pressure are 5kPaG, the residence time to be to react under 1.5 hours the condition in temperature, by transfer line, carry to the complete mixed type first melt polycondensation reaction groove continuously.
In the first melt polycondensation reaction groove, the ethylene glycol solution (concentration: magnesium atom is 0.040 quality %) of magnesium acetate 4 water salt and the ethylene glycol solution (concentration: phosphorus atom is 0.030 quality %) of acid phosphate ester are added continuously in the limit in the reaction liquid phase, the amount of magnesium acetate 4 water salt is the concentration that makes the magnesium in the polyester prepolymer that obtains, calculate with the magnesium atoms metal, be the such amounts of 8 quality ppm, and the amount of ethylhexyldithiophosphoric acid phosphoric acid ester is the concentration that makes the phosphorus in the polyester prepolymer that obtains, calculate with phosphorus atom, be the such amounts of 8 quality ppm, pressure at the polycondensation groove is 2.5kPaA, temperature is 273 ℃, the residence time is to react under 1.0 hours the condition, and reactant is delivered to the second melt polycondensation reaction groove continuously.In the second melt polycondensation reaction groove, be that 2.0kPaA, temperature are that 275 ℃, the residence time are to carry out melt polycondensation reaction under 1.0 hours the condition at pressure, by transfer line, reactant is carried to the 3rd melt polycondensation reaction groove continuously.In the 3rd melt polycondensation reaction groove, be that 2.0kPaA, temperature are that 275 ℃, the residence time are to carry out melt polycondensation reaction under 1.2 hours the condition at pressure.Continuously the polyester prepolymer that obtain be strand form ground by conveying end from the punch die fishplate bar by toothed gear pump and take out, under current, cut off strand, obtain the particle (median size 1.2mm) of the polyester prepolymer B of 4000 mass parts.
The intrinsic viscosity of the polyester prepolymer B that obtains is 0.373dL/g, and end carboxy concentration is 31 equivalent/tons.
(embodiment 4)
The particle of the polyester prepolymer A that 30g is obtained by the Production Example of above-mentioned polyester prepolymer launches to be positioned over the square that the bottom surface is 130mm * 170mm, the stainless steel container made (vat) that the degree of depth is 30mm, put the gas inside temperature into and be 180 ℃ thermostat container (oven) (the IPHH-201M type that Tabaiespec company makes), at the flow of the nitrogen of thermostat container internal circulation is that 50NL/ branch, temperature are that the crystallization that carried out under 180 ℃ 1 hour is handled under 180 ℃ the nitrogen circulation.Here, NL is meant the volume (L) under 0 ℃, 1 air pressure.
The intrinsic viscosity of sample polyester prepolymer A after crystallization is handled is 0.250dL/g.It is heat-treated with glass thermal treatment unit shown in Figure 1.In thermal treatment unit shown in Figure 1, the internal diameter that sample is filled in the sample filling part is in the thermal treatment pipe (1) of glass of 45mm.Through under meter (2), nitrogen ingress pipe (3), nitrogen preheating tube (4), the nitrogen after heating by the oil that is filled in oil bath (5) again is directed to thermal treatment pipe (1).By being in the breaker plate (6) of thermal treatment pipe (1) bottom, the nitrogen that imports is disperseed, have the roughly upwelling of the linear velocity of homogeneous inner formation of thermal treatment pipe (1), by sample layer (7).Nitrogen by sample layer (7) passes through the strainer (8) that is in thermal treatment pipe (1) top, is discharged to the outside of thermal treatment pipe (1) from gas sweetening mouth (9).Thermal treatment pipe (1) has arm (10), can be toward peristome (clogging with the glass bottle stopper usually) the input sample that is positioned at its top or from this peristome sample thief.Again, the temperature of the sample of thermal treatment pipe (1) inside can be measured with the thermometer that possesses thermopair (11) (12).In the temperature of the scope of present embodiment, superficial linear velocity, because the internal temperature of thermal treatment pipe (1) is than low 2 ℃ of the temperature of the oil in the oil bath, so the temperature regulation of oil bath is the high 2 ℃ of such temperature of solid phase polycondensation temperature that liken to target.
The particle of the polyester prepolymer A of 30g after crystallization is handled is thrown into the thermal treatment pipe (1) from the peristome of arm (10), made the nitrogen circulation, inside is replaced into nitrogen.Then, set the flow of nitrogen with under meter (2), make thermal treatment pipe (1) nitrogen superficial linear velocity (here, the meaning of " superficial linear velocity " is the superficial linear velocity (following identical) of internal diameter 45mm part) be 0.30m/ second down at 200 ℃, heat of immersion treatment unit in being adjusted to 202 ℃ first oil bath (5).With this constantly as the starting point of the 1st section solid phase polycondensation under 200 ℃.After 4 hours, from the peristome taking-up intrinsic viscosity test sample of arm (10).After taking out sample, the flow of change nitrogen makes that the superficial linear velocity of nitrogen is down 1.0m/ second at 235 ℃, thermal treatment unit is moved to second oil bath (5) that is adjusted to 237 ℃.With this constantly as the starting point of the heating process under 235 ℃.After 10 minutes, from the peristome taking-up intrinsic viscosity test sample of arm (10).After taking out sample, the flow of change nitrogen makes that the superficial linear velocity of nitrogen is down 0.30m/ second at 230 ℃, thermal treatment unit is moved to the oil bath (5) that is adjusted to 232 ℃.With the starting point of this moment as 230 ℃ the 2nd section solid phase polycondensation.Light since the 2nd section solid phase polycondensation,, take out the intrinsic viscosity test sample, respectively its intrinsic viscosity is measured respectively through 12 hours, 24 hours, 36 hours.Heat-treat condition and measurement result are shown in the table 3.In the table, for example, by in rectangular coordinates, the data near IV=0.747 in the 2nd section solid phase polycondensation operation are coupled together with straight line, with the heat treatment time of IV=0.747 as the 2nd section solid phase polycondensation activity time, itself and the 1st section solid phase polycondensation activity time and heating process time are added together, try to achieve the time (IV=0.747 time of arrival) that intrinsic viscosity (IV) arrives 0.747dL/g.In addition, do not comprise the crystallization step time.
(embodiment 5)
Except with among the embodiment 4, by first oil bath temperature is set at 212 ℃, making the 1st section solid phase polycondensation temperature is 210 ℃, and its solid phase polycondensation time became outside 2 hours, and other and embodiment 4 carry out in the same manner.The result is shown in the table 3.
(embodiment 6)
Except the 1st solid phase polycondensation period among the embodiment 5 was become 4 hours, other and embodiment 5 carry out in the same manner.The result is shown in the table 3.
(comparative example 3)
Save whole operations of the 1st section solid phase polycondensation behind the input sample among the embodiment 5, and heating process and the 2nd section solid phase polycondensation carry out the samely with embodiment 5.The result is shown in the table 3.
(comparative example 4)
Except with among the embodiment 5, by first oil bath temperature is set at 222 ℃, making the 1st section solid phase polycondensation temperature is outside 220 ℃, and other and embodiment 5 carry out in the same manner.The result is shown in the table 3.
(comparative example 5)
Corresponding operating among the embodiment 5 is become: after the 1st section solid phase polycondensation, continuing impregnated under the state of first oil bath (5), the flow of change nitrogen, make that the superficial linear velocity of nitrogen is down 1.0m/ second at 220 ℃, temperature with the oil that made oil bath (5) in 120 minutes is warmed up to 232 ℃ continuously from 212 ℃, peristome from arm (10) after 120 minutes takes out the intrinsic viscosity test sample, continuing impregnated under the state of first oil bath (5), the flow of change nitrogen, make that the superficial linear velocity of nitrogen is down 0.30m/ second at 230 ℃, with this constantly as the 2nd section solid phase polycondensation starting point under 230 ℃, in addition, other and embodiment 5 carry out in the same manner, and the result is shown in the table 3.
