CN108976403B - Process for producing polyester - Google Patents
Process for producing polyester Download PDFInfo
- Publication number
- CN108976403B CN108976403B CN201810896182.3A CN201810896182A CN108976403B CN 108976403 B CN108976403 B CN 108976403B CN 201810896182 A CN201810896182 A CN 201810896182A CN 108976403 B CN108976403 B CN 108976403B
- Authority
- CN
- China
- Prior art keywords
- titanium
- polyester
- phosphorus
- reaction
- temperature
- 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.)
- Active
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- 229920000728 polyester Polymers 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims description 15
- 230000008569 process Effects 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims abstract description 50
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 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 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 91
- 239000010936 titanium Substances 0.000 claims description 90
- 229910052719 titanium Inorganic materials 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007790 solid phase Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- -1 titanium halide Chemical class 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- VXKIZBQIIITYNK-UHFFFAOYSA-N 4,4,4-trihydroxybutyl dihydrogen phosphate Chemical compound C(CC(O)(O)O)COP(=O)(O)O VXKIZBQIIITYNK-UHFFFAOYSA-N 0.000 claims description 3
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 claims description 3
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000016337 monopotassium tartrate Nutrition 0.000 claims description 3
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 claims description 3
- 229940086065 potassium hydrogentartrate Drugs 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- YORDNDZKJQMIAL-UHFFFAOYSA-N 2,2,2-trihydroxyethyl dihydrogen phosphate Chemical compound OC(O)(O)COP(O)(O)=O YORDNDZKJQMIAL-UHFFFAOYSA-N 0.000 claims description 2
- AONAYFNEMQXSTK-UHFFFAOYSA-N 3,3,3-trihydroxypropyl dihydrogen phosphate Chemical compound C(COP(=O)(O)O)C(O)(O)O AONAYFNEMQXSTK-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- NKAAEMMYHLFEFN-ZVGUSBNCSA-M sodium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O NKAAEMMYHLFEFN-ZVGUSBNCSA-M 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 claims 1
- 229940074439 potassium sodium tartrate Drugs 0.000 claims 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 58
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 150000007942 carboxylates Chemical class 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 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 9
- 230000000694 effects Effects 0.000 description 8
- 150000003018 phosphorus compounds Chemical class 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 2
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- XFNIYCBYOUXNEU-UHFFFAOYSA-N 2,2,2-trihydroxyethyl dihydrogen phosphite Chemical compound OC(COP(O)O)(O)O XFNIYCBYOUXNEU-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 1
- BYEFHDZWRALTEN-UHFFFAOYSA-N 4-ethyl-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octane 1-oxide Chemical compound C1OP2(=O)OCC1(CC)CO2 BYEFHDZWRALTEN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 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
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- Polyesters Or Polycarbonates (AREA)
Abstract
A process for preparing polyester from terephthalic acid and diol includes such steps as preparing the titanium-phosphorus composition (A), the coordination compound (B) and the compound (C)nH2n+1The Li, Na, K, Mg and AI salts of the monoacid of COOH (wherein n is an integer of 0 and 1-3) are used as catalysts to prepare the polyester, and the catalysts have good catalytic activity and low b value of the catalytically synthesized poly (glycol terephthalate).
Description
Technical Field
The invention relates to the field of a preparation method of polyester, in particular to the field of preparing a titanium-phosphorus composition by mixing and reacting a titanium compound, dihydric alcohol and a phosphorus-containing compound, and using the titanium-phosphorus composition, a complex and Li, Na, K, Mg and AI salts of monocarboxylic acid as catalysts for synthesizing polyethylene terephthalate glycol ester.
