CN108976403A - The preparation method of polyester - Google Patents
The preparation method of polyester Download PDFInfo
- Publication number
- CN108976403A CN108976403A CN201810896182.3A CN201810896182A CN108976403A CN 108976403 A CN108976403 A CN 108976403A CN 201810896182 A CN201810896182 A CN 201810896182A CN 108976403 A CN108976403 A CN 108976403A
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- CN
- China
- Prior art keywords
- titanium
- polyester
- preparation
- phosphorus
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 47
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 67
- 239000010936 titanium Substances 0.000 claims description 65
- 229910052719 titanium Inorganic materials 0.000 claims description 63
- 229910052698 phosphorus Inorganic materials 0.000 claims description 32
- 239000011574 phosphorus Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- -1 Alkali metal salt Chemical class 0.000 claims description 19
- 239000007790 solid phase Substances 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 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
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000003608 titanium Chemical class 0.000 claims description 9
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 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 6
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000002148 esters Chemical class 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 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
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- 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 3
- 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 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
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 3
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 3
- 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 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims 1
- 235000019253 formic acid Nutrition 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
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- GCTMVWJHICUMRV-UHFFFAOYSA-N octan-3-yl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC(CC)CCCCC)OC1=CC=CC=C1 GCTMVWJHICUMRV-UHFFFAOYSA-N 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 229960003975 potassium Drugs 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 61
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 13
- 150000007942 carboxylates Chemical class 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 229910052787 antimony Inorganic materials 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment 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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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 2
- 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 group 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
- 239000002585 base Substances 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical group [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001384 succinic acid Substances 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- RISRGKINPSVAJP-UHFFFAOYSA-N [Li].C(CCC)(=O)O Chemical compound [Li].C(CCC)(=O)O RISRGKINPSVAJP-UHFFFAOYSA-N 0.000 description 1
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N beta-hydroxy propionic acid Natural products OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XBVVKNHQSFUHLZ-UHFFFAOYSA-N decanedioic acid;sodium Chemical compound [Na].OC(=O)CCCCCCCCC(O)=O XBVVKNHQSFUHLZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- WDABCHFVYNJWNU-UHFFFAOYSA-N formic acid;lithium Chemical compound [Li].OC=O WDABCHFVYNJWNU-UHFFFAOYSA-N 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- JNWGMESTOMYLND-UHFFFAOYSA-N hexanedioic acid;sodium Chemical compound [Na].OC(=O)CCCCC(O)=O JNWGMESTOMYLND-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000016337 monopotassium tartrate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 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
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229940086065 potassium hydrogentartrate Drugs 0.000 description 1
- KYKNRZGSIGMXFH-UHFFFAOYSA-M potassium;2,3-dihydroxybutanedioate;hydron Chemical compound [K+].OC(=O)C(O)C(O)C([O-])=O KYKNRZGSIGMXFH-UHFFFAOYSA-M 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 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
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of preparation method of polyester uses (A) titanium phosphorus composition, (B) complex, (C) to be selected from general formula C using terephthalic acid (TPA) and dihydric alcohol as raw materialnH2n+1The COOH(integer that wherein n is 0 and 1 ~ 3) monoacid Li, Na, K, Mg, AI salt as catalyst preparation polyester, the catalyst activity is good, the poly terephthalic acid binary alcohol esters b value that catalyzes and synthesizes is low.
Description
Technical field
The present invention relates to a kind of preparation method fields of polyester, are by titanium compound, dihydric alcohol and phosphorous in more detail
Compound hybrid reaction prepares titanium phosphorus composition, and titanium phosphorus composition, complex and monocarboxylic Li, Na, K, Mg, AI salt are made
The field of poly terephthalic acid binary alcohol esters synthesis is used for for catalyst.
Background technique
At present in the world 95% or more polyester (PET) be include antimony oxide, antimony acetate or second using antimony-based catalyst
The production of glycol antimony, antimony metal content is generally in 150 ~ 350ug/g in polyester, but antimonial is toxic as one kind, contains a huge sum of money
The compound of category has pollution to environment, toxic antimony can also be precipitated in polyester product use process, thus to health of human body
There are harm, therefore are constantly subjected to global concern, and from the polyester industry early stage of development, people are just continuously being ground always
Study carefully the substitute products of antimony catalyst or reduce antimony and used as polyester catalyst, such as research uses germanium compound, titanium compound.