Table 3
| The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.747 is Dao reaching Shi Jian ⊿ IV=0.500 hour | IV=0.777 is Dao reaching Shi Jian ⊿ IV=0.530 hour | IV=0.797 is Dao reaching Shi Jian ⊿ IV=0.550 hour | ||||||||||
| T1 ℃ | Reaction times hour | IV dL/g | ⊿IV dL/g | Th ℃ | Residence time branch | IV dL/g | ⊿IV dL/g | T2 ℃ | IV dL/g after 12 hours | IV dL/g after 24 hours | IV dL/g after 36 | ||||
| Embodiment | |||||||||||||||
| 4 | 200 | 4 | 0.314 | 0.064 | 235 | 10 | 0.338 | 0.024 | 230 | 0.763 | 0.959 | - | 15.7 | 17.0 | 18.2 |
| |
210 | 2 | 0.309 | 0.059 | 235 | 10 | 0.327 | 0.018 | 230 | 0.778 | 0.971 | 1.052 | 13.3 | 14.1 | 15.3 |
| |
210 | 4 | 0.348 | 0.098 | 235 | 10 | 0.372 | 0.024 | 230 | 0.833 | 0.989 | 1.090 | 13.9 | 14.7 | 15.2 |
| Comparative example 3 | - | 0 | - | - | 235 | 10 | 0.273 | - | 230 | 0.675 | 0.866 | 0.929 | 16.7 | 18.6 | 19.8 |
| Comparative example 4 | 220 | 2 | 0.362 | 0.112 | 235 | 10 | 0.315 | 0.013 | 230 | 0.719 | 0.845 | 0.905 | 16.8 | 19.7 | 21.6 |
| Comparative example 5 | 210 | 2 | 0.309 | 0.059 | 210-230 | 120 | 0.420 | 0.111 | 230 | 0.695 | 0.887 | 0.920 | 19.3 | 21.1 | 22.4 |
(embodiment 7)
Except changing the polyester prepolymer A among the embodiment 5 into polyester prepolymer B, be that other and embodiment 5 carry out in the same manner through outside 8 hours, 16 hours, 32 hours with the time change of the taking-up sample in the 2nd section solid phase polycondensation operation.The intrinsic viscosity IV of polyester prepolymer B after crystallization is handled is 0.380dL/g.The result is shown in the table 4.
(embodiment 8)
Except saving 235 ℃ of heating process behind the 1st section solid phase polycondensation among the embodiment 7, directly move to outside 230 ℃ the 2nd section solid phase polycondensation, other carry out with embodiment 7 the samely.The result is shown in the table 4.
(embodiment 9)
Corresponding operating among the embodiment 7 is become: after the 1st section solid phase polycondensation, continuing impregnated under the state of first oil bath (5), the flow of change nitrogen, make that the superficial linear velocity of nitrogen is down 1.0m/ second at 220 ℃, temperature with the oil that made oil bath (5) in 20 minutes is warmed up to 232 ℃ continuously from 212 ℃, peristome from arm (10) after 20 minutes takes out the intrinsic viscosity test sample, continuing impregnated under the state of first oil bath (5), the flow of change nitrogen, make that the superficial linear velocity of nitrogen is down 0.30m/ second at 230 ℃, this moment is begun as the 2nd section solid phase polycondensation under 230 ℃, in addition, other and embodiment 7 carry out in the same manner, and the result is shown in the table 4.
(comparative example 6)
Except saving the 1st section solid phase polycondensation and the 235 ℃ of heating process behind the input sample among the embodiment 7, directly move to outside 230 ℃ the 2nd section solid phase polycondensation, other carry out with embodiment 7 the samely.The result is shown in the table 4.
Table 4
| The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.873 is Dao reaching Shi Jian ⊿ IV=0.500 hour | IV=0.903 is Dao reaching Shi Jian ⊿ IV=0.530 hour | ||||||||||
| T1 ℃ | Reaction times hour | IV dL/g | ⊿IV dL/g | Th ℃ | Residence time branch | IV dL/g | ⊿IV dL/g | T2 ℃ | IV dL/g after 8 hours | IV dL/g after 16 hours | IV dL/g after 32 | |||
| Embodiment | ||||||||||||||
| 7 | 210 | 2 | 0.448 | 0.068 | 235 | 10 | 0.483 | 0.035 | 230 | 0.875 | 1.035 | - | 10.1 | 11.6 |
| |
210 | 2 | 0.448 | 0.068 | - | 0 | - | 0.000 | 230 | 0.830 | 0.982 | - | 12.3 | 13.8 |
| Embodiment 9 | 210 | 2 | 0.448 | 0.068 | 210-230 | 30 | 0.495 | 0.047 | 230 | 0.848 | 0.967 | - | 12.2 | 14.2 |
| Comparative example 6 | - | 0 | - | - | - | 0 | - | - | 230 | 0.809 | 0.899 | 1.021 | 13.7 | 16.5 |
In above-mentioned any embodiment, comparative example, the sample after this thermal treatment can easily take out from thermal treatment pipe (1), does not also find sample fusion adhesion each other.
In comparative example 3, the solid phase polycondensation operation is the 2nd section solid phase polycondensation operation of pyritous, and solid phase polycondensation speed is little.In comparative example 4, because the difference of the solid phase polycondensation temperature in the 1st section solid phase polycondensation operation and the 2nd section solid phase polycondensation operation is less than 15 ℃, so solid phase polycondensation speed is little.In comparative example 5, when the 1st section solid phase polycondensation operation finishes and the intrinsic viscosity difference of the 2nd section solid phase polycondensation operation when beginning more than 0.10dL/g, solid phase polycondensation speed is little.In comparative example 6, because be the 2nd section solid phase polycondensation operation of pyritous, so solid phase polycondensation speed is little.
(Production Example of PET prepolymer)
The manufacturing of＜PET prepolymer A 〉
Use possesses the PET prepolymer apparatus for continously production with lower device, promptly possesses: the slip preparation vessel with stirrer, ethylene glycol feeding pipe and terephthalic acid feeding pipe; Slip and reactant of esterification are transported to each pipeline of each esterification groove; First and second esterification groove of complete mixed type with stirrer, knockout tower, raw material receiving port, catalyst feed pipeline, reactant gas delivery path road; Reactant of esterification (oligopolymer) is transported to the pipeline of melt polycondensation reaction groove; The complete mixed type first melt polycondensation reaction groove with stirrer, knockout tower, oligopolymer receiving port, catalyst feed pipeline; Second and third melt polycondensation reaction groove of plug flow type with stirrer, knockout tower, oligopolymer receiving port, polymkeric substance conveying end; From the punch die fishplate bar prepolymer is strand form ground by conveying end by toothed gear pump and takes out,, cut off the granulation device (the strand cutter is that リ one one automatic company makes Fitz chilsonator (P-USG100)) of strand with under the water cooling.
At first, in the slip preparation vessel, modulation is added with terephthalic acid/ethylene glycol (mol ratio 1: 1.5) slip of ortho-phosphoric ethylene glycol solution (concentration: phosphorus atom is 0.50 quality %), ortho-phosphoric amount is the concentration that makes the phosphorus in the PET prepolymer that obtains, calculating with phosphorus atom, is the such amounts of 22 quality ppm.Again, two-(beta-hydroxy ethyl) terephthalate of 400 mass parts is thrown in the first esterification groove, fusion under nitrogen atmosphere, remain on temperature and be 262 ℃, pressure and be 96kPaG (below, G represents with respect to atmospheric relative pressure), to wherein with 135 mass parts/hour speed be dropped in synthetic slip in the described slip preparation vessel continuously, making the mean residence time as the PET prepolymer is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, esterification is carried out on the limit, and reaction solution is delivered to the second esterification groove continuously.
In the second esterification groove, in temperature is that 260 ℃, pressure are 5kPaG, the residence time to be under 1.5 hours the condition, the ethylene glycol solution (concentration: the concentration of antimony atoms is 1.8 quality %) of antimonous oxide is added on the limit continuously, esterification is carried out on the limit, by transfer line, to carry to the complete mixed type first melt polycondensation reaction groove, the amount of antimonous oxide is the concentration of the antimony in the resulting PET prepolymer, calculating with antimony atoms, is 183 quality ppm.In the first melt polycondensation reaction groove, the pressure of polycondensation groove be 2.5kPaA (below, A represents absolute pressure), temperature is that 273 ℃, the residence time are to react under 1.0 hours the condition, make the PET prepolymer that obtains by the second melt polycondensation reaction groove, the 3rd melt polycondensation reaction groove, being strand form ground from the punch die fishplate bar by toothed gear pump continuously by the polymkeric substance conveying end takes out, under current, cut off strand, obtain the particle (median size is 1.2mm) of the PET prepolymer A of 4000 mass parts.
The intrinsic viscosity of the PET prepolymer A that obtains is 0.247dL/g, and end carboxy concentration is 55 equivalent/tons.
The manufacturing of＜PET prepolymer B 〉
Use and be used to make the identical PET prepolymer apparatus for continously production of PET prepolymer A, carry out the manufacturing of PET prepolymer B.
At first, in the slip preparation vessel, modulation is added with terephthalic acid/ethylene glycol (mol ratio 1: 1.5) slip of the ethylene glycol solution (concentration: titanium atom is 0.075 quality %) of tetrabutyl titanate, the amount of tetrabutyl titanate is the concentration that makes the titanium in the PET prepolymer that obtains, calculating with titanium atom, is the such amounts of 8 quality ppm.Again, two-(beta-hydroxy ethyl) terephthalate of 400 mass parts is thrown into the first esterification groove, fusion under nitrogen atmosphere, remaining on temperature and be 262 ℃, pressure is 96kPaG, to wherein with 135 mass parts/hour speed be dropped in synthetic slip in the described slip preparation vessel continuously, making the mean residence time as the PET prepolymer is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, esterification is carried out on the limit, and reaction solution is delivered to the second esterification groove continuously.
