JP2004143442A - Method for producing polyester resin - Google Patents
Method for producing polyester resin Download PDFInfo
- Publication number
- JP2004143442A JP2004143442A JP2003335000A JP2003335000A JP2004143442A JP 2004143442 A JP2004143442 A JP 2004143442A JP 2003335000 A JP2003335000 A JP 2003335000A JP 2003335000 A JP2003335000 A JP 2003335000A JP 2004143442 A JP2004143442 A JP 2004143442A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- solid
- prepolymer
- heat treatment
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 37
- 239000004645 polyester resin Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 138
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 133
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 94
- 238000010438 heat treatment Methods 0.000 claims abstract description 66
- 239000007790 solid phase Substances 0.000 claims abstract description 53
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 40
- 239000013638 trimer Substances 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 42
- 238000010586 diagram Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- -1 polyethylene terephthalate Polymers 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000011437 continuous method Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-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
- YWTVATKJDUZQGV-UHFFFAOYSA-N (4-carboxyoxyphenyl) hydrogen carbonate Chemical compound OC(=O)OC1=CC=C(OC(O)=O)C=C1 YWTVATKJDUZQGV-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-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
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 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
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- JHAFEVXNMDQGTR-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[Ge+2] Chemical compound C(C(=O)[O-])(=O)[O-].[Ge+2] JHAFEVXNMDQGTR-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HLHZMRQHTSYSST-UHFFFAOYSA-N methoxyantimony Chemical compound CO[Sb] HLHZMRQHTSYSST-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- BONLISHREBVIRW-UHFFFAOYSA-N tris[2-[2-(2-hydroxyethoxy)ethoxy]ethyl] phosphate Chemical compound OCCOCCOCCOP(=O)(OCCOCCOCCO)OCCOCCOCCO BONLISHREBVIRW-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
【課題】 環状三量体及びエチレングリコールの含有量が少ない高品質のポリエステル樹脂を効率的、且つ工業的に製造する。
【解決手段】 テレフタル酸を主成分とするジカルボン酸と、エチレングリコールを主成分とするジオールとから製造した粒状ポリエステルプレポリマーまたは該プレポリマーの予備固相重合ポリエステルを、不活性ガス、並びに水および／又はエチレングリコールを含有する混合ガス中で熱処理し、次いで固相重合するポリエステル樹脂の製造方法において、混合ガス中の水および／又はエチレングリコールの濃度を０．７５〜５０(体積)％とし、該プレポリマーまたは該予備固相重合ポリエステルを２００℃以上、各々の融点以下の温度で、且つ固体状態で熱処理し、固相重合を２２０℃以上、該プレポリマーまたは該予備固相重合ポリエステルの各々の融点以下、大気圧以上の圧力下で行う方法。
【選択図】 なしPROBLEM TO BE SOLVED: To efficiently and industrially produce a high-quality polyester resin having a small content of a cyclic trimer and ethylene glycol.
SOLUTION: A granular polyester prepolymer produced from a dicarboxylic acid containing terephthalic acid as a main component and a diol containing ethylene glycol as a main component, or a pre-solid-state polymerized polyester of the prepolymer, is mixed with an inert gas, water, and water. In a method for producing a polyester resin that is heat-treated in a mixed gas containing ethylene glycol and then solid-phase polymerized, the concentration of water and / or ethylene glycol in the mixed gas is set to 0.75 to 50 (volume)%, The prepolymer or the pre-solidified polyester is subjected to a heat treatment in a solid state at a temperature of 200 ° C. or higher and each melting point or lower, and the solid state polymerization is performed at 220 ° C. or higher, each of the prepolymer or the pre-solidified polyester. The method is carried out under a pressure of not more than the melting point of the above and at least the atmospheric pressure.
[Selection diagram] None
Description
本発明はポリエステル樹脂の製造方法に関するものであり、更に詳しくは環状三量体の含有量がきわめて少ないポリエステル樹脂を効率的に製造する方法に関するものである。 The present invention relates to a method for producing a polyester resin, and more particularly, to a method for efficiently producing a polyester resin having a very small content of a cyclic trimer.
ポリエチレンテレフタレートに代表されるポリエステル樹脂は、機械的性質、熱的性質、電気的性質などに優れているため、各種用途のフィルム、シート、ボトルなどの成型品に広く使われ、需要量も拡大している。
この様に多用されている工業的に得られるポリエステル樹脂中には、通常、環状三量体を主成分とするオリゴマーが数％含まれている（例えば、飽和ポリエステル樹脂ハンドブック、日刊工業社、１５１ページ参照）。これらのオリゴマーは、ポリエステル樹脂の成形時にフィルム、シート、ボトルなどの表面に析出して表面肌の荒れや白化を引き起こし品質の悪化による商品価値の低下をもたらしたり、フィルムやシートなどでは、オリゴマーが表面に析出すると印刷を困難にするなどの支障を生じ商品として不適格となる。
Polyester resins represented by polyethylene terephthalate have excellent mechanical, thermal, and electrical properties, and are widely used in molded products such as films, sheets, and bottles for various applications, and the demand is growing. ing.
Industrially obtained polyester resins which are frequently used in this way usually contain several% of oligomers having a cyclic trimer as a main component (for example, Saturated Polyester Resin Handbook, Nikkan Kogyosha, 151). Page). These oligomers precipitate on the surface of films, sheets, bottles, etc. during the molding of polyester resins and cause roughening or whitening of the surface skin, resulting in a reduction in commercial value due to deterioration in quality. Precipitation on the surface causes problems such as difficulty in printing and makes the product unsuitable.
更に、オリゴマーはポリエステルの成形工程において、ダイや金型類の汚染原因となり、用いたダイや金型類の清掃および交換頻度が増加するなど成型品製造効率を著しく低下させる。特に近年では、果汁飲料等の加熱殺菌充填を必要とする飲料用ボトルとして、射出成形したプリフォームを再加熱して軟化させた後、延伸ブロー成形する際にブロー金型を加熱しておくか、或いは、延伸ブロー成形した後に別に設けた加熱金型で、ボトルにヒートセットを施すことにより、耐熱性を付与したボトルの伸びが大きい。しかし、ヒートセットを高温で行うためか金型のオリゴマーによる汚れの傾向が著しく、汚れを防止するため、ボトルなどの成形前のポリエステル樹脂中のオリゴマー量がその主成分である環状三量体として４０００ｐｐｍ以下、好ましくは３０００ｐｐｍ以下であることを要求されることが多い。 Furthermore, oligomers cause contamination of dies and dies in the polyester molding process, and significantly reduce the efficiency of molding production, such as increasing the frequency of cleaning and replacing dies and dies used. Particularly in recent years, as a beverage bottle that requires heat sterilization filling such as fruit juice beverages, after the injection molded preform is reheated and softened, the blow mold is heated during stretch blow molding. Alternatively, the bottle provided with heat resistance has a large elongation by heat setting the bottle with a heating mold separately provided after stretch blow molding. However, because the heat setting is performed at a high temperature, the tendency of the oligomers in the mold to stain is remarkable, and in order to prevent stains, the amount of oligomers in the polyester resin before molding such as bottles is a cyclic trimer whose main component is It is often required to be 4000 ppm or less, preferably 3000 ppm or less.
ポリエステル樹脂中の環状三量体含有量を上記の目的に適した量まで低減させるために、ポリエステルプレポリマーの溶融重合に引き続き長時間の固相重合を行う方法が工業的に広く用いられているが、現在知られている処方では固相重合に２０時間程度以上を要するために、より生産性に優れた製造方法が望まれている。 In order to reduce the content of the cyclic trimer in the polyester resin to an amount suitable for the above purpose, a method of performing a solid phase polymerization for a long time after the melt polymerization of the polyester prepolymer is widely used industrially. However, currently known formulations require about 20 hours or more for solid-phase polymerization, and therefore, a production method with higher productivity is desired.
特許文献１及び特許文献２には、平均粒径約３００μｍ以下の溶融微粒子状にしたポリエステル先駆体を、不活性ガス流中、融点以上の温度で重縮合反応させる方法が記載されている。また上記の方法において不活性ガス流中にエチレングリコールが含有されている方法も記載されているが、我々の検討では、溶融状態で重縮合反応を行う上記の方法では、副生物である環状三量体が充分に低減されない点で問題があることが分かった。 Patent Documents 1 and 2 disclose a method of subjecting a molten polyester precursor having an average particle size of about 300 μm or less to a polycondensation reaction in an inert gas stream at a temperature equal to or higher than the melting point. In the above method, a method in which ethylene glycol is contained in an inert gas stream is also described. However, in our study, in the above method of performing a polycondensation reaction in a molten state, cyclic by-products such as cyclic It has been found that there is a problem in that the monomer is not sufficiently reduced.