Because resource is few, price is high, application is restricted germanium compound；Titanium series catalyst since its activity is high, is free of heavy metal, thus
It is constantly subjected to the favor of domestic and international polyester producers, once repeatedly at home and abroad becomes research hotspot, titanium catalyst synthesis and application
In polyester synthesis also it is commonly reported that, the component of titanium catalyst from the titanate esters of facile hydrolysis to modified titanate esters, titaniferous metal salt,
Complex titanium catalyst etc. has numerous studies and report, but its activity is unstable so far, catalysis side reaction is significant, easily leads to polyester
The defect of yellowing etc. is never resolved, and limits its application.In recent report, patent 200710041917.6
A kind of titanium-containing catalyst is described in a kind of production method of polyester and obtains not yellowing polyester, but the catalyst preparation process is multiple
Miscellaneous, intermediate product needs repeatedly washing and vacuum drying, to bring new environmental pollution again, and the catalyst is used to make
There are still stability when standby polyester the problems such as molecular weight does not increase when poor, polyester viscosifies, this be also so far antimony-based catalyst still exist
The most basic reason of main status is occupied in polyester catalyst.
Summary of the invention
The object of the invention is to overcome defect of the existing technology, using new technical characteristic, a kind of combination is provided
Catalyst and the application of realization in the polyester.
In order to reach the purpose of the present invention, the invention adopts the following technical scheme: a kind of preparation method of polyester, to benzene
Dioctyl phthalate and dihydric alcohol are raw material, in the presence of Titanium series catalyst, under the conditions of normal pressure ~ 0.35MPa, 210 ~ 280 DEG C of temperature into
Row esterification, and the water that reaction generates is sloughed by distillation or rectifier unit, prepolymer is obtained, is then gradually depressurized in 60min
To 100 Pa hereinafter, controlled at 230 ~ 300 DEG C of progress polycondensations, stop reaction when polycondensation reaction reaches condensation polymer viscosity,
It is continuously squeezed out, cooling, pelletizing obtains polyester；PET polyester slice therein is put into vacuum drum to dry, control temperature
It is 175 ~ 180 DEG C, is kept for 5 hours, then under the conditions of 220-245 DEG C, 0 ~ 100Pa of vacuum degree, 4 ~ 20h of solid-phase tack producing is obtained
Solid-phase tack producing polyester slice (SSP), wherein Titanium series catalyst composition is as follows:
(A) titanium phosphorus composition；
(B) complex；
(C) it is selected from general formula CnH2n+1COOH(wherein n be 0 and 1 ~ 3 integer) carboxylic acid Li, Na, K, Mg, AI salt；
Wherein, titanium phosphorus composition is prepared by titanium compound, dihydric alcohol and phosphorus-containing compound hybrid reaction, it is characterised in that is being reacted
Titanium compound is added in device, phosphorus compound and dihydric alcohol, temperature are reacted at 105 DEG C to dihydric alcohol boiling point, by decompression or
Normal pressure or normal pressure are passed through the low molecular compound generated in inert gas abjection system, when no low molecular compound distillates, stop
It only reacts, is down to room temperature, the colourless or light yellow liquid product obtained in the reactor is titanium phosphorus composition, wherein Ti content
It is 1: 0.49 ~ 5.33 for the molar ratio of 0.1 ± 6.0%, titanium and phosphorus, the molar ratio of titanium and dihydric alcohol is 1:5.99 ~ 251；For
When prepared by polyester, titanium phosphorus composition dosage is calculated as 5 ~ 85.5mg/kgPTA with titanium, the dosage of complex is 13 ~ 300mg/kgPTA,
General formula is CnH2n+1The COOH(integer that wherein n is 0 and 1 ~ 3) dosage of Li, Na, K, Mg salt of monoacid is 40 ~ 602 mg/
kgPTA。
Titanium compound used in titanium phosphorus composition is prepared in the present invention is selected from general formula (CnH2n+1O)4(wherein n is 1 ~ 8 to Ti
Integer) titanate esters and its hydrolysate, general formula (CnH2n+1O)4The titanate esters and general formula HO of Ti (the wherein integer that n is 1 ~ 8)
(CH2) the nOH(integer that wherein n is 2 ~ 4) and the reaction product of dihydric alcohol, general formula TiX4The hydrolysis of (X CI, Br) halogenated titanium produces
Object, titanium sulfate hydrolysate, these titanium compounds both can be used alone, and can also be used in any combination, at least select one kind,
Experimental studies have found that the titanium that these titanium compounds provide all is equivalent, the content of titanium in the composition under the conditions of the present invention
Control is 0.1 ~ 6%, when being lower than 0.1%, can dramatically increase transportation cost, increase use process energy consumption, when being higher than 6%, catalysis
Agent storage stability is deteriorated.