In the second esterification groove, be that 260 ℃, pressure are 5kPaG, the residence time to be to react under 1.5 hours the condition in temperature, reactant by transfer line, is carried to the complete mixed type first melt polycondensation reaction groove continuously.
In the first melt polycondensation reaction groove, the ethylene glycol solution (concentration: magnesium atom is 0.040 quality %) of magnesium acetate 4 water salt and the ethylene glycol solution (concentration: phosphorus atom is 0.030 quality %) of acid phosphate ester are added continuously in the limit in the reaction liquid phase, the amount of magnesium acetate 4 water salt is the concentration that makes the magnesium in the PET prepolymer that obtains, calculate with the magnesium atoms metal, be the such amounts of 8 quality ppm, and the amount of acid phosphate ester is the concentration that makes the phosphorus in the PET prepolymer that obtains, calculate with phosphorus atom, be the such amounts of 8 quality ppm, the limit is 4.5kPaA at the pressure of polycondensation groove, temperature is 271 ℃, the residence time is to react under 1.0 hours the condition, and reactant is delivered to the second melt polycondensation reaction groove continuously.In the second melt polycondensation reaction groove, be that 3.5kPaA, temperature are that 274 ℃, the residence time are under 1.0 hours the condition at pressure, carry out melt polycondensation reaction, by transfer line, reactant is carried to the 3rd melt polycondensation reaction groove continuously.
In the 3rd melt polycondensation reaction groove, be that 3.5kPaA, temperature are that 275 ℃, the residence time are to carry out melt polycondensation reaction under 1.2 hours the condition at pressure.Continuously the PET prepolymer that obtain be strand form ground by conveying end from the punch die fishplate bar by toothed gear pump and take out, under current, cut off strand, obtain the particle (median size 1.2mm) of the PET prepolymer B of 4000 mass parts.
The intrinsic viscosity of the PET prepolymer B that obtains is 0.308dL/g, and end carboxy concentration is 35 equivalent/tons.
＜crystallization step 〉
The particle of the PET prepolymer A that 30g is obtained by above-mentioned Production Example launches to be positioned over the square that the bottom surface is 130mm * 170mm, the stainless steel container made (vat) that the degree of depth is 30mm, put the gas inside temperature into and be 180 ℃ thermostat container (oven) (the IPHH-201M type that Tabaiespec company makes), at the flow of the nitrogen of thermostat container internal circulation is that 50NL/ branch, temperature are that the crystallization that carried out under 180 ℃ 1 hour is handled under 180 ℃ the nitrogen circulation.Here, NL is meant the volume (L) under 0 ℃ of 1 air pressure.
The intrinsic viscosity of sample PET prepolymer A after crystallization is handled is 0.250dL/g.
Particle to PET prepolymer B carries out same crystallization processing.The intrinsic viscosity IV of sample PET prepolymer B after crystallization is handled is 0.321dL/g.
(embodiment 10)
Thermal treatment unit with glass shown in Figure 1 is heat-treated the particle of the PET prepolymer A of above-mentioned crystallization processing.
For this thermal treatment unit, the same with above-mentioned explanation.
The particle of the PET prepolymer A after crystallization is handled that 30g is above-mentioned is thrown into thermal treatment pipe (1) from the peristome of arm (10), makes the nitrogen circulation, and inside is replaced into nitrogen.Then, set the flow of nitrogen with under meter (2), make the nitrogen in the thermal treatment pipe (1) superficial linear velocity (here, the meaning of " superficial linear velocity " is the superficial linear velocity (following identical) of internal diameter 45mm part) under 200 ℃, be 0.30m/ second, heat of immersion treatment unit in being adjusted to 202 ℃ first oil bath (5).With this constantly as the beginning of the 1st section solid phase polycondensation under 200 ℃.After 4 hours, from the peristome taking-up intrinsic viscosity test sample of arm (10).After taking out sample, the flow of change nitrogen makes that the superficial linear velocity of nitrogen is down 1.0m/ second at 235 ℃, thermal treatment unit is moved to second oil bath (5) that is adjusted to 237 ℃.With this constantly as the beginning of the heating process under 235 ℃.After 10 minutes, from the peristome taking-up intrinsic viscosity test sample of arm (10).
After taking out sample, the flow of change nitrogen makes that the superficial linear velocity of nitrogen is down 0.30m/ second at 235 ℃, thermal treatment unit is moved to the oil bath (5) that is adjusted to 232 ℃.This moment is begun as the 2nd section solid phase polycondensation under 230 ℃.Light since the 2nd section solid phase polycondensation,, take out the intrinsic viscosity test sample respectively through 12 hours, 24 hours, 36 hours.To behind the 1st section solid phase polycondensation, reach the test sample that takes out behind the 2nd section solid phase polycondensation behind the heating process, measure intrinsic viscosity respectively.Heat-treat condition and measurement result are shown in the table 5.In the table, by in rectangular coordinates, to couple together with straight line near the data of IV=0.90, with the heat treatment time of IV=0.90 as the 2nd section solid phase polycondensation activity time, itself and the 1st section solid phase polycondensation activity time and heating process time are added together, try to achieve the time that intrinsic viscosity IV arrives 0.90dL/g.Do not comprise the crystallization step time.
(embodiment 11)
Except with among the embodiment 10 by first oil bath temperature is set at 212 ℃, making the 1st section solid phase polycondensation temperature is 210 ℃, its solid phase polycondensation time became outside 2 hours, other and embodiment 10 carry out in the same manner.The result is shown in table 5.
(embodiment 12)
Except the 1st solid phase polycondensation period among the embodiment 11 was become 4 hours, other and embodiment 11 carry out in the same manner.The result is shown in the table 5.
(embodiment 13)
Except the 1st solid phase polycondensation period among the embodiment 11 was become 8 hours, other and embodiment 11 carry out in the same manner.The result is shown in the table 5.
(comparative example 7)
Whole operations of the 1st section solid phase polycondensation behind the particle of the PET prepolymer A after saving input crystallization among the embodiment 11 and handling, and heating process and the 2nd section solid phase polycondensation carry out with embodiment 11 the samely.The result is shown in the table 5.
(comparative example 8)
Except with among the embodiment 11 by first oil bath temperature is set at 222 ℃, making the 1st section solid phase polycondensation temperature is outside 220 ℃, other and embodiment 11 carry out in the same manner.The result is shown in the table 5.
(embodiment 14)
Change the particle of PET prepolymer B into except the particle of the PET prepolymer A after the crystallization among the embodiment 11 is handled; with the time change of the taking-up sample in the 2nd section solid phase polycondensation operation is outside 8 hours, 16 hours, 32 hours, and other and embodiment 11 carry out in the same manner.The result is shown in the table 6.In the table, by in rectangular coordinates, to couple together with straight line near the data of IV=0.80, with the heat treatment time of IV=0.80 as the 2nd section solid phase polycondensation activity time, itself and the 1st section solid phase polycondensation activity time and heating process time are added together, try to achieve the time that intrinsic viscosity arrives IV=0.80dL/g.Do not comprise the crystallization step time.
(embodiment 15)
Except saving 235 ℃ of heating process behind the 1st section solid phase polycondensation among the embodiment 14, directly move to outside 230 ℃ the 2nd section solid phase polycondensation, other carry out with embodiment 14 the samely.The result is shown in the table 6.
(comparative example 9)
Except the corresponding section among the embodiment 15 is become by first oil bath temperature is set at 222 ℃, making the 1st section solid phase polycondensation temperature is outside 220 ℃, and other and embodiment 15 carry out in the same manner.The result is shown in the table 6.
(comparative example 10)
Except the 1st section solid phase polycondensation and the 235 ℃ of heating process behind the particle of the PET prepolymer B after saving input crystallization among the embodiment 14 and handling, directly move to outside 230 ℃ the 2nd section solid phase polycondensation, other carry out with embodiment 14 the samely.The result is shown in the table 6.