Background
At present, more than 95 percent of Polyester (PET) in the world is produced by using antimony catalysts including antimony trioxide, antimony acetate or ethylene glycol antimony, the content of antimony metal in the polyester is generally 150-350 ug/g, but antimony compounds are toxic and heavy metal-containing compounds, which pollute the environment and can also precipitate toxic antimony in the use process of polyester products, so that the polyester products are harmful to human health, and therefore the Polyester (PET) is always concerned all the time, and from the initial development stage of the polyester industry, people continuously research substitute products of the antimony catalysts or reduce the use of the antimony as the polyester catalysts, such as research on the use of germanium compounds, titanium compounds and the like. Germanium compounds are limited in their application due to their low resources and high prices; the titanium catalyst is favored by polyester manufacturers at home and abroad because of high activity and no heavy metal, and has become a research hotspot at home and abroad for many times, the synthesis of the titanium catalyst and the application of the titanium catalyst to the synthesis of polyester are frequently reported, the components of the titanium catalyst are widely researched and reported from easily hydrolyzed titanate to modified titanate, titanium-containing metal salt, composite titanium catalyst and the like, but the defects of unstable activity, remarkable catalytic side reaction, easy yellowing of polyester and the like are not solved so far, and the application of the titanium catalyst is limited. In recent reports, a titanium-containing catalyst is described in a polyester production method of patent 200710041917.6, and a non-yellowing polyester is obtained, but the catalyst preparation process is complicated, the intermediate product needs to be washed with water and dried in vacuum for many times, so that new environmental pollution is brought, and the catalyst still has the problems of poor stability, no molecular weight reduction when the polyester is tackified and the like when being used for preparing the polyester, which is the most fundamental reason that the antimony-based catalyst still occupies the main position in the polyester catalyst so far.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, adopts new technical characteristics, provides a combined catalyst and realizes application in polyester.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme: a preparation method of polyester comprises the steps of taking terephthalic acid and dihydric alcohol as raw materials, carrying out esterification under the conditions of normal pressure to 0.35MPa and temperature of 210 to 280 ℃ in the presence of a titanium catalyst, removing water generated in the reaction through a distillation or rectification device to obtain a prepolymer, gradually reducing the pressure to be below 100Pa within 60min, controlling the temperature to be 230 to 300 ℃ to carry out polycondensation, stopping the reaction when the viscosity of a polycondensate is reached in the polycondensation reaction, and carrying out continuous extrusion, cooling and grain cutting to obtain the polyester; putting the PET polyester slices into a vacuum drum for drying, controlling the temperature to be 175-180 ℃, keeping for 5 hours, and then performing solid-phase tackifying for 4-20 hours under the conditions of 220-245 ℃ and the vacuum degree of 0-100 Pa to obtain solid-phase tackified polyester slices (SSP), wherein the titanium catalyst comprises the following components:
(A) a titanium phosphorus composition;
(B) a complex;
(C) selected from the general formula CnH2n+1Li, Na, K, Mg, AI salts of carboxylic acids of COOH (wherein n is an integer of 0 and 1 to 3);
the titanium phosphorus composition is prepared by mixing and reacting a titanium compound, a dihydric alcohol and a phosphorus-containing compound, and is characterized in that the titanium compound, the phosphorus compound and the dihydric alcohol are added into a reactor, the temperature is 105 ℃ to the boiling point of the dihydric alcohol for reaction, a low molecular compound generated in an inert gas stripping system is introduced under reduced pressure or normal pressure, and when no low molecular compound is distilled off, the reaction is stoppedStopping reaction, cooling to normal temperature, and obtaining a colorless or light yellow liquid product in a reactor, namely the titanium-phosphorus composition, wherein the titanium content is 0.1 +/-6.0%, the molar ratio of titanium to phosphorus is 1: 0.49-5.33, and the molar ratio of titanium to dihydric alcohol is 1: 5.99 to 251; when the titanium-phosphorus composition is used for preparing polyester, the dosage of the titanium-phosphorus composition is 5-85.5 mg/kgPTA in terms of titanium, the dosage of the complex is 13-300 mg/kgPTA, and the general formula is CnH2n+1The amount of Li, Na, K, Mg salts of the COOH (wherein n is an integer of 0 and 1 to 3) monoacid is 40 to 602 Mg/kgPTA.
The titanium compound used in the preparation of the titanium phosphorus composition of the present invention is selected from the group consisting of compounds of the general formula (C)nH2n+1O）4Titanate of Ti (wherein n is an integer of 1-8), hydrolysate thereof, and general formula (C)nH2n+1O）4Titanate of Ti (wherein n is an integer of 1-8) and a general formula HO (CH)2) Reaction product of dihydric alcohol of nOH (wherein n is an integer of 2-4) and general formula of TiX4The titanium halide hydrolysate and the titanium sulfate hydrolysate (X is CI and Br), the titanium compounds can be used independently or in any combination, at least one of the titanium compounds is selected, experimental researches show that under the condition of the invention, the titanium provided by the titanium compounds is equivalent, the content of the titanium in the composition is controlled to be 0.1-6%, when the content is lower than 0.1%, the transportation cost is obviously increased, the energy consumption in the using process is increased, and when the content is higher than 6%, the storage stability of the catalyst is deteriorated.
The diol used in the preparation of the titanium composition of the present invention has the general formula HO (CH)2) nOH (wherein n is an integer of 2-4), wherein the dihydric alcohol is a raw material of polyester, and the dihydric alcohol with ortho-position and meta-position can be coordinated with titanium atoms to form a stable structure, so that the hydrolysis resistance of the polyester is improved, the molar ratio of titanium to the dihydric alcohol is selected and controlled to be 1: 5.99-251, and when the molar ratio of titanium to the dihydric alcohol is more than 1: 5.99, the composition is unstable, and precipitates can appear; when the molar ratio of the titanium to the dihydric alcohol is less than 1: 251, the amount of the dihydric alcohol is continuously increased, and the influence on the preparation and application of the catalyst is not found, so that the molar ratio of the titanium to the dihydric alcohol is preferably 1: 5.99-251.