Dihydric alcohol used in titanium composition, general formula HO(CH are prepared in the present invention2) nOH(wherein n be 2 ~ 4 it is whole
Number), this kind of dihydric alcohol is both the raw material of polyester, and ortho position therein and meta position dihydric alcohol can be coordinated to constitute with titanium atom again to be stablized
Structure improves its hydrolytic Resistance, and it is 1: 5.99 ~ 251 that the present invention, which selects the molar ratio of control titanium and dihydric alcohol, when titanium and two
When the molar ratio of first alcohol is greater than 1: 5.99, composition is unstable, has sediment appearance；When the molar ratio of titanium and dihydric alcohol is less than
When 1: 251, the amount of dihydric alcohol is continued growing, does not find to have an impact catalyst preparation and application, therefore, the preferred titanium of the present invention
Molar ratio with dihydric alcohol is 1: 5.99 ~ 251.
Preparing phosphorus compound used in titanium composition in the present invention and being selected from general formula is (CnH2n+1O)3Wherein n is 1 ~ 8 to PO(
Integer) phosphate, triphenyl phosphate, tricresyl phosphate hydroxyethyl ester, tricresyl phosphate hydroxypropyl ester, tricresyl phosphate hydroxyl butyl ester, 2- second
Base hexyl diphenyl phosphoester, pentaerythritol phosphate, general formula are (CnH2n+1O)3The P(integer that wherein n is 1 ~ 8) phosphite ester,
Triphenyl phosphite, phosphorous acid trihydroxyethyl ester, three hydroxypropyl ester of phosphorous acid, three hydroxyl butyl ester of phosphorous acid, phosphoric acid, phosphorous acid and
Hypophosphorous acid, but it is not limited to the above phosphorus compound, the present invention, which tests, finds that the phosphorus atoms in this kind of phosphorus compound can
Activity when constituting coordination structure with titanium atom and titanium atom catalyst, polyester can be adjusted, by comparing different structure or carbon chain length
The phosphorus compound of degree, it was demonstrated that the wherein unique effect of phosphorus, these phosphorus compounds that the present invention selects be only based on facilitate application,
Commodity availability and price have carried out preferably, in addition, these phosphorus compounds both can be used alone, can also arbitrarily mix
It uses, for convenient for application, present invention selection is therein at least one kind of, 3 kinds most, wherein the control of the molar ratio of titanium and phosphorus is 1:
In 0.49 ~ 5.33 range, when the molar ratio of titanium and phosphorus is less than 1: 5.33, phosphorus starts obvious and works as titanium to the activity suppression of titanium
When being greater than 1: 0.49 with the molar ratio of phosphorus, phosphorus is obvious to the Active Regulation effect decline of titanium, and polyester can turn yellow because of thermal degradation.
Complex used in the present invention is general formula CnH2n(COOH)2The binary acid of (the wherein integer that n is 0 and 1 ~ 8)
And its alkali metal salt, general formula HOCnH2nThe COOH(integer that wherein n is 1 ~ 5) carboxylic acid, malic acid, tartaric acid, hydrogen tartrate
Potassium, sodium hydrogen tartrate, sodium potassium tartrate tetrahydrate, citric acid, potassium citrate, sodium citrate, ascorbic acid, pentaerythrite, isophthalic diformazan
Acid -5- sodium sulfonate, the study found that the synergistic effect of these complexs and titanium, phosphorus compound is obvious, coefficient effect is to mention
The activity and selectivity of high titanium further avoids polyester yellowing, can also be in addition, these complexs both can be used alone
It is arbitrarily used in mixed way, shows excellent fiting effect, for convenience of applying, present invention selection is therein at least one kind of, and most 3
Kind, wherein the dosage of complex is preferably 15 ~ 300mg/kgPTA.