Table 5
| The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.90 time of arrival hour | |||||||||
| T1 ℃ | Reaction times hour | IV dL/g | ⊿IV dL/g | Th ℃ | Residence time branch | IV dL/g | T2 ℃ | IV dL/g after 12 hours | IV dL/g after 24 hours | IV dL/g after 36 | ||
| Embodiment | ||||||||||||
| 10 | 200 | 4 | 0.314 | 0.064 | 235 | 10 | 0.338 | 230 | 0.763 | 0.959 | --- | 24.6 |
| |
210 | 2 | 0.309 | 0.059 | 235 | 10 | 0.327 | 230 | 0.778 | 0.971 | 1.052 | 21.8 |
| |
210 | 4 | 0.348 | 0.098 | 235 | 10 | 0.372 | 230 | 0.833 | 0.989 | 1.090 | 21.3 |
| Embodiment 13 | 210 | 8 | 0.421 | 0.171 | 235 | 10 | 0.436 | 230 | 0.860 | 1.049 | --- | 22.7 |
| Comparative example 7 | --- | 0 | --- | --- | 235 | 10 | 0.273 | 230 | 0.675 | 0.866 | 0.929 | 30.6 |
| Comparative example 8 | 220 | 2 | 0.362 | 0.112 | 235 | 10 | 0.375 | 230 | 0.719 | 0.845 | 0.905 | 37.2 |
Table 6
| The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.80 time of arrival hour | |||||||||
| T1 ℃ | Reaction times hour | IV dL/g | ⊿IV dL/g | Th ℃ | Residence time branch | IV dL/g | T2 ℃ | IV dL/g after 8 hours | IV dL/g after 16 hours | IV dL/g after 32 hours | ||
| Embodiment 14 | 210 | 2 | 0.407 | 0.086 | 235 | 10 | 0.442 | 230 | 0.792 | 0.853 | 0.976 | 12.3 |
| Embodiment 15 | 210 | 2 | 0.407 | 0.086 | --- | 0 | --- | 230 | 0.760 | 0.816 | 0.936 | 15.7 |
| Comparative example 9 | 220 | 2 | 0.440 | 0.119 | --- | 0 | --- | 230 | --- | 0.767 | 0.878 | 22.8 |
| Comparative example 10 | --- | 0 | --- | --- | --- | 0 | --- | 230 | --- | 0.770 | 0.867 | 21.0 |
In above-mentioned any embodiment, comparative example, the sample after this thermal treatment can easily take out from thermal treatment pipe (1), does not also find sample fusion adhesion each other.
In comparative example 7, the solid phase polycondensation operation is the 2nd section of a pyritous, and solid state polycondensation speed is little.
In comparative example 8,9, because the difference of the solid phase polycondensation temperature in the 1st section and the 2nd section is less than 15 ℃, so solid state polycondensation speed is little, in comparative example 10, because be the 2nd section of pyritous, so solid state polycondensation speed is little.
(embodiment 16)
The manufacturing of＜PET prepolymer C 〉
By the used PET prepolymer apparatus for continously production of the manufacturing of using above-mentioned PET prepolymer A, make dicarboxylic acid and dibasic alcohol carry out esterification, carry out melt polycondensation reaction again, obtain the PET prepolymer of molten state, this PET prepolymer is strand form ground from the punch die fishplate bar to be taken out, cut off, make PET prepolymer C thus.Specific as follows described.
In the slip preparation vessel, modulation contains the slip of the terephthalic acid/ethylene glycol (mol ratio 1: 1.5) of tetra-n-butyl titanate, and the amount of tetra-n-butyl titanate is with respect to PET, is the such amounts of 4 quality ppm as titanium atom.Again, two-(beta-hydroxy ethyl) terephthalate of 400 mass parts is thrown into esterification first groove, fusion under nitrogen atmosphere, remaining on temperature and be 262 ℃, pressure is 96kPaG (G represents with respect to atmospheric relative pressure), to wherein with 135 mass parts/hour speed drop into continuously described in the slip preparation vessel synthetic slip, making the mean residence time as polyester is 4.5 hours, the limit is distilled the water that generates in the knockout tower and is removed, esterification is carried out on the limit, and reaction solution is delivered to esterification second reactive tank continuously.
In the second esterification groove, be that 260 ℃, pressure are 5kPaG, the residence time to be to carry out esterification under 1.5 hours the condition in temperature, by transfer line, carry continuously to the complete mixed type first melt polycondensation reaction groove.
In the first melt polycondensation reaction groove, be that 270 ℃, pressure are 4.0kPaA (A represents absolute pressure), the residence time to be to react under 1.0 hours the condition in temperature, by transfer line, carry continuously to the second melt polycondensation reaction groove.In the second melt polycondensation reaction groove, be that 270 ℃, pressure are 4.0kPaA, the residence time to be to carry out melt polycondensation reaction under 1.0 hours the condition in temperature, by transfer line, carry to the 3rd melt polycondensation reaction groove.In the 3rd melt polycondensation reaction groove, be that 270 ℃, pressure are 4.0kPaA, the residence time to be to carry out melt polycondensation reaction under 1.2 hours the condition in temperature.
The fusion PET prepolymer that will obtain as above-mentioned by toothed gear pump and taking-up pipeline, imports die head like this, is strand form from nib and takes out, after water cooling, by Fitz chilsonator (P-USG100) granulation of リ one one automatic company manufacturing.Prilling process is the strand cutting method, specifically, the limit makes strand form PET prepolymer contact with water to cool off, Bian Yushui is together to the tool orientation conveyance, by pulling the roller clamping and pull with being arranged on a pair of before the cutter, supply with to cutter, cut off, obtain the particle of PET prepolymer C thus with cutter with fixed teeth and turning gear.
Here, the output of fusion PET prepolymer is 60kg/ hour, and temperature is 270 ℃, makes its punch die fishplate bar from circular nib that 4 3mm are arranged be strand form and discharges, and will become 15 ° angle as discharging direction downwards from horizontal direction.
Make this strand form PET prepolymer through the above air cooling distance of 100mm, arrive the water cooling zone of strand cutter, the conveyance of water cooling limit is carried out on the limit in 50 ℃ water, pull with pulling roller, supplies with to cutter.The speed of pulling of strand is 3.00m/ second, adjusts the ratio of the rotation number that pulls roller and turning gear of cutter, and making particle is 1.0mm in the length that pulls direction, carries out granulating.
As a result, obtain shape approximation has the oval column of semicolumn in the two ends that are roughly rectangular parallelepiped at long 1.0mm, wide 1.3mm, thickness 0.9mm the particle of PET prepolymer C.This particulate intrinsic viscosity is 0.290dL/g, and end carboxy concentration is 22 equivalent/tons, and the copolymerization amount of Diethylene Glycol is 2.0 moles of %, and average quality is the 1.5mg/ grain.The back is called " prepolymer C " with the particle of this PET prepolymer C.
＜thermal treatment 〉
＜crystallization step 〉
The prepolymer C that 30g is above-mentioned launches to be positioned over the square that the bottom surface is 130mm * 170mm, the stainless steel container made that the degree of depth is 30mm, put the gas inside temperature into and be 180 ℃ thermostat container (the IPHH-201M type that Tabaiespec company makes), at the flow of the nitrogen of thermostat container internal circulation is that 50NL/ branch, temperature are under 180 ℃ the nitrogen circulation, under Tx=180 ℃, the crystallization that carried out 1 hour is handled.Here, NL is the volume (L) in 0 ℃ of 1 air pressure.The intrinsic viscosity of the sample after crystallization is handled is 0.290dL/g, and the crystallization degree is 53 quality %.
＜thermal treatment unit 〉
With the thermal treatment unit of glass shown in Figure 1 the above-mentioned sample that prepolymer C is carried out after crystallization is handled is heat-treated.About this thermal treatment unit, as mentioned above.
＜the first section solid phase polycondensation operation 〉
The particle of the prepolymer C of 30g after above-mentioned crystallization is handled is thrown in the thermal treatment pipe (1) from the peristome of arm (10), made the nitrogen circulation, inside is replaced into nitrogen.Then, set the flow of nitrogen with gas meter (2), make the nitrogen in the thermal treatment pipe (1) superficial linear velocity (here, the meaning of " superficial linear velocity " is the superficial linear velocity (following identical) of sample layer) under 210 ℃, be 0.30m/ second, heat of immersion treatment unit in being adjusted to 212 ℃ first oil bath (5).To be somebody's turn to do the beginning of the moment as the 1st section solid phase polycondensation operation (T1=210 ℃).After 2 hours, from the about 0.3g intrinsic viscosity mensuration of the peristome taking-up sample of arm (10).
＜heating process 〉
After taking out sample, the flow of change nitrogen makes the superficial linear velocity of nitrogen be 1.0m/ second down at 235 ℃, and the temperature regulation that thermal treatment unit is moved to oil is 237 ℃ second oil bath (5).To be somebody's turn to do the beginning of the moment as heating process (T2=235 ℃).Because the temperature of sample arrives 235 ℃ of needs 10 minutes, so the intensification from T1 to (T1+15 ℃) is in 10 minutes.After beginning 10 minutes from heating process, take out intrinsic viscosity from the peristome of arm (10) and measure and use sample.