また特許文献３には１ｍｍ以下の粒径のポリエステルをジオール含有不活性ガス中、融点直下の温度で熱処理することで重合性を改良し、引き続き高真空下で固相重合を行う方法が記載されている。この方法においては、理由は不明なるも高真空化で固相重合を行うことを要件としており、高真空化のための装置が高価であるために該方法は大規模生産に適していないという問題点があった。また当該文献中には、ポリエステル中の環状三量体の低減については何ら記載されていない。 Patent Document 3 discloses a method of improving the polymerizability by heat-treating a polyester having a particle size of 1 mm or less in a diol-containing inert gas at a temperature just below a melting point, and subsequently performing solid-state polymerization under a high vacuum. ing. This method requires solid-state polymerization at a high vacuum, although the reason is unknown, and the method is not suitable for large-scale production because the equipment for the high vacuum is expensive. There was a point. In addition, the document does not describe anything about the reduction of the cyclic trimer in the polyester.
更に、特許文献４にはポリエステルプレポリマーを粒子状にし、更に固相で重合することからなる線状ポリエステルの製造方法に於いて、粒子を約１４０℃〜ポリエステルの融点より約２℃低い温度で、約０．１〜約１００時問、３００〜７０００ｐｐｍ（体積）の水又は少なくとも１個のＯＨ基を有する有機化合物を含有する不活性ガスと接触させることにより、局部的網状構造を形成しているポリマー主鎖を切断しポリエステル成形品中のゲルを低減させる方法が開示されている。しかしながら、環状三量体については何ら触れられておらず、また、この所定濃度の水又は有機化合物を含有する不活性ガスによる処理では、所定の分子量まで重合を進める間に環状三量体を極度に低減するのは困難である。
Further,
特許文献５には、ジカルボン酸成分とグリコール成分との重縮合反応によって得られる粗製ポリエステルを、該グリコール成分が少なくとも１００ｐｐｍの割合で含有される不活性ガス雰囲気下で、１８０℃以上、該粗製ポリエステルの融点以下の温度で加熱処理する工程を包含するポリエステルの製造方法が記載されているが、この方法では、製品ポリエステル中にエチレングリコールモノマーが残留する問題がある。
本発明は、環状三量体及びエチレングリコールの含有量が少ない高品質のポリエステル樹脂を効率的に製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for efficiently producing a high-quality polyester resin having a small content of a cyclic trimer and ethylene glycol.
上記目的を達成するための本発明方法は、テレフタル酸を主成分とするジカルボン酸と、エチレングリコールを主成分とするジオールとをエステル化反応及び重縮合反応させることにより製造された粒状ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合した粒状ポリエステルを、不活性ガス、並びに水および／又はエチレングリコールを含有する混合ガス中で熱処理し、次いで固相重合を行うポリエステル樹脂の製造方法において、混合ガス中のガス状水および／又はエチレングリコールの濃度を０．７５(体積)％以上、５０(体積)％以下とし、該プレポリマーまたは該プレポリマーの予備固相重合ポリエステルを２００℃以上、各々の融点以下の温度で、且つ固体状態で熱処理し、固相重合を２２０℃以上、該プレポリマーまたは該プレポリマーの予備固相重合ポリエステルの各々の融点以下の温度で、大気圧以上の圧力下で行うことを特徴とするポリエステル樹脂の製造方法を要旨とするものである。 In order to achieve the above object, a method of the present invention is a granular polyester prepolymer produced by subjecting a dicarboxylic acid containing terephthalic acid as a main component and a diol containing ethylene glycol as a main component to an esterification reaction and a polycondensation reaction. Alternatively, a granular polyester obtained by pre-solid-phase polymerization of the polyester prepolymer is heat-treated in a mixed gas containing an inert gas and water and / or ethylene glycol, and then subjected to solid-state polymerization. The concentration of gaseous water and / or ethylene glycol in the gas is 0.75 (volume)% or more and 50 (volume)% or less, and the prepolymer or the pre-polymerized polyester of the prepolymer is heated to 200 ° C. or more, respectively. At a temperature equal to or lower than the melting point, and heat-treated in a solid state to perform solid-state polymerization at 220 ° C or higher. A gist of the present invention is a method for producing a polyester resin, which is carried out at a temperature not higher than the melting point of each of the prepolymer or the pre-solidified polyester of the prepolymer at a pressure not lower than the atmospheric pressure.
本発明方法の好適な態様は次の通りである。
［ポリエステルプレポリマーを熱処理する場合］
熱処理前のポリエステルプレポリマーの固有粘度が０．１ｄｌ／ｇ以上、０．５ｄｌ／ｇ以下であること；ポリエステルプレポリマーの熱処理前の固有粘度（Ａ）と、熱処理後の固有粘度（Ｂ）との差（Ｂ−Ａ）が、−０．３ｄｌ／ｇ以上となる条件で熱処理すること；固相重合は、２２０℃以上、ポリエステルプレポリマーの融点より２℃低い温度以下の温度で行うこと；ポリエステルプレポリマーが、平均粒径１０〜１５００μｍの微粒子であること；及びポリエステルプレポリマー中における熱処理前の環状三量体量（Ｃ）と熱処理後の環状三量体量（Ｄ）との差（Ｃ−Ｄ）が、３０００ｐｐｍ以上であることを挙げることが出来る。
Preferred embodiments of the method of the present invention are as follows.
[When heat treating polyester prepolymer]
The intrinsic viscosity of the polyester prepolymer before heat treatment is 0.1 dl / g or more and 0.5 dl / g or less; the intrinsic viscosity (A) of the polyester prepolymer before heat treatment and the intrinsic viscosity (B) of the polyester prepolymer after heat treatment. Heat treatment under the condition that the difference (BA) is -0.3 dl / g or more; the solid-state polymerization is performed at a temperature of 220 ° C or more and a temperature of 2 ° C or less lower than the melting point of the polyester prepolymer; The polyester prepolymer is fine particles having an average particle size of 10 to 1500 μm; and the difference between the amount of cyclic trimer (C) in the polyester prepolymer before heat treatment and the amount of cyclic trimer (D) after heat treatment ( CD) is 3000 ppm or more.
［ポリエステルプレポリマーを予備固相重合したポリエステルを熱処理する場合］
熱処理前のポリエステルプレポリマーを予備固相重合したポリエステルの固有粘度が０．１ｄｌ／ｇ以上、０．５ｄｌ／ｇ以下であること；ポリエステルプレポリマーを予備固相重合したポリエステルの熱処理前の固有粘度（Ａ）と、熱処理後の固有粘度（Ｂ）との差（Ｂ−Ａ）が、−０．３ｄｌ／ｇ以上となる条件で熱処理すること；固相重合は、２２０℃以上、ポリエステルプレポリマーを予備固相重合したポリエステルの融点より２℃低い温度以下の温度で行うこと；ポリエステルプレポリマーを予備固相重合したポリエステルが、平均粒径１０〜１５００μｍの微粒子であること；及びポリエステルプレポリマーを予備固相重合したポリエステル中における熱処理前の環状三量体量（Ｃ）と熱処理後の環状三量体量（Ｄ）との差（Ｃ−Ｄ）が、２０００ｐｐｍ以上であることを挙げることが出来る。
[When heat-treating polyester obtained by pre-solid-phase polymerization of polyester prepolymer]
Intrinsic viscosity of the polyester obtained by pre-solid-phase polymerization of the polyester prepolymer before heat treatment is 0.1 dl / g or more and 0.5 dl / g or less; (A) and heat treatment under the condition that the difference (BA) between the intrinsic viscosity (B) after the heat treatment is -0.3 dl / g or more; Is carried out at a temperature not higher than 2 ° C. lower than the melting point of the polyester subjected to the pre-solid phase polymerization; the polyester obtained by the pre-solid phase polymerization of the polyester prepolymer is fine particles having an average particle size of 10 to 1500 μm; The difference (C) between the amount of cyclic trimer (C) before heat treatment and the amount of cyclic trimer (D) after heat treatment in the pre-solid-phase polymerized polyester. D) is, can be mentioned that this is 2000ppm or more.
本発明方法により、ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステルを、所定の温度下、所定量の水および/又はエチレングリコールを含有する不活性ガス中で熱処理を行い、引き続き実質常圧の雰囲気下で固相重合を行うことにより得られるポリエステル樹脂は、環状三量体及びエチレングリコール含有量が少なくフィルム、シート、ボトルなどの成型に適しており、このような高品質のポリエステル樹脂を効率的に製造することができるので、本発明方法は工業的に有用な方法である。 According to the method of the present invention, the polyester prepolymer or the polyester obtained by pre-solid-state polymerization of the polyester prepolymer is subjected to a heat treatment at a predetermined temperature in an inert gas containing a predetermined amount of water and / or ethylene glycol, and subsequently substantially Polyester resin obtained by performing solid-phase polymerization under an atmosphere of normal pressure has a low cyclic trimer and ethylene glycol content, and is suitable for molding of a film, a sheet, a bottle, and the like. Since the resin can be produced efficiently, the method of the present invention is an industrially useful method.