Titanium composition used in the inventionIs selected from the group consisting of phosphorus compounds of the formula (C)nH2n+1O）3PO (wherein n is an integer of 1-8), triphenyl phosphate, trihydroxyethyl phosphate, trihydroxypropyl phosphate, trihydroxybutyl phosphate, 2-ethylhexyl diphenyl phosphate, pentaerythritol phosphate, and a compound represented by the general formula (C)nH2n+1O）3P (wherein n is an integer of 1-8) phosphite, triphenyl phosphite, trihydroxyethyl phosphite, trihydroxypropyl phosphite, trihydroxybutyl phosphite, phosphoric acid, phosphorous acid and hypophosphorous acid, but not limited to the above phosphorus compounds, the invention experiments find that the phosphorus atoms in the phosphorus compounds can form a coordination structure with titanium atoms and can adjust the activity of titanium atoms in catalyzing polyester, the invention proves the unique effect of phosphorus therein by comparing phosphorus compounds with different structures or carbon chain lengths, the phosphorus compounds selected by the invention are only optimized based on convenient application, commercial availability and price, in addition, the phosphorus compounds can be used singly or randomly mixed, for convenient application, the invention selects at least 1 and at most 3 of the phosphorus compounds, wherein the molar ratio of titanium to phosphorus is controlled within the range of 1: 0.49-5.33, when the molar ratio of titanium to phosphorus is less than 1: 5.33, inhibition of activity of phosphorus to titanium starts to be significant, and when the molar ratio of titanium to phosphorus is more than 1: 0.49, activity regulation of phosphorus to titanium is reduced significantly, and the polyester turns yellow by thermal degradation.
The complexes used in the present invention are of the formula CnH2n（COOH）2(wherein n is an integer of 0 and 1 to 8) dibasic acids and alkali metal salts thereof, general formula of HOCnH2nCOOH (wherein n is an integer of 1-5) hydroxy acid, malic acid, tartaric acid, potassium hydrogen tartrate, sodium potassium tartrate, citric acid, potassium citrate, sodium citrate, ascorbic acid, pentaerythritol and 5-sodium sulfoisophthalate, researches show that the coordination compounds have obvious synergistic effect with titanium and phosphorus compounds, the synergistic effect is to improve the activity and selectivity of titanium and further avoid the yellowing of polyester, in addition, the coordination compounds can be used independently or randomly and show excellent coordination effect, namely, the coordination compounds can be used in a mixed modeThe invention is convenient to use, at least 1 and at most 3 of the complexes are selected, and the dosage of the complexes is preferably 15-300 mg/kgPTA.
The general formula used in the present invention is CnH2n+1The Li, Na, K, Mg and AI salts of carboxylic acid of COOH (wherein n is an integer of 0 and 1-3) can be further cooperated with titanium and the like in the preparation process of polyester, so that more excellent catalytic performance is shown, the tackifying of PET polyester is facilitated, the Li, Na, K, Mg and AI salts can be used in the polyester independently or in a mixed manner, at least 1 and at most 3 of the Li, Na, K, Mg and AI salts are selected, and the total dosage in the polyester is 40-602 Mg/kgPTA.
The preparation method of the titanium phosphorus composition comprises the steps of vacuumizing a reaction system or introducing inert gas at normal pressure or normal pressure to promote the removal of low molecular compounds in the system, wherein the reaction temperature is generally controlled within the range from 105 ℃ to the boiling point of dihydric alcohol, when the temperature is lower than 105 ℃, the reaction needs to be carried out under the high vacuum condition of 0-50 Pa, the reaction speed is obviously reduced, when the temperature is higher than the boiling point of the dihydric alcohol participating in the reaction, the pressure of the system needs to be increased, the operation condition is complicated, the energy consumption is increased, the reaction temperature is kept within the range from 105 ℃ to the boiling point of the dihydric alcohol, and the reactant is kept in a boiling state along with the change of the pressure within the range from 0Pa to the normal pressure; at normal pressure, by introducing an inert gas such as N2、CO2Or He, typically N2The discharge of low molecular compounds in the system is promoted, the aim of quickly and efficiently preparing the titanium-phosphorus composition is achieved, and the flow of inert gas is generally controlled to be 0.01-1.0L/min-L reactor.