＜the 2 section solid phase polycondensation operation 〉
After taking out sample, the flow of change nitrogen makes the superficial linear velocity of nitrogen be 0.30m/ second down at 230 ℃, and the temperature regulation that thermal treatment unit is moved to oil is 232 ℃ the 3rd oil bath (5).To be somebody's turn to do the beginning of the moment as the 2nd section solid phase polycondensation operation (T3=230 ℃).Light since the 2nd section solid phase polycondensation, as required,, take out intrinsic viscosity mensuration sample respectively through 8 hours, 16 hours, 32 hours.
To behind the 1st section solid phase polycondensation, the test sample that takes out when reaching the 2nd section solid phase polycondensation behind the heating process is measured intrinsic viscosity respectively.Heat-treat condition and measurement result are shown in 7[VII-A] in.In the table, by in rectangular coordinates, to couple together with straight line near the data before and after the IV=0.80, try to achieve the heat treatment time of IV=0.80 with interpolation, as the 2nd section solid phase polycondensation activity time, itself and the 1st section solid phase polycondensation activity time and heating process time are added together, try to achieve the time when reaching intrinsic viscosity IV=0.80dL/g, do not comprise the time of crystallization step
(comparative example 11)
The heating process in not implementing embodiment 16 fully, other and embodiment 16 carry out in the same manner.The result is shown in 7[VII-A] in.
During this example,, compare so arrive time and the embodiment 13 of IV=0.80dL/g owing to do not implement 235 ℃ heating process, elongated.
(embodiment 17)
Except with embodiment 16＜manufacturing of PET prepolymer C in the output of fusion PET prepolymer change to 100kg/ hour, other and embodiment 16＜manufacturing of PET prepolymer C carry out in the same manner.
As a result, the two ends that are roughly rectangular parallelepiped that obtain approaching long 1.0mm, wide 1.6mm, thickness 1.2mm have the PET prepolymer particle C ' of oval column of the shape of semicolumn.The intrinsic viscosity of this particle C ' is 0.290dL/g, and end carboxy concentration is 22 equivalent/tons, and the copolymerization amount of Diethylene Glycol is 2.0 moles of %, and average quality is the 2.3mg/ grain.
Except using this PET prepolymer particle C ', other and embodiment 16＜thermal treatment〉handle in the same manner.The result is shown in 7[VII-A].
(comparative example 12)
The heating process in not implementing embodiment 17, other and embodiment 17 carry out in the same manner.The result is shown in 7[VII-A] in.
During this example,, compare so arrive time and the embodiment 17 of IV=0.80dL/g owing to do not implement 235 ℃ heating process, elongated.In addition, lighted the straight line of 16 hours, 32 hours intrinsic viscosity measurement result since the 2nd section solid phase polycondensation, inserted in IV=0.80 outward, extrapolated the time that arrives IV=0.80dL/g by drawing a connection.
(comparative example 13)
Except the temperature with the heating process among the embodiment 16 changes to 220 ℃, other and embodiment 16 carry out in the same manner.The result is shown in 7[VII-A] in.
During this example,, be 10 ℃, do not satisfy (formula 1), compare so arrive time and the embodiment 16 of IV=0.80dL/g owing to the temperature head between the 1st section solid phase polycondensation operation and the heating process is less, elongated.
(comparative example 14)
Except the heat-up rate in the heating process of embodiment 16 being set at 0.42 ℃/minute and will be set at the heating-up time 60 minutes, other and embodiment 16 carry out in the same manner.The result is shown in 7[VII-A] in.
During this example, owing to arrive 235 ℃ time above 30 minutes, longer, compare so arrive time and the embodiment 13 of IV=0.80dL/g, elongated.
(embodiment 18)
The manufacturing of＜PET prepolymer D 〉
Except with embodiment 16＜manufacturing of PET prepolymer C in synthetic slip in the slip preparation vessel change to the slip of the terephthalic acid/isophthalic acid/ethylene glycol (mol ratio is 0.97: 0.03: 1.5) that contains tetra-n-butyl titanate, and the amount of this tetra-n-butyl titanate is with respect to resultant PET, as titanium atom is the such amounts of 8 quality ppm, the pressure of the first melt polycondensation reaction groove is changed to 3.8kPaA, the temperature of second and third melt polycondensation reaction groove is changed to 275 ℃, pressure changes to 3.8kPaA, the punch die fishplate bar is changed to punch die fishplate bar with 10 nib numbers, the output of molten polyester was changed to outside 78kg/ hour, other are identical with embodiment 16, obtain PET prepolymer particle.As a result, the two ends that are roughly rectangular parallelepiped that obtain approaching long 1.0mm, wide 1.0mm, thickness 0.7mm have the particle of PET prepolymer D of oval column of the shape of semicolumn.This particulate intrinsic viscosity is 0.323dL/g, and end carboxy concentration is 26 equivalent/tons, and the copolymerization amount of m-phthalic acid, Diethylene Glycol is respectively 2.9 moles of %, 2.2 moles of %, and average quality is the 1.4mg/ grain.The back is called " prepolymer D " with the particle of this PET prepolymer D.
＜thermal treatment 〉
Except sample being changed above-mentioned prepolymer D, the condition of the 1st section solid phase polycondensation operation, heating process, the 2nd section solid phase polycondensation operation is changed to table 7[VII-B respectively] shown in condition, measure time change with sample for to cross outside 16 hours, 32 hours from starting point with taking out intrinsic viscosity in the 2nd section solid phase polycondensation, other and embodiment 16 carry out＜thermal treatment in the same manner 〉.
The intrinsic viscosity of the sample after crystallization is handled is 0.331dL/g.Heat-treat condition and measurement result are shown in 7[VII-B] in.
(comparative example 15)
The heating process in not implementing embodiment 18, other and embodiment 18 carry out in the same manner.The result is shown in 7[VII-B] in.
During this example,, compare so arrive time and the embodiment 15 of IV=0.80dL/g owing to do not implement 225 ℃ heating process, elongated.
(embodiment 19)
Except the condition with the 1st section and the 2nd section solid phase polycondensation operation among the embodiment 18 change to respectively the table 7[VII-C] shown in condition, the time change that taking-up intrinsic viscosity in the 2nd section solid phase polycondensation is measured with sample is outside 24 hours, and other and embodiment 18 carry out＜thermal treatment in the same manner 〉.The result is shown in 7[VII-C] in.
In the table, by in rectangular coordinates, the 24th hour data and the data before it are coupled together with straight line, try to achieve the heat treatment time of IV=0.70 with interpolation, as the 2nd section solid phase polycondensation activity time, itself and the 1st section solid phase polycondensation activity time and heating process time are added together, try to achieve the time when reaching intrinsic viscosity IV=0.70dL/g, do not contain the time of crystallization step.
(embodiment 16)
The heating process in not implementing embodiment 19, other and embodiment 19 carry out in the same manner.The result is shown in 7[VII-C] in.
During this example,, compare so arrive time and the embodiment 19 of IV=0.70dL/g owing to do not implement 235 ℃ heating process, elongated.
(embodiment 20)
Except the condition with the 1st section solid phase polycondensation operation among the embodiment 19 change to the table 7[VII-C] shown in condition, other and embodiment 19 carry out in the same manner.The result is shown in 7[VII-C] in.
(comparative example 17)
The heating process in not implementing embodiment 20, other and embodiment 20 carry out in the same manner.The result is shown in 7[VII-C] in.
During this example,, compare so arrive time and the embodiment 20 of IV=0.70dL/g owing to do not implement 235 ℃ heating process, elongated.