以下、本発明を詳細に説明する。
本発明におけるポリエステル樹脂の製造方法は、ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステル（以下、予備固相重合ポリエステルと称することもある）を所定の混合ガス中で熱処理し、次いで固相重合することからなるポリエステルの製造方法であり、ポリエステルプレポリマーは、従来公知の溶融重合方法で製造することが出来、またポリエステルプレポリマーを予備固相重合したポリエステルも従来公知の固相重合方法で製造することが出来る。
Hereinafter, the present invention will be described in detail.
In the method for producing a polyester resin in the present invention, a polyester prepolymer or a polyester obtained by pre-solid-state polymerization of the polyester pre-polymer (hereinafter, also referred to as a pre-solid-state polymerization polyester) is heat-treated in a predetermined mixed gas, This is a method for producing polyester comprising solid-phase polymerization.A polyester prepolymer can be produced by a conventionally known melt polymerization method. It can be manufactured by a method.
［ポリエステルプレポリマーの製造方法］
ポリエステルプレポリマーは、テレフタル酸を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分とを、エステル化反応を経て重縮合させることにより得られたものであり、テレフタル酸が全ジカルボン酸成分の９５モル％以上を占めるジカルボン酸成分と、エチレングリコールが全ジオール成分の９５モル％以上を占めるジオール成分との重縮合体であるのが好ましく、それらによるエチレンテレフタレート単位が繰り返し構成単位の９０モル％以上を占めるものであるのが好ましい。エチレンテレフタレート単位が９０モル％未満では、固相重合後のポリエステル樹脂として機械的強度や耐熱性が劣る傾向となる。
[Production method of polyester prepolymer]
The polyester prepolymer is obtained by polycondensing a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing ethylene glycol as a main component through an esterification reaction. It is preferable that a polycondensate of a dicarboxylic acid component occupying 95 mol% or more of the dicarboxylic acid component and a diol component in which ethylene glycol accounts for 95 mol% or more of the total diol component, and the ethylene terephthalate unit formed by such a polycondensate is a repeating structural unit. Occupies at least 90 mol% of the total. When the amount of the ethylene terephthalate unit is less than 90 mol%, the mechanical strength and heat resistance of the polyester resin after the solid phase polymerization tend to be inferior.
尚、エチレンテレフタレート単位を主たる繰り返し構成単位とする前記ポリエステルプレポリマーは、テレフタル酸以外のジカルボン酸成分として、例えば、フタル酸、イソフタル酸、１，４−フェニレンジオキシジカルボン酸、１，３−フェニレンジオキシジ酢酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、４，４’−ジフェニルケトンジカルボン酸、４，４’−ジフェノキシエタンジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸等の脂環式ジカルボン酸、及びコハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカジカルボン酸、ドデカジカルボン酸等の脂肪族ジカルボン酸等の一種又は二種以上が、共重合成分として用いられていてもよい。 In addition, the polyester prepolymer having an ethylene terephthalate unit as a main repeating structural unit includes, as a dicarboxylic acid component other than terephthalic acid, for example, phthalic acid, isophthalic acid, 1,4-phenylenedioxydicarboxylic acid, 1,3-phenylene Rangeoxydiacetic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenyl Aromatic dicarboxylic acids such as sulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, and succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid , Azelaic acid, sebacic acid, undeca Carboxylic acids, one or two or more of such aliphatic dicarboxylic acids such as dodeca dicarboxylic acids may be used as a copolymerization component.
又、エチレングリコール以外のジオール成分として、例えば、トリメチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、ジエチレングリコール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等の脂肪族ジオール、１，２−シクロヘキサンジオール、１，４−シクロヘキサンジオール、１，１−シクロヘキサンジメチロール、１，４−シクロヘキサンジメチロール等の脂環式ジオール、及び、キシリレングリコール、４，４’−ジヒドロキシビフェニル、２，２−ビス（４’−ヒドロキシフェニル）プロパン、２，２−ビス（４’−β−ヒドロキシエトキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−β−ヒドロキシエトキシフェニル）スルホン酸等の芳香族ジオール等の一種又は二種以上が、共重合成分として用いられていてもよい。 As diol components other than ethylene glycol, for example, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol Aliphatic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexane dimethylol, alicyclic diols such as 1,4-cyclohexane dimethylol, and xylylene glycol; 4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, (4-hydroxyphenyl) sulfone, bis (4-beta-hydroxyethoxyphenyl) one or two or more of such aromatic diols such as sulfonic acid, may be used as a copolymerization component.
更に、例えば、グリコール酸、ｐ−ヒドロキシ安息香酸、ｐ−β−ヒドロキシエトキシ安息香酸等のヒドロキシカルボン酸やアルコキシカルボン酸、及び、ステアリルアルコール、ベンジルアルコール、ステアリン酸、安息香酸、ｔ−ブチル安息香酸、ベンゾイル安息香酸等の単官能成分、トリカルバリル酸、トリメリット酸、トリメシン酸、ピロメリット酸、没食子酸、トリメチロールエタン、トリメチロールプロパン、グリセロール、ペンタエリスリトール等の三官能以上の多官能成分等の一種又は二種以上が、共重合成分として用いられていてもよい。 Further, for example, hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, and stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid , Monofunctional components such as benzoyl benzoic acid, etc .; trifunctional or higher functional components such as tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, etc. May be used as the copolymerization component.
前記ポリエステルプレポリマーは、前記テレフタル酸を主成分とするジカルボン酸成分とエチレングリコールを主成分とするジオール成分とを、エステル化反応を経て、重縮合触媒の存在下に重縮合させることにより製造されるが、基本的には、ポリエステル樹脂の慣用の製造方法による。即ち、前記テレフタル酸を主成分とするジカルボン酸成分とエチレングリコールを主成分とするジオール成分とを、必要に応じて用いられる共重合成分等と共に、スラリー調製槽に投入し、攪拌下混合して原料スラリーとなし、エステル化反応槽で常圧〜加圧下、加熱下で、エステル化反応させた後、得られたエステル化反応生成物としてのポリエステル低分子量体を重縮合槽に移送し、重縮合触媒の存在下に、常圧から漸次減圧としての減圧下、加熱下で、溶融重縮合させポリエステルプレポリマーを得る。
なお、これらは連続式又は回分式でなされ、又、エステル化反応槽、及び重縮合槽は、それぞれ一段としても多段としてもよい。
The polyester prepolymer is produced by subjecting the dicarboxylic acid component containing terephthalic acid as a main component and the diol component containing ethylene glycol as a main component to polycondensation through an esterification reaction in the presence of a polycondensation catalyst. However, basically, it is based on a conventional method for producing a polyester resin. That is, the dicarboxylic acid component containing terephthalic acid as a main component and the diol component containing ethylene glycol as a main component are put into a slurry preparation tank together with a copolymer component used as necessary, and mixed under stirring. A raw material slurry is formed, an esterification reaction is performed in the esterification reaction tank under normal pressure to under pressure, and under heating, and then the resulting polyester low molecular weight product as an esterification reaction product is transferred to a polycondensation tank, In the presence of a condensation catalyst, melt polycondensation is carried out under reduced pressure from normal pressure to gradually reduced pressure to obtain a polyester prepolymer.
In addition, these are performed by a continuous type or a batch type, and the esterification reaction tank and the polycondensation tank may each be single-stage or multi-stage.
前記プレポリマー製造方法において、エステル化反応は、２００〜２７０℃程度の温度、１×１０5〜４×１０5 Ｐａ程度の圧力下でなされ、エステル化反応率を、通常９０％以上、好ましくは９３％以上とした後、溶融重縮合に移行させ、溶融重縮合は、重縮合触媒の存在下、好ましくは燐化合物の共存下に、２４０〜２９０℃程度の温度、１．３３〜１３３３Ｐａ程度の減圧下でなされる。
エステル化反応は、触媒の非存在下で行うこともできるが、触媒としてゲルマニウム化合物、アンチモン化合物、チタン化合物等の存在下行ってもよい。これらの触媒としては、後記の重縮合触媒として挙げた公知の触媒化合物から適宜選択して使用することが出来る。
In the prepolymer production method, the esterification reaction is carried out at a temperature of about 200 to 270 ° C. and a pressure of about 1 × 10 5 to 4 × 10 5 Pa, and the esterification reaction rate is usually 90% or more, preferably After making it 93% or more, it is shifted to melt polycondensation, and the melt polycondensation is carried out in the presence of a polycondensation catalyst, preferably in the presence of a phosphorus compound, at a temperature of about 240 to 290 ° C. and about 1.33 to 1333 Pa. It is done under reduced pressure.