The invention relates to a preparation method of polyester, in particular to a preparation method of polyethylene terephthalate (PET), poly (1.3-trimethylene terephthalate) (PTT) and poly (1.4-butylene terephthalate) (PBT), wherein the preparation method of PET polyester comprises the steps of carrying out esterification under the conditions of normal pressure to 0.35MPa and temperature of 220 to 280 ℃ in the presence of a titanium catalyst, removing water generated in the reaction through a distillation or rectification device to obtain a prepolymer, then reducing the pressure to be below 100Pa, carrying out polycondensation at the temperature of 250 to 300 ℃, stopping the reaction when the viscosity of a polycondensate is reached in the polycondensation reaction, and carrying out continuous extrusion, cooling and cuttingGranulating to obtain polyester; putting the PET polyester chip into a vacuum drum for drying, controlling the temperature to be 175-180 ℃, keeping for 5 hours, and then performing solid-phase tackifying for 4-20 hours at the temperature of 220-245 ℃ and under the vacuum degree of 0-100 Pa to obtain a solid-phase tackified polyester chip (SSP); the PTT polyester is prepared by carrying out esterification reaction under the conditions of normal pressure to 0.3MPa and the temperature of 210 to 260 ℃ in the presence of a titanium catalyst, removing water generated by the reaction through a distillation or rectification device to obtain a prepolymer, then carrying out polycondensation at the temperature of 240 to 270 ℃ under reduced pressure of less than 100Pa, stopping the reaction when the viscosity of a polycondensate is reached by the polycondensation reaction, and carrying out continuous extrusion, cooling and grain cutting to obtain the PTT polyester; the PBT polyester is prepared in the presence of a titanium catalyst at a temperature of 2.0-5.0 x 104And (2) esterifying at the temperature of 220-250 ℃ under Pa, removing water generated in the reaction through a distillation or rectification device to obtain a prepolymer, then decompressing to below 100Pa, controlling the temperature to be 230-260 ℃ to perform polycondensation, stopping the reaction when the viscosity of a polycondensate is reached in the polycondensation reaction, and performing continuous extrusion, cooling and grain cutting to obtain the PBT polyester.
This is further illustrated by the following examples.
The specific implementation mode is as follows:
example 1:
57.1g of tetrabutyl titanate, 25g of trimethyl phosphate and 173g of 1.4-butanediol were added to a stirred reactor, heated and evacuated to (1.3 to 3.0). times.104Pa, boiling at the temperature of 170-190 ℃, recycling generated distillate through a distillation device, removing vacuum and cooling to normal temperature after the distillate is completely transparent, adding 1.4-butanediol to adjust the total weight to be 200g, and obtaining a titanium-phosphorus composition solution A containing 4% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 1.06, and the molar ratio of titanium to 1.4-butanediol is 1: 11.5.
Preparation of polyester: adding 1.0kg of terephthalic acid, 465g of ethylene glycol, 0.125g of titanium-phosphorus composition solution A, 0.03g of glycolic acid and 0.05g of sodium potassium tartrate as complex and 0.3g of lithium formate into a 2.5L stainless steel reaction kettle, esterifying under the condition of 0.05-0.3 MPa, removing water generated in the reaction by a rectifying device, reducing the pressure to normal pressure when the temperature is raised to 255 ℃, continuously raising the temperature to 260-280 ℃ until no water is discharged, vacuumizing and reducing the pressure gradually to below 100Pa within 45min, controlling the temperature to be 285-300 ℃, judging the end point of the polymerization reaction according to the rotating speed of a stirrer or the power of a motor, relieving the vacuum by using nitrogen when the viscosity of the corresponding polymer is 0.650dl/g (allowable error is 0.01), stopping the reaction, recording the total time of polycondensation, extruding the polymer in a fine strip form, cooling and cutting into particles to obtain polyester chips, testing the b value of the polyester chips, the results are shown in Table 1; the polyester chip is placed into a vacuum rotary drum for drying and pre-crystallization, then solid-phase tackifying is carried out for 6 hours under the conditions of 230-240 ℃ and 0-100 Pa of vacuum degree, so as to obtain solid-phase tackified polyester chip (SSP), and the intrinsic viscosity and the b value of the solid-phase tackified polyester chip are tested, and the results are shown in table 1.
Example 2:
21.6g of tetramethyl titanate and 23.8g of isopropyl titanate are mixed and hydrolyzed, about 11.2g of the solid product obtained by separation is added into a reactor with stirring, 60g of trimethyl phosphite and 130g of ethylene glycol are added, the mixture is heated to boiling under normal pressure, and N is introduced2And adjusting N2The flow rate is 0.5 liter/min.liter reactor, the generated distillate is collected by a distillation device, when the distillate is completely transparent, the temperature is reduced to normal temperature, and the glycol is added to adjust the temperature to 200g, thus obtaining the titanium-phosphorus composition solution B containing 5.0 percent of titanium, wherein the molar ratio of titanium to phosphorus is 1: 2.32, and the molar ratio of titanium to glycol is 1: 10.
Preparation of polyester: the same procedure was followed as in example 1 to prepare a polyester wherein the titanium phosphorus composition solution B was 0.100g, the complex was 0.12g of sebacic acid and 0.05g of malic acid, and the carboxylate was 0.30g of magnesium acetate; the solid phase tackifying time of the polyester was 15h, and the test results are shown in Table 1.