Table 7
[VII-A]
| Prepolymer particulate quality mg/ grain | The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.80 time of arrival hour | ||||||||
| T1 ℃ | Reaction times hour | IV dL/g | T2 ℃ | The heating-up time branch | IV dL/g | T3 ℃ | IV dL/g after 8 hours | IV dL/g after 16 hours | IV dL/g after 32 hours | |||
| Embodiment 16 | 1.5 | 210 | 2 | 0.380 | 235 | 10 | 0.392 | 230 | 0.708 | 0.817 | 0.942 | 16.9 |
| Comparative example 11 | 1.5 | 210 | 2 | 0.380 | --- | --- | --- | 230 | 0.600 | 0.694 | 0.816 | 31.9 |
| Embodiment 17 | 2.3 | 210 | 2 | 0.352 | 235 | 10 | 0.360 | 230 | 0.657 | 0.765 | 0.879 | 20.8 |
| Comparative example 12 | 2.3 | 210 | 2 | 0.352 | --- | --- | --- | 230 | 0.557 | 0.637 | 0.762 | 38.9 |
| Comparative example 13 | 1.5 | 210 | 2 | 0.380 | 220 | 10 | 0.384 | 230 | 0.610 | 0.701 | 0.822 | 26.9 |
| Comparative example 14 | 1.5 | 210 | 2 | 0.380 | 235 | 60 | 0.419 | 230 | 0.652 | 0.737 | 0.850 | 24.1 |
[VII-B]
| Prepolymer particulate quality mg/ grain | The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.80 time of arrival hour | |||||||
| T1 ℃ | Reaction times hour | IV dL/g | T2 ℃ | The heating-up time branch | IV dL/g | T3 ℃ | IV dL/g after 16 hours | IV dL/g after 32 hours | |||
| Embodiment 18 | 1.4 | 200 | 4 | 0.390 | 225 | 10 | 0.403 | 220 | 0.781 | 0.904 | 22.6 |
| Comparative example 15 | 1.4 | 200 | 4 | 0.390 | --- | --- | --- | 220 | 0.696 | 0.806 | 35.1 |
[VII-C]
| Prepolymer particulate quality mg/ grain | The 1st section solid phase polycondensation operation | Heating process | The 2nd section solid phase polycondensation operation | IV=0.70 time of arrival hour | ||||||
| T1 ℃ | Reaction times hour | IV dL/g | T2 ℃ | The heating-up time branch | IV dL/g | T3 ℃ | IV dL/g after 24 hours | |||
| Embodiment 19 | 1.4 | 210 | 2 | 0.399 | 235 | 10 | 0.423 | 215 | 0.850 | 17.7 |
| Comparative example 16 | 1.4 | 210 | 2 | 0.399 | --- | --- | --- | 215 | 0.702 | 25.8 |
| Embodiment 20 | 1.4 | 220 | 2 | 0.453 | 235 | 10 | 0.472 | 215 | 0.774 | 20.3 |
| Comparative example 17 | 1.4 | 220 | 2 | 0.453 | --- | --- | --- | 215 | 0.746 | 22.2 |
(embodiment 21)
＜fusion adherence test 〉
PET particulate fusion tackiness when adjusting thermal treatment, use be implemented into the heating process of embodiment 13 the PET particle (below, be called " particle C behind the heating process "), carry out in the fusion adherence test of bearing under the state of load with fusion adherence test device shown in Figure 2.
Below, this fusion adherence test device is described.
In fusion adherence test device as shown in Figure 2, the internal diameter that sample is filled in the sample filling part is in the glass thermal treatment pipe (21) of 14mm.Via gas meter (22), nitrogen ingress pipe (23), nitrogen preheating tube (24), the oil of being filled by oil bath (25) carries out heated nitrogen and is led thermal treatment pipe (21).By being in the breaker plate (26) of thermal treatment pipe (21) bottom, the nitrogen that imports is disperseed, have the roughly upwelling of the linear velocity of homogeneous inner formation of thermal treatment pipe (21), by sample layer (27).Nitrogen by sample layer (27) passes through the strainer (28) that is in thermal treatment pipe (21) top, is discharged to the outside of thermal treatment pipe (21) from gas sweetening mouth (29).Here, the temperature of the sample that thermal treatment pipe (21) is inner is measured with the thermometer that possesses thermopair by being pre-charged with other sample, is confirmed to be the temperature that equates with oil temperature in the oil bath.By stainless steel wire cloth (30), stainless steel hollow leg (31) can be placed on the top of sample layer (27) again.On pillar (31), can will place the pedestal (33) fixing (quality of pillar (31) is 80g, and the total mass of pin (32) and pedestal (33) is 42g) that counterweight is used with pin (32) again.
Toward thermal treatment pipe (21) drop into 8g as the heating process of sample after particle C, place wire cloth (30) and pillar (31) thereon after, nitrogen is circulated, inside is replaced into nitrogen.Then, set the flow of nitrogen with gas meter (22), make the nitrogen in the thermal treatment pipe (21) superficial linear velocity (here, the meaning of " superficial linear velocity " is the superficial linear velocity (following identical) of sample layer segment) be down 0.40m/ second at 230 ℃, impregnated with molten adherence test device in being adjusted to 235 ℃ oil bath (25).Kept 10 minutes, the temperature that makes the sample layer is 235 ℃ like this.Then, with 10 minutes, the temperature of the oil that oil bath (25) is filled was reduced to 230 ℃.With this constantly as the beginning of the fusion adherence test under 230 ℃.From beginning by 1st hour, sample layer (27) load that is born just is equivalent to the quality (80g is heavy) of pillar (30).At 1st hour, go up mount pin (32) and pedestal (33) at pillar (30), the load that sample bore is that 122g is heavy.In the time of the 1.5th hour, put counterweight on pedestal (33), loading is the 160g weight.After, per 0.5 hour, just increase the load that 196g is heavy, 231g is heavy, 265g is heavy, 298g is heavy, 330g is heavy, be that 1039g is heavy from the 4.5th hour to the 5th hour load.The 5th hour, fusion adherence test device is taken out from oil bath, place 10 minutes the cooling after, stop the nitrogen that circulates, remove counterweight (comprising pillar, pin, pedestal).Sample is removed and is placed on the sieve that mesh is 2.0mm, leaves standstill and carries out gradation, measures fusion adherence ratio (mass ratio of the sample on the sieve).
The fusion adherence ratio is 0.4 quality %, and it is good that the result shows 230 ℃, the refractory under load melts tackiness.
(embodiment 22)
＜fusion adherence test 〉
Except the sample among the embodiment 21 being changed to the PET particle of the heating process that is implemented among the embodiment 19, set the flow of nitrogen with under meter (22), make that superficial linear velocity is down 0.40m/ second at 215 ℃, be adjusted to 235 ℃ oil bath (25) with 10 minutes the cooling temperature change to 215 ℃, this refractory that changes to constantly under 215 ℃ is melted outside the beginning of adherence test, and other carry out similarly to Example 21.
The fusion adherence ratio is 11 quality %.
(embodiment 23)
Except the time change with the 1st section solid phase polycondensation operation among the embodiment 19 is 4 hours, other are identical with embodiment 19, proceed to heating process.Resulting PET particulate intrinsic viscosity is 0.476Dl/g.
＜fusion adherence test 〉
Except the sample among the embodiment 22 being changed to the PET particle that above-mentioned intrinsic viscosity is 0.476dL/g, other and embodiment 22 carry out in the same manner.
The fusion adherence ratio is 0.3 quality %, and the result shows that the sample more used than embodiment 22 is good.
(embodiment 24)
The prepolymer D that uses embodiment 18 to be put down in writing, the heat treated heat treatment test under the solid state is carried out in enforcement continuously.That is, prepolymer D is supplied with continuously to the fluidized-bed of complete mixed type, at superficial linear velocity be under 3.2m/ second, 120 ℃ the air atmosphere, carry out the 1st section crystallization under 60 minutes the condition of mean residence time and handle (crystallization step), discharge continuously.Make resulting sample through transfer line, supply with to fluidized-bed continuously with plug flow, at superficial linear velocity be under 1.3m/ second, 180 ℃ the nitrogen atmosphere, carry out the 2nd section crystallization under 15 minutes the condition of mean residence time and handle (crystallization step), discharge continuously.Make resulting sample through transfer line, supply with to moving-bed continuously, under 210 ℃ the nitrogen atmosphere, carry out the 1st section solid phase polycondensation under 120 minutes the condition of mean residence time and handle (the 1st section solid phase polycondensation operation), discharge continuously.The sample that obtains is placed cooling for the time being under nitrogen atmosphere.The intrinsic viscosity of placing cooled sample is 0.347dL/g.
Supply with continuously to the fluidized-bed of complete mixed type placing the refrigerative sample for the time being, be under 3.2m/ second, 180 ℃ the air atmosphere, heat up again under 10 minutes the condition of mean residence time, discharge continuously at superficial linear velocity.Make resulting sample through transfer line, supply with to fluidized-bed continuously with plug flow, be under 1.6m/ second, 240 ℃ the nitrogen atmosphere, carry out hyperthermic treatment (heating process) under 15 minutes the condition of mean residence time at superficial linear velocity, discharge continuously.The temperature that is about to out the sample in heating process exit is 232 ℃.Make resulting sample through transfer line, supply with to moving-bed continuously, under 215 ℃ the nitrogen atmosphere, mean residence time is to carry out the 2nd section solid phase polycondensation under 14 hours the condition to handle, discharge continuously.
The sample that obtains is placed cooling under nitrogen atmosphere.The intrinsic viscosity of placing cooled sample is 0.737dL/g.
(embodiment 25)
Get the sample in the heating process exit among the embodiment 24.The intrinsic viscosity of this sample is 0.386dL/g.With the thermal treatment pipe (1) of this sample of 30g from the peristome input of arm (10) thermal treatment unit shown in Figure 1, make the nitrogen circulation, inside is replaced into nitrogen.Use gas meter (2) to set the flow of nitrogen then, make the superficial linear velocity of the nitrogen in the thermal treatment pipe (1) be 0.30m/ second down, heat of immersion treatment unit in being adjusted to 212 ℃ oil bath (5) at 210 ℃.With this constantly as the beginning of the 2nd solid phase polycondensation under 210 ℃.Since the 2nd section solid phase polycondensation moment of 32 hours and 64 hours, from the peristome of arm (10), take out intrinsic viscosity and measure and use sample.