The esterification reaction can be performed in the absence of a catalyst, but may be performed in the presence of a germanium compound, an antimony compound, a titanium compound, or the like as a catalyst. These catalysts can be appropriately selected and used from known catalyst compounds listed as polycondensation catalysts described below.
重縮合触媒としては、ポリエステル樹脂製造の重縮合触媒として従来より慣用されている触媒が用いられ、例えば、二酸化ゲルマニウム、四酸化ゲルマニウム、水酸化ゲルマニウム、蓚酸ゲルマニウム、ゲルマニウムテトラエトキシド、ゲルマニウムテトラ−ｎ−ブトキシド等のゲルマニウム化合物、三酸化アンチモン、五酸化アンチモン、酢酸アンチモン、メトキシアンチモン等のアンチモン化合物、テトラ−ｎ−プロピルチタネート、テトラ−ｉ−プロピルチタネート、テトラ−ｎ−ブチルチタネート、蓚酸チタン、蓚酸チタンカリウム等のチタン化合物等を、単独で或いは併用して、或いはこれらに更に、マグネシウム、コバルト等の有機酸塩等を併用して用いられる。その使用量は、得られるポリエステルプレポリマーに対して１〜４００ｐｐｍとなる量とするのが好ましく、３〜３００ｐｐｍとなる量とするのが特に好ましい。 As the polycondensation catalyst, a catalyst conventionally used as a polycondensation catalyst for producing a polyester resin is used.Examples include germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium tetra-n. -Germanium compounds such as butoxide, antimony trioxide, antimony pentoxide, antimony acetate, antimony compounds such as methoxyantimony, tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, titanium oxalate, oxalic acid A titanium compound such as titanium potassium or the like is used alone or in combination, or an organic acid salt such as magnesium or cobalt is used in combination therewith. The amount used is preferably 1 to 400 ppm with respect to the obtained polyester prepolymer, and particularly preferably 3 to 300 ppm.
溶融重縮合時には、前記重縮合触媒と共に、正燐酸、トリス（トリエチレングリコール）ホスフェート、エチルジエチルホスホノアセテート、エチルアシッドホスフェート、トリエチレングリコールアシッドホスフェート、亜燐酸等の燐化合物を安定剤として共存させるのが好ましい。その使用量は、得られるポリエステルプレポリマーに対して１〜１０００ｐｐｍとなる量とするのが好ましく、２〜２００ｐｐｍとなる量とするのが特に好ましい。
更に、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸マグネシウム、水酸化マグネシウム、マグネシウムアルコキシド、炭酸マグネシウム、水酸化カリウム、水酸化カルシウム、酢酸カルシウム、炭酸カルシウム等のアルカリ金属、アルカリ土類金属の化合物も前記重縮合触媒と共に使用することも出来る。
At the time of melt polycondensation, phosphorus compounds such as orthophosphoric acid, tris (triethylene glycol) phosphate, ethyl diethyl phosphonoacetate, ethyl acid phosphate, triethylene glycol acid phosphate, and phosphorous acid are coexisted with the polycondensation catalyst as a stabilizer. Is preferred. The amount used is preferably 1 to 1000 ppm with respect to the obtained polyester prepolymer, and particularly preferably 2 to 200 ppm.
Further, compounds of alkali metals such as lithium acetate, sodium acetate, potassium acetate, magnesium acetate, magnesium hydroxide, magnesium alkoxide, magnesium carbonate, potassium hydroxide, calcium hydroxide, calcium acetate, calcium carbonate, and alkaline earth metals are also described above. It can also be used with a polycondensation catalyst.
上記のような方法で溶融重合後に得られる本発明のポリエステルプレポリマーは、その固有粘度が０．１ｄｌ／ｇ以上、０．５ｄｌ／ｇ以下であるものが好ましく、中でも０．４ｄｌ／ｇ以下、特に０．３ｄｌ／ｇ以下であるものがより好ましい。ポリエステルプレポリマーの固有粘度を０．５ｄｌ／ｇ以下とする場合には、溶融重縮合反応は２段以上の多段工程を要せず一段で行うこともできるので設備コスト面で有利である。 The polyester prepolymer of the present invention obtained after the melt polymerization by the method as described above preferably has an intrinsic viscosity of 0.1 dl / g or more and 0.5 dl / g or less, among which 0.4 dl / g or less. In particular, those having 0.3 dl / g or less are more preferable. When the intrinsic viscosity of the polyester prepolymer is set to 0.5 dl / g or less, the melt polycondensation reaction can be performed in one step without requiring two or more steps, which is advantageous in terms of equipment cost.
また、ポリエステルプレポリマーは、エチレングリコールを０．００１〜１０重量％含有するものが好ましい。少量のエチレングリコールを含むポリエステルプレポリマーは、重合度が高くても粘度が低く、粒状化が容易であり、例えば噴射ノズルから気相中に噴射するスプレークーラーを用いることが出来、その後の固相重合での重合速度を高められることが期待される。 ポ リ エ ス テ ル In addition, the polyester prepolymer preferably contains 0.001 to 10% by weight of ethylene glycol. The polyester prepolymer containing a small amount of ethylene glycol has a low viscosity even if the degree of polymerization is high, and is easy to granulate.For example, a spray cooler that injects into a gas phase from an injection nozzle can be used. It is expected that the polymerization rate in the polymerization can be increased.
溶融重縮合後のポリエステルプレポリマーは粒状化されるが、通常、重縮合槽の底部に設けられた抜き出し口からストランド状に押出して、水冷しながら若しくは水冷後、カッターで切断し、ペレット状、チップ状等の粒状体とされる。
本発明のポリエステルプレポリマーが、上記の如き好ましい固有粘度範囲に存するものは、溶融粘度が低いため粒状化方法として重合槽出口から押し出されるストランドを水中に押し出しながらカッティングして得る方法や噴射ノズルから気相中又は液相中に粒体状に噴射して得る方法、更には、液滴を生じさせ、例えばコンベア上で冷却固化させる方法をとることができる。
ポリエステルプレポリマー粒状体の平均粒径は１０〜１５００μmが好ましい。より好ましくは５０μｍから１０００μｍ、更に好ましくは１００μｍから５００μｍである。平均粒径が１５００μｍを越えると固相重合速度が遅くなり、また平均粒径が１０μｍ以下であると空中への飛散が起こりやすく取り扱い上好ましくない。
Although the polyester prepolymer after melt polycondensation is granulated, it is usually extruded into a strand form from a discharge port provided at the bottom of the polycondensation tank, and cut with a cutter while cooling with water or after cooling with water, and pelletized. It is a granular material such as a chip.
The polyester prepolymer of the present invention has a preferable intrinsic viscosity range as described above, and has a low melt viscosity.As a granulation method, a method in which a strand extruded from a polymerization vessel outlet is cut out while being extruded into water, or from a spray nozzle. A method of spraying particles into a gas phase or a liquid phase to obtain particles, or a method of generating droplets and cooling and solidifying the droplets on a conveyor, for example, can be used.
The average particle size of the polyester prepolymer granules is preferably from 10 to 1500 μm. More preferably, the thickness is 50 μm to 1000 μm, and still more preferably, 100 μm to 500 μm. When the average particle size exceeds 1500 μm, the solid-state polymerization rate becomes slow. When the average particle size is 10 μm or less, scattering into the air tends to occur, which is not preferable in handling.
［ポリエステルプレポリマーの予備固相重合方法］
前記で得られたポリエステルプレポリマー粒状体の予備固相重合は、ポリエステルプレポリマーを収容した反応塔に２２０℃〜ポリエステルプレポリマーの融点より２℃低い（融点−２℃）温度程度の温度で、大気圧以上で窒素、二酸化炭素、アルゴン等の不活性ガスを流通させることにより行うことが出来る。重合温度としては好ましくは、２３０℃以上、該プレポリマーの融点−２℃以下である。重合温度が２２０℃より低いと、充分な予備固相重合速度が得られない。
また、反応塔に流通させる不活性ガスは、フィード時点でガス中に水素及びエチレングリコールを実質的に含まないものが用いられる。
[Preliminary solid-state polymerization method of polyester prepolymer]
Preliminary solid phase polymerization of the polyester prepolymer granules obtained above is carried out at a temperature of about 220 ° C. to about 2 ° C. lower than the melting point of the polyester prepolymer (melting point −2 ° C.) in a reaction tower containing the polyester prepolymer. It can be carried out by flowing an inert gas such as nitrogen, carbon dioxide, argon or the like at atmospheric pressure or higher. The polymerization temperature is preferably 230 ° C. or higher and the melting point of the prepolymer is −2 ° C. or lower. If the polymerization temperature is lower than 220 ° C., a sufficient preliminary solid phase polymerization rate cannot be obtained.
As the inert gas to be passed through the reaction tower, a gas that does not substantially contain hydrogen and ethylene glycol in the gas at the time of feed is used.