General formula used in the present invention is CnH2n+1The COOH(integer that wherein n is 0 and 1 ~ 3) Li, Na of carboxylic acid, K,
Mg, AI salt can further cooperate with titanium etc. in polyester preparation process, to show superior catalytic performance, and have
It conducive to the thickening of PET polyester, may be used alone, can also be used in combination in the polyester, present invention selection therein at least 1
Kind, most 3 kinds, total dosage in the polyester is 40 ~ 602 mg/kgPTA.
The preparation method of titanium phosphorus composition in the present invention, be by reaction system is vacuumized or normal pressure or normal pressure be passed through it is lazy
Property gas promotes the low molecular compound in abjection system, reaction temperature general control in 105 DEG C to dihydric alcohol boiling spread,
When temperature is lower than 105 DEG C of reactions, reaction needs under 0 ~ 50Pa high vacuum condition, and reaction speed is substantially reduced, and works as temperature
When degree is higher than the dihydric alcohol boiling temperature for participating in reaction, need to improve system pressure, this can be such that operating condition complicates and increase
Energy consumption, reaction temperature are maintained at 105 DEG C in dihydric alcohol boiling point temperature range, with pressure in 0Pa to normal pressure range, make anti-
Object is answered to be maintained at fluidized state；It can also be by being passed through inert gas such as N when normal pressure2、CO2Or He, generally use N2In promotion system
Low molecular compound discharge, achieved the purpose that rapidly and efficiently to prepare titanium phosphorus composition, inert gas flow general control exists
0.01 ~ 1.0L/minL reactor.
A kind of preparation method of polyester of the present invention, refers to polyethylene terephthalate (PET), poly terephthalic acid-
The preparation method of 1.3- propylene glycol ester (PTT) and poly terephthalic acid -1.4- butanediol ester (PBT), wherein preparing PET polyester is
It in the presence of Titanium series catalyst, is esterified under the conditions of normal pressure ~ 0.35MPa, 220 ~ 280 DEG C of temperature, and passes through distillation or essence
Distillation unit slough reaction generate water, obtain prepolymer, be then decompressed to 100 Pa hereinafter, controlled at 250 ~ 300 DEG C into
Row polycondensation stops reaction when polycondensation reaction reaches condensation polymer viscosity, is continuously squeezed out, and cooling, pelletizing obtains polyester；It should
PET polyester slice is put into vacuum drum dry, controlled at 175 ~ 180 DEG C, is kept for 5 hours, then 220 ~ 245 DEG C,
Under the conditions of 0 ~ 100Pa of vacuum degree, 4 ~ 20h of solid-phase tack producing obtains solid-phase tack producing polyester slice (SSP)；Preparing PTT polyester is in titanium
In the presence of catalyst, esterification is carried out under the conditions of normal pressure ~ 0.3MPa, 210 ~ 260 DEG C of temperature, and pass through distillation or rectifying dress
It sets and sloughs the water that reaction generates, obtain prepolymer, be then decompressed to 100 Pa hereinafter, contracting controlled at 240 ~ 270 DEG C
It is poly-, stop reaction when polycondensation reaction reaches condensation polymer viscosity, continuously squeezed out, cooling, pelletizing obtains PTT polyester；Prepare PBT
Polyester is in the presence of Titanium series catalyst, 2.0 ~ 5.0 × 104Pa, it is esterified under the conditions of 220 ~ 250 DEG C of temperature, and is passed through
Distillation or rectifier unit slough the water that reaction generates, and obtain prepolymer, then it is decompressed to 100 Pa hereinafter, controlled at 230 ~
260 DEG C of progress polycondensations stop reaction when polycondensation reaction reaches condensation polymer viscosity, are continuously squeezed out, and cooling, pelletizing obtains PBT
Polyester.