The intrinsic viscosity of these samples is respectively 0.741dL/g and 0.853dL/g.Again, the time of intrinsic viscosity arrival 0.70dL/g and 0.80dL/g was respectively 30.6 hours, 51.1 hours.
In addition, in this example, the 1st section solid phase polycondensation operation, heating process carry out with 210 ℃ continuous moving-bed, 232 ℃ continuous fluidized bed respectively, and the 2nd section solid phase polycondensation operation implemented with 210 ℃ fixed bed in batches.
(comparative example 18)
After being taken at the 1st section solid phase polycondensation processing among the embodiment 24, under nitrogen atmosphere, place the refrigerative sample.The intrinsic viscosity of this sample is 0.347dL/g.Except that using this sample, other and embodiment 25 heat-treat in the same manner, choose intrinsic viscosity mensuration sample.
The intrinsic viscosity of these samples is respectively 0.681dL/g and 0.777dL/g.Again, the time of intrinsic viscosity arrival 0.70dL/g and 0.80dL/g was respectively 40.3 hours, 73.7 hours.
In this comparative example, owing to do not implement heating process, so result and embodiment 25 comparisons, solid state polycondensation speed is little.
In addition, in this embodiment, the 1st section solid phase polycondensation operation carried out with 210 ℃ continuous moving-bed, do not carry out heating process, the 2nd section solid phase polycondensation operation with 210 ℃ in batches fixed bed implement.
The application is willing to that based on the spy of application on October 21st, 2005 spy of application on September 1st, 2005-307326 number 1 is willing to that the spy of application on September 7th, 2005-253286 number 1 is willing to 2005-259383 number and the spy of application on May 8th, 2006 is willing to 2006-129284 number and requires right of priority, and above-mentioned patent application is quoted by this specification sheets through reference.
Claims (41)
1. the manufacture method of a polyester is characterized in that, has:
Esterification step (a) in the presence of catalyst for esterification reaction, makes with the terephthalic acid to be the dicarboxylic acid composition of main component and to be that the glycol component of main component is carried out esterification with ethylene glycol, obtains oligopolymer,
Melt phase polycondensation operation (b) makes the oligopolymer that obtains carry out melt polycondensation reaction, obtains the polyester prepolymer,
Granulating operation (c), the polyester prepolymer granulating with obtaining obtains polyester prepolymer particle, and heat treatment step (d) carries out solid state polycondensation by making the polyester prepolymer particle that obtains, and obtains polyester,
Described method satisfies the prerequisite of following (1)～(3),
1. each operation (a) and (b) and (c) be successive processes;
2. the polyester prepolymer particulate intrinsic viscosity that obtains in operation (c) is more than the 0.18dL/g, below the 0.40dL/g;
3. the polyester prepolymer particulate end carboxy concentration that in operation (c), obtains be per 1 ton of this particle have more than 1 equivalent, below 50 equivalents.
2. the manufacture method of polyester as claimed in claim 1 is characterized in that, the melt polycondensation reaction that passes through successive processes of operation (b) divides 1 section or 2 sections to carry out.
3. the manufacture method of polyester as claimed in claim 1 or 2 is characterized in that, the miniaturation method of operation (c) is a topical application.
4. the manufacture method of polyester as claimed in claim 1 or 2 is characterized in that, the miniaturation method of operation (c) is the strand cutting method.
5. as the manufacture method of each the described polyester in the claim 1～4, it is characterized in that the median size of the polyester prepolymer that obtains is more than the 0.1mm, below the 3.0mm in operation (c).
6. as the manufacture method of each described polyester in the claim 1～5, it is characterized in that the catalyst for esterification reaction in the operation (a) contains tungsten compound and/or titanium compound.
7. as the manufacture method of each the described polyester in the claim 1～6, it is characterized in that the intrinsic viscosity of the polyester that obtains is more than 0.70dL/g in operation (d).
8. as the manufacture method of each the described polyester in the claim 1～7, it is characterized in that operation (d) is a successive processes.
9. the manufacture method of a polyester, it is characterized in that, comprise thermal treatment, described thermal treatment is that intrinsic viscosity is heat-treated at solid state at the polyester prepolymer more than the 0.18dL/g, below the 0.40dL/g, the intrinsic viscosity of this polyester prepolymer is increased more than the 0.50dL/g, obtain polyester
Described thermal treatment is divided into the n stage, and satisfies following conditions,
1) temperature of described heat treated j section (Tj) is more than 190 ℃, below 230 ℃, and the intrinsic viscosity rising value of j section is more than 0.03dL/g;
2) have the combination of 1 group of j section and k section at least, wherein, the temperature of described heat treated j section (Tj (℃)) and the temperature of k section (Tk (℃)) satisfy following (formula 1a);
(formula 1a) Tj+15≤Tk≤245
3) in the combination of described j section, k section, the difference of the intrinsic viscosity when intrinsic viscosity when the j section finishes and k section begin is below 0.10dL/g;
4) n is the integer more than 2, and j and k are the integers that satisfies 1≤j＜k≤n.
10. before described j section, there is the c section with the crystallization of polyester in the manufacture method of polyester as claimed in claim 9, its temperature (Tca (℃)) satisfy following (formula 2a),
(formula 2a) 100≤Tca≤200.
11. the manufacture method of polyester as claimed in claim 10, described c section is implemented with fluidized-bed.
12. as the manufacture method of each the described polyester in the claim 9～11, between described j section and k section, have the h section, its temperature (Tha (℃)) satisfy following (formula 3a),
(formula 3a) Tk≤Tha≤250.
13. the manufacture method of polyester as claimed in claim 12, described h section is implemented with fluidized-bed.
14. the manufacture method as each the described polyester in the claim 9～13 is characterized in that, described thermal treatment is carried out continuously.
15. as the manufacture method of each the described polyester in the claim 9～14, described j section and/or k section are implemented with the continous way moving-bed.
16. as the manufacture method of each the described polyester in the claim 9～15, the median size of described polyester prepolymer is more than the 0.5mm, below the 3.0mm.
17. as the manufacture method of each the described polyester in the claim 9～16, the end carboxy concentration of described polyester prepolymer is at 100 equivalents/below the ton.
18. as the manufacture method of each the described polyester in the claim 9～17, described polyester contains titanium compound.
19. the manufacture method of a polyester is characterized in that, comprises thermal treatment, this thermal treatment is that intrinsic viscosity is heat-treated at solid state at the polyester prepolymer more than the 0.18dL/g, below the 0.40dL/g, the intrinsic viscosity of this polyester prepolymer is increased more than the 0.50dL/g, obtain polyester
Described thermal treatment all contains in order: temperature T 1a (℃) under make the 1st section of described polyester prepolymer crystallization; The polyester prepolymer that makes crystallization temperature T 2a (℃) under carry out the 2nd section of solid phase polycondensation; Make the 2nd section product that obtains be warming up to temperature T 3a (℃) the 3rd section; Make the 3rd section product that obtains temperature T 4a (℃) under carry out the 4th section of solid phase polycondensation,
Described the 2nd section intrinsic viscosity rising value more than 0.03dL/g,
The difference of the intrinsic viscosity when described the 2nd section intrinsic viscosity when finishing begins with the 4th section below 0.10dL/g,
Described T1a, T2a, T3a, T4a (℃) satisfy following (formula 4a)～(formula 7a),
(formula 4a) 100≤T1a≤200,
(formula 5a) 190≤T2a≤230,
(formula 6a) T4a≤T3a≤250,
(formula 7a) T2a+15≤T4a≤245.
20. the manufacture method of a polyethylene terephthalate, it is characterized in that, intrinsic viscosity is in the thermal treatment of the process of the polyethylene terephthalate prepolymer more than the 0.18dL/g, below the 0.40dL/g under solid state, making intrinsic viscosity is the above polyethylene terephthalate of 0.70dL/g, thermal treatment comprises following 1 in order) the 1st section solid phase polycondensation operation and 2) the 2nd section solid phase polycondensation operation
1) the 1st section solid phase polycondensation operation:
This operation be in temperature (T1b) be more than 200 ℃, below 225 ℃, under the inert gas atmosphere or under the decompression, mean residence time is that the rising value of under the condition more than 0.5 hour, below 10 hours the polyethylene terephthalate prepolymer being heat-treated the intrinsic viscosity that makes this prepolymer is the operation more than the 0.03dL/g;
2) the 2nd section solid phase polycondensation operation:
In temperature (T2b) is more than 215 ℃, below 240 ℃, inert gas atmosphere down or decompression down, mean residence time is the operation to heat-treating through the prepolymer of the 1st section solid phase polycondensation operation under the condition more than 2 hours;
Wherein, said temperature T1b (℃) and T2b (℃) satisfy following (formula 1b),
T1b+15≤T2b (formula 1b).