反応塔に流通させる不活性ガスの空塔速度は、０．００１〜１００ｍ／分、圧力は大気圧〜１ＭＰａの範囲である。ここで空塔速度とは導入する不活性ガスの流量を反応塔の断面積で除した値を指す。
又、ポリエステルプレポリマー微粒子は、予備固相重合前に粒状体同士の融着を防ぐために、結晶化処理を行ってもよい。結晶化処理の手法としては、例えばパドル式の撹拌装置で昇温しながら結晶化処理を行う方法、あるいは不活性ガス気流下流動状態で結晶化処理を行う方法が挙げられる。結晶化処理は、通常６０〜２２０℃で行われる。
予備固相重合は回分法でも連続法でも可能であるが工業的には連続法が有利である。
The superficial velocity of the inert gas flowing through the reaction tower is 0.001 to 100 m / min, and the pressure is in the range of atmospheric pressure to 1 MPa. Here, the superficial velocity indicates a value obtained by dividing the flow rate of the inert gas to be introduced by the sectional area of the reaction tower.
Further, the polyester prepolymer fine particles may be subjected to a crystallization treatment before the preliminary solid phase polymerization in order to prevent fusion of the granular materials. As a method of the crystallization treatment, for example, a method of performing the crystallization treatment while raising the temperature with a paddle-type stirring device, or a method of performing the crystallization treatment in a flowing state under an inert gas stream can be mentioned. The crystallization treatment is usually performed at 60 to 220 ° C.
Preliminary solid-phase polymerization can be performed by a batch method or a continuous method, but a continuous method is industrially advantageous.
予備固相重合時間は、予備固相重合ポリエステルの分子量が所望のレベルに到達するのに必要な時間であればよく、通常１分から１０時間、好ましくは５分から７時間、更に好ましくは１０分から５時間の範囲から選定される。この範囲より短い時間では予備固相重合後のポリエステルの分子量を上昇させるのが困難であり、一方この範囲を超えて長時間に過ぎると、本発明の目的とする環状三量体含有量の少ない高品質のポリエステル樹脂を効率良く製造することが困難になる。 The pre-solid-state polymerization time may be any time required for the molecular weight of the pre-solid-phase polymerization polyester to reach a desired level, and is usually 1 minute to 10 hours, preferably 5 minutes to 7 hours, more preferably 10 minutes to 5 hours. It is selected from a range of time. If the time is shorter than this range, it is difficult to increase the molecular weight of the polyester after the pre-solid-state polymerization, while if the time is longer than this range, the cyclic trimer content intended for the present invention is low. It becomes difficult to efficiently produce high quality polyester resin.
上記のような方法で予備固相重合後に得られる本発明の予備固相重合ポリエステルは、その固有粘度が０．１ｄｌ／ｇ以上、０．５ｄｌ／ｇ以下であるものが好ましく、中でも０．４８ｄｌ／ｇ以下、特に０．４５ｄｌ／ｇ以下であるものがより好ましい。 The preliminarily solid-state polymerized polyester of the present invention obtained after the preliminarily solid-phase polymerization by the method described above preferably has an intrinsic viscosity of 0.1 dl / g or more and 0.5 dl / g or less, and particularly 0.48 dl. / G, more preferably 0.45 dl / g or less.
本発明におけるポリエステルプレポリマー粒状体または該ポリエステルプレポリマーを予備固相重合したポリエステル粒状体の熱処理は、加熱された不活性ガス並びに水および/又はエチレングリコールを含有する混合ガスと該粒状体を接触させることにより行なわれる。
不活性ガスとしては、反応に悪影響を及ぼさない気体であれば特に制限されず、例えば窒素、アルゴン、二酸化炭素、ヘリウム等が挙げられるが、入手の容易さや価格の面で窒素が有利である。又、混合ガス中には、水および/又はエチレングリコールを含有させるが、環状三量体の低減の効果が大であることよりエチレングリコールであることが好ましい。
The heat treatment of the polyester prepolymer granules or the polyester granules obtained by pre-solid-state polymerization of the polyester prepolymer in the present invention includes contacting the granules with a heated inert gas and a mixed gas containing water and / or ethylene glycol. This is done by letting
The inert gas is not particularly limited as long as it does not adversely affect the reaction. Examples of the inert gas include nitrogen, argon, carbon dioxide, and helium. Nitrogen is advantageous in terms of availability and price. Further, water and / or ethylene glycol is contained in the mixed gas, but ethylene glycol is preferable because the effect of reducing the cyclic trimer is large.
熱処理に導入する混合ガス中のガス状水および/又はエチレングリコールの濃度は、０．７５（体積)％以上、５０(体積)％以下とすることが必要であり、好ましくは０．８０（体積)％以上、更に好ましくは２．０（体積)％以上、３０(体積)％以下、特に好ましくは５．０（体積)％以上、２０(体積)％以下である。０．７５（体積)％より少ないと、環状三量体の低減が不十分であり、他方５０(体積)％を越えると熱処理中の分子量低下が大きく所定の重合度まで到達させるのに長時間を要し好ましくない。 The concentration of gaseous water and / or ethylene glycol in the mixed gas introduced into the heat treatment needs to be 0.75 (volume)% or more and 50 (volume)% or less, and preferably 0.80 (volume)%. )%, More preferably 2.0 (vol)% to 30 (vol)%, particularly preferably 5.0 (vol)% to 20 (vol)%. If it is less than 0.75 (volume)%, the reduction of the cyclic trimer is insufficient, while if it exceeds 50 (volume)%, the molecular weight decreases greatly during the heat treatment and it takes a long time to reach a predetermined degree of polymerization. Is not preferred.
熱処理は、２００℃以上、ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステルの各々の融点以下の温度で行われ、且つ固体状態で行うことが必要である。この温度範囲を超えて低すぎると充分な速度で環状三量体が低減できず、またこの温度範囲を超えた高温の場合には、該プレポリマーまたは該予備固相重合ポリエステルの粒子同士の融着が起こり好ましくない。ここで、固体状態とは、ポリエステルプレポリマーまたは該予備固相重合ポリエステルの粒子同士が融着しない状態を意味する。ポリエステルプレポリマーまたは該予備固相重合ポリエステルの熱処理温度として、好ましくは２００℃〜各々の融点より２℃低い温度（融点−２℃）の範囲で選ばれる。 (4) The heat treatment is performed at a temperature of 200 ° C. or higher and lower than the melting point of each of the polyester prepolymer or the polyester obtained by preliminarily solid-state polymerization of the polyester prepolymer, and needs to be performed in a solid state. If the temperature is lower than this temperature range, the cyclic trimer cannot be reduced at a sufficient speed, and if the temperature is higher than this temperature range, the fusion of the particles of the prepolymer or the pre-solid-state polymerized polyester can occur. Wearing is not preferred. Here, the solid state means a state in which particles of the polyester prepolymer or the preliminary solid-phase polymerized polyester do not fuse together. The heat treatment temperature of the polyester prepolymer or the pre-solid-state polymerized polyester is preferably selected from the range of 200 ° C to a temperature 2 ° C lower than the melting point of each (melting point -2 ° C).
又、ポリエステルプレポリマー微粒子は、前記予備固相重合を行う前と同様、必要に応じ熱処理前に粒状体同士の融着を防ぐために，結晶化処理を行ってもよい。結晶化処理の手法として、例えば、パドル式撹拌装置で昇温しながら結晶化処理を行う方法、あるいは不活性ガス気流下流動状態で結晶化処理を行う方法等が用いられる。結晶化処理は、通常６０〜２２０℃で行われる。 Further, the polyester prepolymer fine particles may be subjected to a crystallization treatment before the heat treatment, if necessary, in order to prevent the fusion of the granular materials as before the preliminary solid phase polymerization. As a method of the crystallization treatment, for example, a method of performing the crystallization treatment while raising the temperature with a paddle type stirring device, a method of performing the crystallization treatment in a flowing state under an inert gas stream, or the like is used. The crystallization treatment is usually performed at 60 to 220 ° C.
熱処理の方法としては、ポリエステルプレポリマーまたは予備固相重合ポリエステルの粒子と混合ガスが充分接触する方式であればよく、例えば、該プレポリマー粒子または予備固相重合ポリエステル粒子が存在する塔に混合ガスを流通させる方法、プレポリマー粒子または予備固相重合ポリエステル粒子が存在する回転容器に混合ガスを流通させる方法などである。熱処理と固相重合反応は同一反応器内でおこなうことも出来、又、熱処理はバッチ処理でも連続処理でも可能であるが工業的には連続法が有利である。
熱処理を竪型反応塔で行う場合、導入する混合ガスの空塔速度は０．００１〜１００ｍ／分、圧力は大気圧〜１ＭＰａの範囲である。ここで空塔速度とは熱処理に導入する混合ガスの流量を反応塔の断面積で除した値を指す。
The method of the heat treatment may be any method in which the mixed gas sufficiently contacts the polyester prepolymer or the particles of the pre-solid phase polymerized polyester. And a method of flowing a mixed gas through a rotating container in which prepolymer particles or preliminary solid-phase polymerized polyester particles are present. The heat treatment and the solid-state polymerization reaction can be carried out in the same reactor, and the heat treatment can be carried out by a batch process or a continuous process, but a continuous process is industrially advantageous.