Example 3:
adding 74.5g of tetrabutyl titanate, 10g of titanium sulfate hydrolysate containing 55.7% of titanium, 56g of 2-ethylhexyl diphenyl phosphate and 240g of 1.4-butanediol into a reactor with stirring, vacuumizing until the pressure in the system is 0-50 Pa, heating and controlling the reaction temperature to be 105-120 ℃, recovering the generated distillate through a distillation device, removing the vacuum after the materials are completely transparent, cooling to the normal temperature, adding 1.4-butanediol to adjust to 320g, and obtaining the titanium-phosphorus composition solution C containing 5.0% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 0.49, and the molar ratio of titanium to 1.4-butanediol is 1: 7.98.
Preparation of polyester: 760g of terephthalic acid, 500g of 1.4-butanediol, 1.300g of a titanium phosphorus composition solution C, 0.01g of sodium oxalate as a complex, and 0.4g of aluminum acetate as a carboxylate were placed in a 2.5 liter stainless steel reactor at (2.0 to 5.0). times.104And (2) carrying out esterification under the condition of Pa, controlling heating and keeping at 240-245 ℃ when the temperature is increased to 240 ℃, removing distillate generated by the reaction through a distillation or rectification device, decompressing the obtained prepolymer to be below 100Pa after the esterification is finished, controlling the temperature to be 230-260 ℃ for polycondensation, stopping the reaction when the viscosity of the polycondensate is 1.000dl/g (allowable error is 0.01) after the polycondensation is finished, continuously extruding, cooling and granulating to obtain the PBT polyester, and testing the b value of the PBT polyester, wherein the results are shown in Table 1.
Example 4:
31.6g of tetraisopropyl titanate, 5.0g of a titanium 53.8% titanium tetrachloride hydrolyzate, 31g of triethyl phosphite and 130g of 1.3-propanediol were charged into a reactor with stirring, heated to boiling under normal pressure, and N was introduced thereinto2And adjusting N2The flow rate is 1.0 liter/min.L reactor, the generated distillate is collected by a distillation device, when the distillate is completely transparent, the temperature is reduced to normal temperature, 1.3-propylene glycol is added to adjust the temperature to 200g, and the titanium-phosphorus composition solution D containing 4.0 percent of titanium is obtained, wherein the molar ratio of titanium to phosphorus is 1: 1.12, and the molar ratio of titanium to 1.3-propylene glycol is 1: 10.24.
Preparation of polyester: adding 665g of terephthalic acid, 730g of 1.3-propylene glycol, 0.660g of titanium phosphorus composition solution D and 0.01g of succinic acid serving as a complex and 0.4g of magnesium acetate serving as a carboxylate into a 2.5-liter stainless steel reaction kettle, carrying out esterification under the condition of normal pressure to 0.3MPa, reducing the temperature to normal pressure when the temperature is increased to 210-230 ℃, continuously heating and keeping the temperature at 240-250 ℃, removing a distillate generated in the reaction through a distillation or rectification device, reducing the pressure of the obtained prepolymer to below 100Pa after the esterification is finished, carrying out polycondensation at 240-270 ℃, stopping the reaction when the viscosity of a polycondensate is 0.920dl/g (allowable error is 0.01) after the polycondensation reaction is finished, continuously extruding, cooling and carrying out grain cutting to obtain PTT polyester, and testing the b value of the PTT polyester, wherein the results are shown in Table 1.
Example 5:
a stirred reactor was charged with 7.43g of a hydrolysate of titanium tetrachloride containing 53.8% of titanium, 30g of trimethylol ethyl phosphate, 124g of ethylene glycol, heated to boiling under normal pressure, and N was passed through the reactor2And adjusting N2The flow rate is 0.01L/min.L reactor, the generated distillate is recovered by a distillation device, after the distillate is completely transparent, the temperature is reduced to normal temperature, and the ethylene glycol is added to adjust the temperature to 200g, so that titanium-phosphorus composition solution E containing 2.0 percent of titanium is obtained, wherein the molar ratio of titanium to phosphorus is 1: 1.56, and the molar ratio of titanium to ethylene glycol is 1: 23.94.
Preparation of polyester: a polyester was prepared in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution E was 0.250g, the amount of the complex was 0.01g, the amount of the complex was 0.04g, the amount of the carboxylate was 0.1g, and the amount of the lithium acetate was 0.1g, and the solid-phase thickening time of the polyester was 6 hours, and the results of the test are shown in Table 1.