21. the manufacture method of polyethylene terephthalate as claimed in claim 20, it is characterized in that, before the 1st section solid phase polycondensation operation, be arranged on that temperature (Tcb) is heat-treated the polyethylene terephthalate prepolymer more than 140 ℃, below 200 ℃ and the crystallization step that makes the one partial crystallizationization.
22. manufacture method as claim 20 or 21 described polyethylene terephthalates, it is characterized in that this thermal treatment has between the 1st section solid phase polycondensation operation and the 2nd section solid phase polycondensation operation: under the inert gas atmosphere or under the decompression, mean residence time below 30 minutes, T1b (℃) operation (heating process) that the prepolymer through the 1st section solid phase polycondensation operation is heated up.
23. the manufacture method as each the described polyethylene terephthalate in the claim 20～22 is characterized in that, the thermal treatment under the solid state is carried out continuously.
24. as the manufacture method of each the described polyethylene terephthalate in the claim 20～23, the 1st section solid phase polycondensation operation and/or the 2nd section solid phase polycondensation operation are implemented with the continous way moving-bed.
25. the manufacture method as each the described polyethylene terephthalate in the claim 21～24 is characterized in that crystallization step is implemented with fluidized-bed.
26. as the manufacture method of each the described polyethylene terephthalate in the claim 22～25, heating process is implemented with fluidized-bed.
27. the manufacture method as each the described polyethylene terephthalate in the claim 20～26 is characterized in that, the median size of described polyethylene terephthalate prepolymer is more than the 0.5mm, below the 3.0mm.
28. the manufacture method as each the described polyethylene terephthalate in the claim 20～27 is characterized in that, the end carboxy concentration of described polyethylene terephthalate prepolymer is at 100 equivalents/below the ton.
29. as the manufacture method of each the described polyethylene terephthalate in the claim 20～28, polyethylene terephthalate contains titanium compound.
30. the manufacture method of a polyethylene terephthalate, it is characterized in that, making intrinsic viscosity is that the polyethylene terephthalate prepolymer that 0.18dL/g is above, 0.40dL/g is following is heat-treated under solid state, making intrinsic viscosity is more than the 0.70dL/g, the thermal treatment of solid state contains the 1st section solid phase polycondensation operation, heating process and the 2nd section solid phase polycondensation operation in order, and each operation satisfies following 1)～3)
1) the 1st section solid phase polycondensation operation: under inert gas atmosphere or the operation of under the decompression polyethylene terephthalate prepolymer being heat-treated, and its heat treated temperature (T1c) is more than 190 ℃, below 225 ℃;
2) heating process: under inert gas atmosphere or under the decompression, to heat up through the polyethylene terephthalate prepolymer of the 1st section solid phase polycondensation operation heat treated temperature (T1c) or the temperature below it since the 1st section solid phase polycondensation operation, be warming up to temperature (T2c), 30 minutes with interior from temperature T 1c (℃) be warming up to (T1c+15) ℃, and temperature T 1c (℃) and T2c (℃) satisfy following (formula 1c) and (formula 2c)
T1c+15≤T2c (formula 1c)
205 ℃≤T2c≤240 ℃ (formula 2c)
3) the 2nd section solid phase polycondensation operation: to heat-treating through the polyethylene terephthalate prepolymer of the 1st section solid phase polycondensation operation and heating process, and its heat treated temperature (T3c) is more than 190 ℃, below 240 ℃ under inert gas atmosphere or under the decompression.
31. the manufacture method of polyethylene terephthalate as claimed in claim 30, before the 1st section solid phase polycondensation operation, have crystallization step, described crystallization step is to be the operation of more than 110 ℃, below 200 ℃ the polyethylene terephthalate prepolymer being heat-treated in temperature (Tx).
32. as the manufacture method of claim 30 or 31 described polyethylene terephthalates, the intrinsic viscosity of polyethylene terephthalate prepolymer of supplying with the 2nd section solid phase polycondensation operation is more than 0.35dL/g.
33. as the manufacture method of each the described polyethylene terephthalate in the claim 30～32, the thermal treatment under the solid state is carried out continuously.
34. as the manufacture method of each the described polyethylene terephthalate in the claim 30～33, the 1st section solid phase polycondensation operation and/or the 2nd section solid phase polycondensation operation are implemented with the continous way moving-bed.
35. as the manufacture method of each the described polyethylene terephthalate in the claim 31～34, crystallization step is implemented with fluidized-bed.
36. as the manufacture method of each the described polyethylene terephthalate in the claim 30～35, heating process is implemented with fluidized-bed.
37. as the manufacture method of each the described polyethylene terephthalate in the claim 30～36, the polyethylene terephthalate prepolymer is a particle, its average quality is more than the 0.1mg/ grain, below the 30mg/ grain.
38. as the manufacture method of each the described polyethylene terephthalate in the claim 30～37, the end carboxy concentration of described polyethylene terephthalate prepolymer is at 100 equivalents/below the ton.
39. as the manufacture method of each the described polyethylene terephthalate in the claim 30～38, polyethylene terephthalate contains titanium compound.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP253286/2005 | 2005-09-01 | ||
| JP2005253286A JP4784213B2 (en) | 2005-09-01 | 2005-09-01 | Polyester manufacturing method |
| JP259383/2005 | 2005-09-07 | ||
| JP2005259383A JP4784216B2 (en) | 2005-09-07 | 2005-09-07 | Method for producing polyethylene terephthalate |
| JP2005307326 | 2005-10-21 | ||
| JP307326/2005 | 2005-10-21 | ||
| JP129284/2006 | 2006-05-08 | ||
| JP2006129284 | 2006-05-08 | ||
| PCT/JP2006/317256 WO2007026838A1 (en) | 2005-09-01 | 2006-08-31 | Method for producing polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101253215A true CN101253215A (en) | 2008-08-27 |
| CN101253215B CN101253215B (en) | 2012-06-27 |
Family
ID=37926012
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680031678XA Expired - Fee Related CN101253215B (en) | 2005-09-01 | 2006-08-31 | Method for producing polyester |
| CNA2006800316794A Pending CN101258180A (en) | 2005-09-01 | 2006-08-31 | Apparatus for heat treatment of polyester particle and method of multistage solid-phase polycondensation of polyester particle |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800316794A Pending CN101258180A (en) | 2005-09-01 | 2006-08-31 | Apparatus for heat treatment of polyester particle and method of multistage solid-phase polycondensation of polyester particle |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4784213B2 (en) |
| CN (2) | CN101253215B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947069A (en) * | 2017-04-19 | 2017-07-14 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN109081907A (en) * | 2018-06-29 | 2018-12-25 | 浙江尤夫高新纤维股份有限公司 | High viscosity polyester and preparation method thereof |
| CN109679126A (en) * | 2018-12-27 | 2019-04-26 | 东莞市澳中电子材料有限公司 | A kind of hot bending PET protection film and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007112995A (en) * | 2005-09-21 | 2007-05-10 | Mitsubishi Chemicals Corp | Apparatus for heat treatment of polyester particle and method for multistage solid-phase polycondensation of polyester particle |
| KR102554522B1 (en) * | 2014-12-10 | 2023-07-11 | 닛산 가가쿠 가부시키가이샤 | Ion complex material having ability to inhibit adhesion of biological materials, and method for producing same |
| CN117414758A (en) * | 2023-12-15 | 2024-01-19 | 宝得智(厦门)科技有限公司 | Liquid methylbenzotriazole granulator |
-
2005
- 2005-09-01 JP JP2005253286A patent/JP4784213B2/en not_active Expired - Fee Related
-
2006
- 2006-08-31 CN CN200680031678XA patent/CN101253215B/en not_active Expired - Fee Related
- 2006-08-31 CN CNA2006800316794A patent/CN101258180A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947069A (en) * | 2017-04-19 | 2017-07-14 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN106947069B (en) * | 2017-04-19 | 2019-06-04 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN109081907A (en) * | 2018-06-29 | 2018-12-25 | 浙江尤夫高新纤维股份有限公司 | High viscosity polyester and preparation method thereof |
| CN109679126A (en) * | 2018-12-27 | 2019-04-26 | 东莞市澳中电子材料有限公司 | A kind of hot bending PET protection film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101258180A (en) | 2008-09-03 |
| CN101253215B (en) | 2012-06-27 |
| JP4784213B2 (en) | 2011-10-05 |
| JP2007063458A (en) | 2007-03-15 |
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