It is further illustrated below by embodiment.
Specific embodiment:
Embodiment 1:
57.1g butyl titanate, 25g trimethyl phosphate and 173g 1.4- butanediol are added in the reactor with stirring, adds
Heat is simultaneously evacuated to (1.3 ~ 3.0) × 104Pa, boiling is kept within the scope of 170 ~ 190 DEG C, generated by distilling apparatus recycling
Distillate releases vacuum and is simultaneously cooled to room temperature after fully transparent, and it is 200g to get arriving that 1.4- butanediol, which is added, and adjusts gross weight
The titanium phosphorus composition solution A of titaniferous 4%, it is 1 that wherein the molar ratio of titanium and phosphorus, which is the molar ratio of 1: 1.06, titanium and 1.4- butanediol:
11.5。
The preparation of polyester: in 2.5 liters of stainless steel cauldrons, be added 1.0kg terephthalic acid (TPA), 465g ethylene glycol,
0.125g titanium phosphorus composition solution A, complex are 0.03g hydroxyacetic acid and 0.05 sodium potassium tartrate tetrahydrate, and carboxylate is 0.3g formic acid
Lithium is esterified under the conditions of 0.05 ~ 0.3MPa, and sloughs the water that reaction generates by rectifier unit, when temperature rise is to 255 DEG C
When, it is depressurized to normal pressure, then proceedes to be warming up to 260 ~ 280 DEG C, until anhydrous discharge, hereafter vacuumizes decompression and in 45min
Gradually 100Pa is decompressed to hereinafter, judging polymerization reaction according to agitator speed or power of motor controlled at 285 ~ 300 DEG C
Terminal releases vacuum with nitrogen when corresponding polymer viscosity is 0.650dl/g (allowable error 0.01), stops reaction, note
Polycondensation total time is recorded, polymer is squeezed out with shredded forms, cooling, pelletizing obtains polyester slice, tests its b value, as a result see
Table 1；The polyester slice is put into vacuum drum it is dry and pre-crystallized, then in 230 ~ 240 DEG C, vacuum degree 0 ~ 100Pa condition
Lower progress solid-phase tack producing 6h, obtains solid-phase tack producing polyester slice (SSP), tests its inherent viscosity and b value, the results are shown in Table 1.
Embodiment 2:
21.6g tetramethoxy titanate ester and 23.8g isopropyl titanate are subjected to mixed hydrolysis, about by isolated solid product
11.2g is added in the reactor with stirring, adds 60g Trimethyl phosphite and 130g ethylene glycol, is heated to boiling under normal pressure
It rises, is passed through N2And adjust N2Flow is that 0.5 liter/min rises reactor, the distillate generated is collected by distilling apparatus, when complete
After all-transparent, be cooled to room temperature, by be added ethylene glycol be adjusted to 200g to get arrive titaniferous 5.0% titanium phosphorus composition solution B,
It is 1: 10 that wherein the molar ratio of titanium and phosphorus, which is the molar ratio of 1: 2.32, titanium and ethylene glycol,.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution B is
0.100g, complex are decanedioic acid 0.12g and malic acid 0.05g, and carboxylate is magnesium acetate 0.30g；When the solid-phase tack producing of polyester
Between be 15h, test result is shown in Table 1.
Embodiment 3:
With stirring reactor in be added 74.5g butyl titanate, 10g titaniferous 55.7% titanium sulfate hydrolysate,
56g2- ethylhexyl diphenyl phosphate and 240g 1.4- butanediol, being evacuated to system pressure is 0 ~ 50Pa, and heating is simultaneously
Reaction temperature is controlled at 105 ~ 120 DEG C, the distillate generated by distilling apparatus recycling releases vacuum, drop after fully transparent
To room temperature, 1.4- butanediol is added and is adjusted to 320g to get the titanium phosphorus composition solution C of titaniferous 5.0% is arrived, wherein titanium and phosphorus
Molar ratio is 1: 0.49, the molar ratio of titanium and 1.4- butanediol is 1: 7.98.