Example 6:
19.1g of tetraoctyl titanate, 12.5g of trioctyl phosphite and 120g of 1.3-butanediol were placed in a stirred reactor, heated to boiling and CO was passed through2And regulating CO2And collecting the generated distillate through a distillation device in a reactor with the flow rate of 0.03L/min & L, cooling to normal temperature after the distillate is completely transparent, and adding 1.4-butanediol to adjust the temperature to 400g to obtain a titanium-phosphorus composition solution F containing 0.4% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 0.88, and the molar ratio of titanium to 1.3-butanediol is 1: 40.
Preparation of polyester: a polyester was prepared in the same manner as in example 1, wherein the titanium phosphorus composition solution F was 1.500g, the complex was oxalic acid 0.03g and sodium oxalate 0.02g, the carboxylate was lithium butyrate 0.40g, and the solid phase thickening time of the polyester was 6 hours, and the test results are shown in Table 1.
Example 7:
a stirred reactor was charged with 22.43g of a hydrolysate containing 53.5% titanium tetrabromide and 21.54g of a hydrolysate containing 55.7% titanium sulfate, 107g of trimethylol ethyl phosphite, 54.4g of trimethylolpropane phosphate and 186g of ethylene glycol, and the pressure was reduced to a system pressure (4-6). times.104Pa, heating to 150-160 ℃, collecting the generated distillate through a distillation device, and when the distillate is completely transparentThen, the temperature is reduced to normal temperature, and ethylene glycol is added to regulate the temperature to 400G, thus obtaining a composition solution G containing 6 percent of titanium, wherein the molar ratio of titanium to phosphorus is 1: 1.4, and the molar ratio of titanium to ethylene glycol is 1: 5.99.
Preparation of polyester: a polyester was prepared in the same manner as in example 1, wherein the titanium phosphorus composition solution G was 0.100G, the compounding agents were citric acid 0.06G and sodium sebacate 0.10G, the carboxylic acid salts were sodium formate 0.10G, potassium acetate 0.10G and sodium butyrate 0.10G, and the solid-phase thickening time of the polyester was 5 hours, and the test results are shown in Table 1.
Example 8:
adding 2.38g of tetraisopropyl titanate and 130g of ethylene glycol into a reactor with stirring, heating to a boiling point under normal pressure to obtain a white solid ethylene glycol titanium particle dispersion reaction product, stopping heating, cooling to 50 ℃, adding 8g of triphenyl phosphite, continuing heating to boil, introducing He gas, adjusting the flow rate of the He gas to be 0.3L/min.L, collecting distillate through a distillation device, cooling to normal temperature after the white solid is dissolved and completely transparent, adding ethylene glycol to adjust to 400g, and obtaining a titanium-phosphorus composition solution H containing 0.1% of titanium, wherein the molar ratio of titanium to total phosphorus is 1: 5.33, and the molar ratio of titanium to ethylene glycol is 1: 251.
Preparation of polyester: a polyester was prepared in the same manner as in example 1, except that 7.500g of the titanium phosphorus composition solution H, 0.04g of pentaerythritol as a complex, 0.05g of malic acid, 0.30g of aluminum acetate as a carboxylate, and that the solid-phase thickening time of the polyester was 12 hours, and the test results were shown in Table 1.
Example 9:
adding 23.8g of tetraoctyl titanate and 175g of butanediol (90) into a reactor with stirring, heating to a boiling point under normal pressure to obtain a 1.4-butanediol titanium pale yellow liquid product, stopping heating, cooling to 50 ℃, adding 4.0g of tributyl phosphate and 5.0g of trihydroxybutyl phosphite, vacuumizing, reducing pressure, heating to 160-180 ℃, collecting a distillate through a distillation device, cooling to normal temperature after no low molecular distillate exists and the product is completely transparent, and adding 1.4-butanediol to adjust to 400g to obtain a titanium-phosphorus composition solution I containing 0.5% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 0.76, and the molar ratio of titanium to 1.4-butanediol is 1: 46.3.
Preparation of polyester: a polyester was produced in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution I was 3.000 g; the complex is 0.01g of pentaerythritol, 0.01g of 1-hydroxypropionic acid and 0.08g of potassium hydrogen tartrate; the carboxylate is lithium formate 0.04g, the solid phase tackifying time of the polyester is 18h, and the test results are shown in Table 1.
Example 10:
57.1g of tetrabutyl titanate, 43.4g of trioctyl phosphate, 8.2g of phosphorous acid and 240g of 1.2-propanediol are placed in a stirred reactor, heated to boiling at atmospheric pressure, and CO is introduced2Gas and CO regulation2The gas flow is 0.3L/min.L reactor, the generated distillate is collected by a distillation device, when no low molecular distillate exists and the distillate is completely transparent, the temperature is reduced to normal temperature, 1.2-propylene glycol is added to adjust the temperature to 400g, and the titanium-phosphorus composition solution J containing 2 percent of titanium is obtained, wherein the molar ratio of titanium to phosphorus is 1: 1.2, and the molar ratio of titanium to 1.3-propylene glycol is 1: 18.9.