When the heat treatment is performed in a vertical reaction tower, the superficial velocity of the mixed gas to be introduced is 0.001 to 100 m / min, and the pressure is in the range of atmospheric pressure to 1 MPa. Here, the superficial velocity indicates a value obtained by dividing the flow rate of the mixed gas introduced into the heat treatment by the cross-sectional area of the reaction tower.
熱処理時間としては、ポリエステルプレポリマーまたは予備固相重合ポリエステル中の環状三量体が十分減少するのに必要な時間であればよいが、通常１０分〜２０時間、好ましくは３０分〜１５時間、更に好ましくは１時間〜１０時間である。この範囲未満の場合、充分に環状三量体を減少させるのが困難であり、この範囲を超える場合、本発明の目的である環状三量体含有量の少ないポリエステル樹脂を効率的に製造することが困難になる。 The heat treatment time may be a time necessary for sufficiently reducing the cyclic trimer in the polyester prepolymer or the pre-solid-state polymerized polyester, and is usually 10 minutes to 20 hours, preferably 30 minutes to 15 hours. More preferably, it is 1 hour to 10 hours. If it is less than this range, it is difficult to sufficiently reduce the cyclic trimer, and if it exceeds this range, it is possible to efficiently produce a polyester resin having a low cyclic trimer content which is the object of the present invention. Becomes difficult.
本発明による熱処理は、熱処理中に、混合ガスに含まれる水及び／又はエチレングリコールが主鎖を切断し固有粘度が減少することがあるため、ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステルの各々の熱処理前の固有粘度（Ａ）と、熱処理後の固有粘度（Ｂ）との差（Ｂ−Ａ）が、−０．３ｄｌ／ｇ以上となるようにするのが好ましく、さらに好ましくは−０．２ｄｌ／ｇ以上、より好ましくは−０．１ｄｌ／ｇ以上である。
固有粘度差（Ｂ−Ａ）が−０．３ｄｌ／ｇ未満では引き続き行う固相重合において、ポリエステル樹脂に必要とされる重合度にまで重合度を上げるのに時間がかかり効率的でない。固有粘度差（Ｂ−Ａ）は大きい方が好ましいが、上限はポリエステルプレポリマーまたは予備固相重合ポリエステルの固有粘度と固相重合後の所望製品の固有粘度により決まり画一的に特定できないが、通常０．５ｄｌ／ｇである。
In the heat treatment according to the present invention, during the heat treatment, water and / or ethylene glycol contained in the mixed gas may cut the main chain and decrease the intrinsic viscosity. Therefore, the polyester prepolymer or the polyester prepolymer is subjected to pre-solid-state polymerization. It is preferable that the difference (BA) between the intrinsic viscosity (A) of each of the polyesters before the heat treatment and the intrinsic viscosity (B) after the heat treatment is -0.3 dl / g or more. It is preferably at least -0.2 dl / g, more preferably at least -0.1 dl / g.
If the intrinsic viscosity difference (BA) is less than -0.3 dl / g, it takes a long time to increase the degree of polymerization to the degree of polymerization required for the polyester resin in subsequent solid phase polymerization, which is not efficient. Although it is preferable that the intrinsic viscosity difference (BA) is large, the upper limit is determined by the intrinsic viscosity of the polyester prepolymer or the pre-solid-phase polymerized polyester and the intrinsic viscosity of the desired product after solid-phase polymerization, and cannot be specified uniformly. Usually, it is 0.5 dl / g.
更に、熱処理前のポリエステルプレポリマー中の環状三量体量（Ｃ）と熱処理後のポリエステルプレポリマー中の環状三量体量（Ｄ）との差（Ｃ−Ｄ）は、３０００ｐｐｍ以上とするのが好ましく、さらに好ましくは４０００ｐｐｍ以上である。環状三量体量の差（Ｃ−Ｄ）が３０００ｐｐｍに満たない場合、引き続き行う固相重合よって必要とされる量まで環状三量体量を低減することが困難になるので、この差（Ｃ−Ｄ）の値は大きければ大きいほどよい。 Further, the difference (C-D) between the amount of cyclic trimer (C) in the polyester prepolymer before the heat treatment and the amount of cyclic trimer (D) in the polyester prepolymer after the heat treatment is 3000 ppm or more. Is more preferable, and more preferably 4000 ppm or more. If the difference (CD) in the amount of the cyclic trimer is less than 3000 ppm, it will be difficult to reduce the amount of the cyclic trimer to the amount required by the subsequent solid-phase polymerization. The larger the value of -D), the better.
また、熱処理前の予備固相重合ポリエステル中の環状三量体量（Ｃ）と熱処理後の予備固相重合ポリエステル中の環状三量体量（Ｄ）との差（Ｃ−Ｄ）は、２０００ｐｐｍ以上とするのが好ましく、さらに好ましくは２５００ｐｐｍ以上である。環状三量体量の差（Ｃ−Ｄ）が２０００ｐｐｍに満たない場合、引き続き行う固相重合よって必要とされる量まで環状三量体量を低減することが困難になるので、この差（Ｃ−Ｄ）の値は大きければ大きいほどよい。
予備固相重合ポリエステルを熱処理した場合、環状三量体量低減速度と固有粘度上昇速度がバランス良く改良され、所望の性能のポリエステル樹脂を短時間に得られるという理由でポリエステルプレポリマーの熱処理より好ましい。
The difference (C-D) between the amount of cyclic trimer (C) in the preliminary solid-phase polymerized polyester before the heat treatment and the amount of cyclic trimer (D) in the preliminary solid-phase polymerized polyester after the heat treatment was 2000 ppm. It is preferably at least 2500 ppm, more preferably at least 2500 ppm. If the difference (CD) in the amount of cyclic trimer is less than 2000 ppm, it will be difficult to reduce the amount of cyclic trimer to the amount required by the subsequent solid-phase polymerization. The larger the value of -D), the better.
When the preliminary solid-phase polymerized polyester is heat-treated, the cyclic trimer amount reduction rate and the intrinsic viscosity rise rate are improved in a well-balanced manner, and it is preferable to the heat treatment of the polyester prepolymer because a polyester resin having a desired performance can be obtained in a short time. .
熱処理後のポリエステルプレポリマーまたは予備固相重合ポリエステルは、次いで固相重合されるが、固相重合は、熱処理終了後のプレポリマーまたは予備固相重合ポリエステルを収容した反応塔に、２２０℃〜ポリエステルプレポリマーまたは予備固相重合ポリエステルの各々の融点より２℃低い（融点−２℃）温度程度の温度で、大気圧以上で窒素、二酸化炭素、アルゴン等の不活性ガスを流通させることにより行われる。重合温度として好ましくは、２３０℃以上、該プレポリマーまたは予備固相重合ポリエステルの各々の融点より２℃低い（融点−２℃）温度以下である。重合温度が２２０℃より低いと、充分な固相重合速度が得られない。
又、反応塔に流通させる不活性ガスは、フィード時点でガス中に水及びエチレングリコールを実質的に含まないものが用いられる。
反応塔に流通させる不活性ガスの空塔速度は、０．００１〜１００ｍ／分、圧力は大気圧〜１ＭＰａの範囲である。ここで空塔速度とは反応塔に導入する不活性ガスの流量を反応塔の断面積で除した値を指す。
固相重合は回分法でも連続法でも可能であるが工業的には連続法が有利である。
After the heat treatment, the polyester prepolymer or the pre-solid-state polymerized polyester is then subjected to solid-phase polymerization. It is carried out by flowing an inert gas such as nitrogen, carbon dioxide, argon or the like at a temperature of about 2 ° C. lower than the melting point of each of the prepolymer or the pre-solid-state polymerized polyester (melting point−2 ° C.) at atmospheric pressure or higher. . The polymerization temperature is preferably 230 ° C. or higher and a temperature lower than the melting point of each of the prepolymer or the pre-solid-phase polymerized polyester by 2 ° C. (melting point−2 ° C.). If the polymerization temperature is lower than 220 ° C., a sufficient solid-state polymerization rate cannot be obtained.
As the inert gas to be passed through the reaction tower, a gas which does not substantially contain water and ethylene glycol in the gas at the time of feeding is used.
The superficial velocity of the inert gas flowing through the reaction tower is 0.001 to 100 m / min, and the pressure is in the range of atmospheric pressure to 1 MPa. Here, the superficial velocity refers to a value obtained by dividing the flow rate of the inert gas introduced into the reaction tower by the cross-sectional area of the reaction tower.