The preparation of polyester: in 2.5 liters of stainless steel cauldrons, be added 760g terephthalic acid (TPA), 500g1.4- butanediol,
1.300g titanium phosphorus composition solution C, complex are sodium oxalate 0.01g, carboxylate is aluminum acetate 0.4g, (2.0 ~ 5.0) ×
104It is esterified under the conditions of Pa, when temperature rises to 240 DEG C, control is heated and maintained at 240 ~ 245 DEG C, passes through distillation or essence
Distillation unit slough reaction generate distillate, after the completion of esterification, will obtain prepolymer be decompressed to 100 Pa hereinafter, controlled at
230 ~ 260 DEG C of progress polycondensations stop anti-when it is 1.000dl/g (allowable error 0.01) that polycondensation reaction, which reaches condensation polymer viscosity,
It answers, is continuously squeezed out, cooling, pelletizing obtains PBT polyester, tests its b value, the results are shown in Table 1.
Embodiment 4:
With stirring reactor in be added 31.6g tetraisopropyl titanate, 5.0g titaniferous 53.8% titanium tetrachloride hydrolysis
Product, 31g triethyl phosphite and 130g1.3- propylene glycol, normal heating are passed through N to boiling2And adjust N2Flow is 1.0 liters
/ minL reactor collects the distillate generated by distilling apparatus and is cooled to room temperature after fully transparent, passes through addition
1.3- propylene glycol is adjusted to 200g to get the titanium phosphorus composition solution D of titaniferous 4.0% is arrived, the molar ratio of titanium and phosphorus is 1: 1.12,
The molar ratio of titanium and 1.3- propylene glycol is 1: 10.24.
The preparation of polyester: in 2.5 liters of stainless steel cauldrons, be added 665g terephthalic acid (TPA), 730g1.3- propylene glycol,
0.660g titanium phosphorus composition solution D, complex are succinic acid 0.01g, and carboxylate is magnesium acetate 0.4g, in normal pressure ~ 0.3MPa item
It is esterified under part, when temperature rises to 210 ~ 230 DEG C, is down to normal pressure, continued to be heated and maintained at 240 ~ 250 DEG C, pass through steaming
Evaporate or rectifier unit slough reaction generate distillate, after the completion of esterification, will obtain prepolymer be decompressed to 100 Pa hereinafter,
240 ~ 270 DEG C of progress polycondensations stop instead when polycondensation reaction reaches when condensation polymer viscosity is 0.920dl/g (allowable error 0.01)
It answers, is continuously squeezed out, cooling, pelletizing obtains PTT polyester, tests its b value, the results are shown in Table 1.
Embodiment 5:
Hydrolysate, the 30g tricresyl phosphate hydroxyl second of the titanium tetrachloride of 7.43g titaniferous 53.8% are added in the reactor with stirring
Base ester, 124g ethylene glycol are heated to boiling under normal pressure, are passed through N2And adjust N2Flow is 0.01L/minL reactor, is passed through
The distillate that distilling apparatus recycling generates is cooled to room temperature after fully transparent, is adjusted to 200g by the way that ethylene glycol is added, i.e.,
The titanium phosphorus composition solution E of titaniferous 2.0% is obtained, wherein the molar ratio of titanium and phosphorus is that the molar ratio of 1: 1.56, titanium and ethylene glycol is
1∶23.94。
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution E is
0.250g, complex are 0.01g adipic acid sodium and ascorbic acid 0.04g, carboxylate are potassium acetate 0.1g and lithium acetate 0.1g, are gathered
The solid-phase tack producing time of ester is 6h, and test result is shown in Table 1.
Embodiment 6:
Four monooctyl ester of 19.1g metatitanic acid, three monooctyl ester of 12.5g phosphorous acid, 120g1.3- butanediol are added in the reactor with stirring,
It is heated to boiling, is passed through CO2And adjust CO2Flow is 0.03L/minL reactor, collects evaporating for generation by distilling apparatus
Object out is cooled to room temperature after fully transparent, is adjusted to 400g by addition 1.4- butanediol to get the titanium of titaniferous 0.4% is arrived
Phosphorus composition solution F, wherein the molar ratio of titanium and phosphorus is 1: 0.88, and the molar ratio of titanium and 1.3- butanediol is 1: 40.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution F is
1.500g, complex are oxalic acid 0.03g and sodium oxalate 0.02g, carboxylate are butyric acid lithium 0.40g, the solid-phase tack producing time of polyester
For 6h, test result is shown in Table 1.