Preparation of polyester: a polyester was produced in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution J was 0.400 g; the complex is 0.30g of isophthalic acid-5-sodium sulfonate; the carboxylate is lithium formate 0.1g, potassium acetate 0.1g and magnesium acetate 0.2g, the solid phase tackifying time of the polyester is 4h, and the test results are shown in Table 1.
Example 11:
adding 14.4g of tetramethyl titanate and 150g of butanediol into a reactor with stirring, heating to the boiling point under normal pressure to obtain a 1.4-butanediol titanium pale yellow liquid product, stopping heating, cooling to 50 ℃, adding 15.7g of trihydroxybutyl phosphate, 9.8g of phosphoric acid and 13.3g of tributyl phosphate, heating to the boiling point, introducing CO, and stirring2And regulating CO2The flow rate is 0.01L/min.L reactor, the generated distillate is collected by a distillation device, when no low molecular distillate exists and the distillate is completely transparent, the temperature is reduced to normal temperature, 1.4-butanediol is added to adjust the temperature to 400g, and the titanium-phosphorus composition solution K containing 1.0 percent of titanium is obtained, wherein the molar ratio of titanium to phosphorus is 1: 2.4, and the molar ratio of titanium to 1.4-butanediol is 1: 20.
Preparation of polyester: 8ppm A polyester was prepared in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution K was 0.800 g; the complex is 0.15g of isophthalic acid-5-sodium sulfonate and 0.05g of sodium hydrogen tartrate; the carboxylate is 0.20g of potassium acetate, the solid phase tackifying time of the polyester is 12h, and the test results are shown in Table 1.
Example 12:
adding 4.78g of tetraisopropyl titanate, 9g of pentaerythritol phosphate and 180g of ethylene glycol into a reactor with stirring, heating to boil, collecting generated distillate through a distillation device, cooling to normal temperature after no low molecular distillate is generated and the distillate is completely transparent, and adding ethylene glycol to adjust the temperature to 400g to obtain a titanium-phosphorus composition solution L containing 0.2% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 2.97, and the molar ratio of titanium to ethylene glycol is 1: 174.
Preparation of polyester: 20ppm A polyester was prepared in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution L was 10.0 g; the coordination compound comprises 0.10g of succinic acid and 0.20g of m-phthalic acid-5-sodium sulfonate; the carboxylate is 0.05g of lithium acetate, the solid-phase tackifying time of the polyester is 12h, and the test results are shown in Table 1.
Example 13:
adding 59.6g of tetraisopropyl titanate, 48.9g of triphenyl phosphate, 3.9g of hypophosphorous acid and 140g of ethylene glycol into a reactor with stirring, vacuumizing until the pressure in the system is 0-100 Pa, heating and controlling the reaction temperature to be 105-110 ℃, heating to boil, cooling to normal temperature after no low molecular distillate exists and the solution is completely transparent, and adding ethylene glycol to adjust the temperature to 400g to obtain a titanium-phosphorus composition solution M containing 2.5% of titanium, wherein the molar ratio of titanium to phosphorus is 1: 1.0, and the molar ratio of titanium to ethylene glycol is 1: 10.8.
Preparation of polyester: a polyester was produced in the same manner as in example 1, wherein the amount of the titanium phosphorus composition solution M was 0.300 g; the complex is 0.05g of sodium oxalate and 0.05g of 3-hydroxycaproic acid; the carboxylate is 0.25g of lithium acetate, the solid-phase tackifying time of the polyester is 6h, and the test results are shown in Table 1.
Comparative example:
a polyester was prepared in the same manner as in example 1, with 0.35g of ethylene glycol antimony as catalyst, and with a solid phase tackifying time of 6h, and the test results are shown in Table 1.
The invention uses the symbols: MPa is MPa; pa: handkerchief; h: hours; min: the method comprises the following steps of (1) taking minutes; l is liter; mg: mg; g: g; kg: kilogram; percent: and (4) percent by mass.
The intrinsic viscosity (in dl/g, abbreviated form of decilites/grams) of the polyester in the present invention was measured by Ubbelohde viscometer; the b value was measured by a color difference meter.
As can be seen from examples 1 to 13 and comparative examples, the present invention has the following advantages:
1. the synthesized titanium composition shows remarkable catalytic activity in catalyzing Polyester (PET) reaction;
2. the titanium composition catalyst synthesized by the method is used as a polyester catalyst, so that the preparation process of using an antimony catalyst can be omitted, the production cost of polyester is reduced, and the environmental pollution in the production and post-processing processes of polyester is eliminated.