The solid phase polymerization can be performed by a batch method or a continuous method, but the continuous method is industrially advantageous.
固相重合時間としては、生成ポリエステル樹脂の分子量が所望のレベルに到達するのに必要な時間であればよく、通常１分から２０時間、好ましくは５分から１５時間、更に好ましくは１０分から１０時間である。この範囲より短い時間ではポリエステル樹脂の分子量を充分に上昇させるのが困難であり、一方この範囲を超えて長時間に過ぎると、本発明の目的とする環状三量体含有量の少ない高品質のポリエステル樹脂を効率良く製造することが困難になる。
ポリエステルプレポリマーは熱処理の前に予備固相重合を行うと、予備固相重合を行わない場合よりも、ポリエステル樹脂の所望の固有粘度までの到達時間を短くすることができる。
The solid phase polymerization time may be any time necessary for the molecular weight of the produced polyester resin to reach a desired level, and is usually 1 minute to 20 hours, preferably 5 minutes to 15 hours, and more preferably 10 minutes to 10 hours. is there. If the time is shorter than this range, it is difficult to sufficiently increase the molecular weight of the polyester resin, while if the time is longer than this range, high-quality, low cyclic trimer content aimed at by the present invention is obtained. It becomes difficult to efficiently produce a polyester resin.
Performing preliminary solid-phase polymerization of the polyester prepolymer before the heat treatment can shorten the time required to reach the desired intrinsic viscosity of the polyester resin as compared with the case where the preliminary solid-phase polymerization is not performed.
本発明方法により固相重合後に得られるポリエステル樹脂は、その固有粘度が０．６０ｄｌ／ｇ〜１．２０ｄｌ／ｇ、好ましくは０．６５ｄｌ／ｇ〜１．１０ｄｌ／ｇ、より好ましくは０．７０ｄｌ／ｇ〜１．００ｄｌ／ｇである。ポリエステル樹脂の固有粘度が０．６０ｄｌ／ｇより低いと、特にブロー成形に用いた場合に肉厚ムラが発生しやすく、又１．２０ｄｌ／ｇを超えて高粘度であると、特に射出成形時にヒケが発生しやすいので、成形加工性に問題があり、その用途が制限され商品価値が低くなる。さらに、固相重合後に得られるポリエステル樹脂中の環状三量体含有量は、４０００ｐｐｍ以下であり、極めて高品質である。 The polyester resin obtained after the solid phase polymerization by the method of the present invention has an intrinsic viscosity of 0.60 dl / g to 1.20 dl / g, preferably 0.65 dl / g to 1.10 dl / g, more preferably 0.70 dl / g. / G to 1.00 dl / g. When the intrinsic viscosity of the polyester resin is lower than 0.60 dl / g, thickness unevenness is likely to occur particularly when used for blow molding, and when the viscosity is higher than 1.20 dl / g, especially during injection molding, Since sink marks are liable to occur, there is a problem in moldability, its use is restricted, and its commercial value is reduced. Furthermore, the content of the cyclic trimer in the polyester resin obtained after the solid phase polymerization is 4000 ppm or less, which is extremely high quality.
以下、実施例により本発明をさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
なお、以下の実施例中「部」とあるのは重量部を意味し、本発明における各種物性の測定法は以下に示すとおりである。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the following examples, "parts" means parts by weight, and the methods for measuring various physical properties in the present invention are as follows.
（１）融点
ポリエステルプレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステル約１０ｍｇをアルミ製パンに入れて作成した試料を、示差走査熱量計ＤＳＣ２２０Ｃ（セイコー電子社製）を用いて２０℃／分の速度で昇温し、単位時間あたりの結晶融解熱が最も大きくなる点を融点とした。
(1) Melting point A sample prepared by placing about 10 mg of a polyester prepolymer or a polyester obtained by preliminarily solid-state polymerization of the polyester prepolymer in an aluminum pan was subjected to a differential scanning calorimeter DSC220C (manufactured by Seiko Denshi) at 20 ° C. / The temperature was raised at a rate of minutes, and the point at which the heat of crystal fusion per unit time was the largest was defined as the melting point.
（２）平均粒径
ＪＩＳ Ｋ００６９に記載の方法により積算分布曲線を作成し、積算百分率が５０％になるときの値を平均粒径とした。
(2) Average particle size An integrated distribution curve was created by the method described in JIS K0069, and the value when the integrated percentage became 50% was defined as the average particle size.
（３）固有粘度
フェノール／テトラクロロエタン（５０／５０重量比）を溶媒として、試料を加熱溶解後、室温まで冷却し、ウベローデ型粘度計を用いて３０℃で測定した。
(3) Intrinsic viscosity Using phenol / tetrachloroethane (50/50 weight ratio) as a solvent, a sample was heated and dissolved, cooled to room temperature, and measured at 30 ° C. using an Ubbelohde viscometer.
（４）環状三量体量
ポリエステル２００ｍｇをクロロホルム／ヘキサフルオロイソプロパノール（容量比３／２）混液２ｍｌに溶解し、さらにクロロホルム２０ｍｌを加えて希釈した。これにメタノール１０ｍｌを加え、試料を再析出させ、濾過した後の濾液を得た。得られた濾液を乾固後、残査をジメチルホルムアミド２５ｍｌに溶解させた液について、環状三量体量を液体クロマトグラフで分析定量した。
ポリエステルとしては、熱処理前後のプポリエステルレポリマーまたは該ポリエステルプレポリマーを予備固相重合したポリエステルと固相重合後のポリマーについて測定した。
(4) Amount of cyclic trimer 200 mg of polyester was dissolved in 2 ml of a mixed solution of chloroform / hexafluoroisopropanol (volume ratio: 3/2), and further diluted with 20 ml of chloroform. 10 ml of methanol was added thereto to reprecipitate the sample, and a filtrate after filtration was obtained. After the obtained filtrate was dried, a residue obtained by dissolving the residue in 25 ml of dimethylformamide was analyzed and quantified for the amount of cyclic trimer by liquid chromatography.
As the polyester, the polyester after pre-polymerization before and after the heat treatment or the polyester obtained by pre-solid-state polymerization of the polyester prepolymer and the polymer after solid-phase polymerization were measured.
（５）エチレングリコール及び／又は水濃度（混合ガス中）
図１に示す装置の前段容器中のエチレングリコール（ＥＧ）または水が熱処理中に減少した量Ｍ（ｍｏｌ）と流通させた窒素の総量Ｖ（Ｌ）より次式を用いて求めた。
(5) Ethylene glycol and / or water concentration (in mixed gas)
The amount of ethylene glycol (EG) or water in the pre-stage vessel of the apparatus shown in FIG. 1 was reduced from the amount M (mol) during the heat treatment and the total amount V (L) of the circulated nitrogen was determined using the following equation.
実施例１
テレフタル酸およびエチレングリコールを、テレフタル酸１３．０部とエチレングリコール５．８２部となる様にスラリー調製槽に連続的に供給し、スラリーを調製した。該スラリーを第１段のエステル化反応槽へ連続的に供給し、略常圧下２６０℃で連続的にエステル化反応を行い、エステル反応率８４％のビス（２−ヒドロキシエチル）テレフタレート及びその低重合体を調製した。反応物を第２段のエステル化反応槽に連続的に供給し、略常圧下２５５℃で連続して反応を行い、エステル反応率９５％のビス（２−ヒドロキシエチル）テレフタレートおよびその低重合体を調製した。
Example 1
Terephthalic acid and ethylene glycol were continuously supplied to a slurry preparation tank so as to be 13.0 parts of terephthalic acid and 5.82 parts of ethylene glycol to prepare a slurry. The slurry was continuously supplied to the first-stage esterification reaction tank, and the esterification reaction was continuously performed at 260 ° C. under substantially normal pressure, and bis (2-hydroxyethyl) terephthalate having an ester conversion of 84% and a low ester thereof were used. A polymer was prepared. The reactants are continuously supplied to the second-stage esterification reaction tank, and the reaction is continuously carried out at about normal pressure at 255 ° C., and bis (2-hydroxyethyl) terephthalate having an ester conversion of 95% and a low polymer thereof are obtained. Was prepared.
第２段のエステル化反応槽からの反応物を第１段の重縮合反応槽に連続的に供給し、正リン酸０．０１１部及び三酸化二アンチモン０．０３８部を連続的に上記の反応物に加え、１ｋＰａ〜２０ｋＰａの減圧下２８０℃で連続的に反応を行い、次いで、生成した反応物を第２段の重縮合反応槽に連続的に供給し１０Ｐａ〜１０ｋＰａの減圧下２８０℃で連続的に重縮合反応を行った。 The reactants from the second-stage esterification reactor are continuously fed to the first-stage polycondensation reactor, and 0.011 part of orthophosphoric acid and 0.038 part of diantimony trioxide are continuously added as described above. In addition to the reactants, the reaction is continuously performed at 280 ° C. under a reduced pressure of 1 kPa to 20 kPa, and then the generated reactant is continuously supplied to a second-stage polycondensation reaction tank, and the reaction is performed at 280 ° C. under a reduced pressure of 10 Pa to 10 kPa. To continuously carry out a polycondensation reaction.
重縮合反応生成物を反応槽からストランドとして連続的に水中に抜き出し、カットしてペレット化した。このときペレットは透明で実質結晶化されていなかった。得られたペレットを回転式ミルにより粉砕し、粉砕品（ポリエステルプレポリマー）を得た。プレポリマーの分析結果を表１のプレポリマー欄に示す。 (4) The polycondensation reaction product was continuously drawn out of water as a strand from the reaction tank, cut, and pelletized. At this time, the pellet was transparent and was not substantially crystallized. The obtained pellets were pulverized by a rotary mill to obtain a pulverized product (polyester prepolymer). The prepolymer analysis results are shown in the prepolymer column of Table 1.
次いで、図１に示す装置を用いて上記粉砕品（プレポリマー）の熱処理を行った。粉砕品３ｇを２４０℃のオイルバス中に保持した内径２５ｍｍのガラスチューブ（２）に入れ、下方より窒素およびエチレングリコールよりなる混合ガスを１Ｌ／分の速度で流通させ、４時間熱処理を行った。このとき、ガラスチューブ内の粉砕品の高さは約１ｃｍであり、粉砕品中央部に熱電対をセットし、サンプル温度がオイルバス温度と同温度になっていることを確認しながら熱処理を行った。
混合ガスは、オイルバス中に保持した容器（１）中のエチレングリコール中に窒素ガスを流通させることにより調製し、ガラスチューブ（２）に移送した。混合ガス中のエチレングリコール含有量のコントロールは、オイルバスの温度を変えることにより行った。
熱処理条件を表２に記載し、また熱処理後のプレポリマー品の分析結果を表１の熱処理品欄に示す。
Next, the above pulverized product (prepolymer) was subjected to a heat treatment using the apparatus shown in FIG. 3 g of the pulverized product was placed in a glass tube (2) having an inner diameter of 25 mm held in an oil bath at 240 ° C., and a mixed gas consisting of nitrogen and ethylene glycol was passed from below at a rate of 1 L / min, and heat treatment was performed for 4 hours. . At this time, the height of the crushed product in the glass tube was about 1 cm, a thermocouple was set at the center of the crushed product, and heat treatment was performed while confirming that the sample temperature was the same as the oil bath temperature. Was.
The mixed gas was prepared by flowing nitrogen gas through ethylene glycol in the container (1) held in the oil bath, and transferred to the glass tube (2). The ethylene glycol content in the mixed gas was controlled by changing the temperature of the oil bath.
The heat treatment conditions are shown in Table 2, and the analysis results of the prepolymer product after the heat treatment are shown in the heat treated product column of Table 1.
熱処理終了後、同じガラスチューブ内で引き続いて固相重合を行った。固相重合は、常圧下熱処理時に流通させたエチレングリコール含有窒素ガスを、エチレングリコールを含まない窒素ガス（流通量１Ｌ／分）に切り替えることによりおこなった。２５０℃で５時間固相重合を行った。固相重合条件を表２に記載し、また得られたポリエステルポリマーの分析結果を表１の固相重合後製品欄に示す。 後 After the heat treatment, solid-state polymerization was performed in the same glass tube. The solid-phase polymerization was performed by switching the ethylene glycol-containing nitrogen gas passed during the heat treatment under normal pressure to a nitrogen gas not containing ethylene glycol (flow rate 1 L / min). Solid-state polymerization was performed at 250 ° C. for 5 hours. The solid-state polymerization conditions are shown in Table 2, and the analysis results of the obtained polyester polymer are shown in Table 1 in the column of products after solid-phase polymerization.
実施例２、比較例１〜６
実施例１で得られたポリエステルプレポリマーの粉砕品を用い、熱処理条件及び固相重合条件を表２に示すように変えた以外は実施例１に示す条件で熱処理、固相重合を行った。
但し、比較例４では熱処理を施さなかった。また、比較例６では熱処理中に溶融したため、固相重合は行わなかった。
得られたポリエステルポリマーの分析結果を表１の固相重合後製品欄に示す。
Example 2, Comparative Examples 1 to 6
Using the pulverized polyester prepolymer obtained in Example 1, heat treatment and solid state polymerization were performed under the conditions shown in Example 1 except that the heat treatment conditions and solid state polymerization conditions were changed as shown in Table 2.
However, in Comparative Example 4, no heat treatment was performed. Further, in Comparative Example 6, solid-state polymerization was not performed because the material was melted during the heat treatment.
The analysis results of the obtained polyester polymer are shown in the column of products after solid-phase polymerization in Table 1.
実施例３
実施例１で得られたポリエステルプレポリマーの粉砕品３ｇを２４０℃のオイルバス中に保持した内径２５ｍｍのガラスチューブ（２）に入れ、下方より窒素ガスを１Ｌ／分の速度で流通させ、３０分間予備固相重合を行った。このとき、ガラスチューブ内の粉砕品の高さは約１ｃｍであり、粉砕品中央部に熱電対をセットし、サンプル温度がオイルバス温度と同温度になっていることを確認しながら予備固相重合を行った。
窒素ガスは、オイルバス中に保持した容器（１）の中を経由せずに、直接ガラスチューブ底部より流通するようにして予備固相重合を行った。
得られた予備固相重合ポリエステルの分析結果を表１の予備固相重合欄に示す。
Example 3
3 g of the crushed product of the polyester prepolymer obtained in Example 1 was placed in a glass tube (2) having an inner diameter of 25 mm held in an oil bath at 240 ° C., and nitrogen gas was allowed to flow from below at a rate of 1 L / min. Preliminary solid-state polymerization was performed for minutes. At this time, the height of the crushed product in the glass tube is about 1 cm, a thermocouple is set at the center of the crushed product, and the preliminary solid phase is checked while confirming that the sample temperature is the same as the oil bath temperature. Polymerization was performed.
Preliminary solid-phase polymerization was performed by flowing nitrogen gas directly from the bottom of the glass tube without passing through the container (1) held in the oil bath.
The analysis results of the obtained pre-solid-state polymerization polyester are shown in Table 1 in the column of pre-solid-state polymerization.
予備固相重合終了後、同じガラスチューブ内で引き続いて熱処理を行った。熱処理は、予備固相重合時に流通させた窒素ガスを、エチレングリコールを含有する窒素ガス（流通量１Ｌ／分）に切り替えることによりおこなった。２４０℃で１時間熱処理を行った。これ以外は実施例１と同様に行った。熱処理条件を表２に記載し、また得られた予備固相重合ポリエステルの分析結果を表１の熱処理品欄に示す。
熱処理終了後、同じガラスチューブ内で引き続いて固相重合を行った。固相重合は、常圧下熱処理時に流通させたエチレングリコール含有窒素ガスを、エチレングリコールを含まない窒素ガス（流通量１Ｌ／分）に切り替えることによりおこなった。２４０℃で２．５時間固相重合を行った。得られたポリエステルポリマーの分析結果を表１の固相重合後製品欄に示す。
After the completion of the pre-solid-state polymerization, heat treatment was subsequently performed in the same glass tube. The heat treatment was performed by switching the nitrogen gas circulated during the preliminary solid phase polymerization to a nitrogen gas containing ethylene glycol (flow rate 1 L / min). Heat treatment was performed at 240 ° C. for 1 hour. Other than that, it carried out similarly to Example 1. The heat treatment conditions are shown in Table 2, and the results of analysis of the obtained pre-solid-state polymerized polyester are shown in the heat treated product column of Table 1.
After the heat treatment, solid-state polymerization was performed in the same glass tube. The solid-phase polymerization was performed by switching the ethylene glycol-containing nitrogen gas passed during the heat treatment under normal pressure to a nitrogen gas not containing ethylene glycol (flow rate 1 L / min). Solid phase polymerization was performed at 240 ° C. for 2.5 hours. The analysis results of the obtained polyester polymer are shown in the column of products after solid-phase polymerization in Table 1.
１ エチレングリコール容器
２ ガラスチューブ反応器
３ オイルバス
４ オイルバス
1 ethylene glycol container 2 glass tube reactor 3
Claims (7)
The difference (CD) between the amount of cyclic trimer (C) before heat treatment and the amount of cyclic trimer (D) after heat treatment in the polyester obtained by pre-solid-state polymerization of the polyester prepolymer is 2000 ppm or more. The method for producing a polyester resin according to any one of claims 1 to 5, characterized in that:
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