Table 1:
Claims (9)
1. a preparation method of polyester comprises the steps of taking terephthalic acid and dihydric alcohol as raw materials, carrying out esterification under the conditions of normal pressure to 0.5MPa and temperature of 210 to 280 ℃ in the presence of a titanium catalyst, removing low molecular compounds generated in the reaction through a distillation or rectification device to obtain a prepolymer, then reducing the pressure to be below 100Pa, controlling the temperature to be 230 to 300 ℃ for polycondensation, stopping the reaction when the viscosity of a polycondensate is reached in the polycondensation reaction, and carrying out continuous extrusion, cooling and grain cutting to obtain the polyester; putting the obtained PET polyester slices into a vacuum drum for drying, controlling the temperature to be 175-180 ℃, keeping for 5 hours, and then performing solid-phase tackifying for 4-20 hours at the temperature of 220-245 ℃ and under the vacuum degree of 0-100 Pa to obtain solid-phase tackified polyester slices (SSP); the titanium catalyst used had the following composition:
(A) a titanium phosphorus composition;
(B) a complex;
(C) selected from the group consisting of those of the formula CnH2n+1Li, Na, K, Mg, of a COOH monoacid,An Al salt, n is 0 and an integer of 1 to 3;
the titanium-phosphorus composition is prepared by mixing and reacting a titanium compound, dihydric alcohol and a phosphorus-containing compound, and is characterized in that the titanium compound, the dihydric alcohol and the phosphorus-containing compound are added into a reactor, the reaction is carried out under reduced pressure or normal pressure or by introducing inert gas in the range from 105 ℃ to the boiling point of the dihydric alcohol, low molecular compounds generated in a system are removed, when no low molecular compound is distilled off, the reaction is stopped, the reaction is cooled to normal temperature, and a colorless or pale yellow liquid product obtained in the reactor is the titanium-phosphorus composition, wherein the titanium content is 0.1-6%, the molar ratio of titanium to phosphorus is 1: 0.49-5.33, and the molar ratio of titanium to dihydric alcohol is 1: 5.99 to 251; when the titanium-phosphorus composition is used for preparing polyester, the dosage of the titanium-phosphorus composition is 5-85.5 mg/kgPTA in terms of titanium, the dosage of the complex is 13-300 mg/kgPTA, and the general formula is CnH2n+1The amount of Li, Na, K, Mg, Al salts of the COOH monoacid is 40-602 Mg/kgPTA, and n is 0 and an integer of 1-3.
2. The method for preparing polyester according to claim 1, wherein the titanium compound is selected from the group consisting of Ti (C)nH2n+1O)4Titanate and hydrolysate thereof, reaction product of titanate and dihydric alcohol, general formula of TiX4At least one of titanium halide and titanium sulfate hydrolysate, n is an integer of 1-8, and X is Cl or Br.
3. The method of claim 1, wherein the diol is selected from the group consisting of the diols of the formula HO (CH)2）nOne of OH diols, n is an integer of 2-4.
4. The process for producing a polyester according to claim 1, wherein the phosphorus-containing compound is selected from the group consisting of compounds represented by the general formula (C)nH2n+1O）3Phosphate of PO having the formula (C)nH2n+1O）3P phosphite, triphenyl phosphate, triphenyl phosphite, trihydroxyethyl phosphate, trihydroxypropyl phosphate, trihydroxybutyl phosphate, 2-ethylhexyl diphenyl phosphate, quaternary phosphoniumAt least one of pentaerythritol phosphate, wherein n is an integer of 1-8.
5. The process for preparing a polyester according to claim 1, wherein said complex is selected from the group consisting of those having the formula CmH2m（COOH）2A dibasic acid of the general formula CmH2m（COOH）2Alkali metal salt of dibasic acid of the formula HOCnH2nAt least one of COOH hydroxy acid, malic acid, tartaric acid, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, citric acid, potassium citrate, sodium citrate, ascorbic acid, pentaerythritol and sodium 5-sulfoisophthalate, wherein m is an integer of 0 and 1-8, and n is an integer of 1-5.
6. The method for preparing polyester according to claim 1, wherein the low molecular compound generated in the system is removed by reaction under reduced pressure or normal pressure or by introducing inert gas, wherein reduced pressure means that the pressure in the system is controlled to be 0 to 105Pa。
7. The process for producing a polyester, according to claim 1, wherein the low molecular compound produced in the system is removed by reacting under reduced pressure or atmospheric pressure or by introducing an inert gas, characterized in that the inert gas introduced is N2Or He or carbon dioxide.
8. The method for preparing polyester according to claim 1, wherein the low molecular compound generated in the system is removed by reacting under reduced pressure or normal pressure or by introducing an inert gas, characterized in that the flow rate of the inert gas is 0.01 to 1.0L/min-L in the reactor.
9. A process for the preparation of a polyester, according to claim 1, characterized by the preparation of polyethylene terephthalate (PET), poly-1.3-trimethylene terephthalate (PTT) and poly-1.4-tetramethylene terephthalate (PBT).
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