Embodiment 7:
The hydrolysate and 21.54g titaniferous of the titanium tetrabromide of 53.5 % of 22.43g titaniferous are added in the reactor with stirring
Hydrolysate, 107g phosphorous acid trihydroxyethyl ester, 54.4g tricresyl phosphate hydroxypropyl ester and the 186g ethylene glycol of 55.7% titanium sulfate,
It is decompressed to system pressure (4 ~ 6) × 104Pa, 150 ~ 160 DEG C are warming up to, the distillate generated are collected by distilling apparatus, when complete
After all-transparent, it is cooled to room temperature, ethylene glycol is added and is adjusted to 400g to get the composition solution G of titaniferous 6% is arrived, wherein titanium and phosphorus
Molar ratio be the molar ratio of 1: 1.4, titanium and ethylene glycol be 1: 5.99.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution G is
0.100g, complex be citric acid 0.06g and decanedioic acid sodium 0.10g, carboxylate be sodium formate 0.10g, potassium acetate 0.10g and fourth
The solid-phase tack producing time of sour sodium 0.10g, polyester are 5h, and test result is shown in Table 1.
Embodiment 8:
2.38g tetraisopropyl titanate is added in the reactor with stirring and 130g ethylene glycol, normal heating to boiling point obtain
White solid titanium ethylene glycolate particle dispersion reaction product stops heating, and when being cooled to 50 DEG C, 8g triphenyl phosphite is added,
Continue to be heated to boiling, being passed through He gas and adjusting He throughput is 0.3L/minL reactor, is distillated by distilling apparatus collection
Object is cooled to room temperature after white solid object dissolves and is fully transparent, and ethylene glycol is added and is adjusted to 400g to get titaniferous is arrived
0.1% titanium phosphorus composition solution H, it is 1: 251 that wherein the molar ratio of titanium and total phosphorus, which is the molar ratio of 1: 5.33, titanium and ethylene glycol,.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution H is
7.500g, complex are pentaerythrite 0.04g and malic acid 0.05g, carboxylate are aluminum acetate 0.30g, the solid-phase tack producing of polyester
Time is 12h, and test result is shown in Table 1.
Embodiment 9:
Four monooctyl ester of 23.8g metatitanic acid is added in the reactor with stirring and 175g butanediol (90), normal heating to boiling point obtain
To 1.4- butanediol titanium light yellow liquid product, stop heating, when being cooled to 50 DEG C, 4.0g tributyl phosphate is added and 5.0g is sub-
Tricresyl phosphate hydroxyl butyl ester vacuumizes and depressurizes and be warming up to 160 ~ 180 DEG C, distillate is collected by distilling apparatus, when no low molecule
Distillate and it is fully transparent after, be cooled to room temperature, by be added 1.4- butanediol be adjusted to 400g to get arrive titaniferous 0.5% titanium
Phosphorus composition solution I, it is 1: 46.3 that wherein the molar ratio of titanium and phosphorus, which is the molar ratio of 1: 0.76, titanium and 1.4- butanediol,.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution I is
3.000g；Complex is pentaerythrite 0.01g, 1- hydracrylic acid 0.01g and potassium hydrogen tartrate 0.08g；Carboxylate is lithium formate
The solid-phase tack producing time of 0.04g, polyester are 18h, and test result is shown in Table 1.
Embodiment 10:
With stirring reactor in be added 57.1g butyl titanate, 43.4g trioctyl phosphate, 8.2g phosphorous acid and
240g1.2- propylene glycol, normal heating are passed through CO to boiling2Gas simultaneously adjusts CO2Throughput is 0.3L/minL reactor, is passed through
Distilling apparatus collect generate distillate, when no low molecule distillate and it is fully transparent after, be cooled to room temperature, pass through be added 1.2-
Propylene glycol be adjusted to 400g to get arrive titaniferous 2% titanium phosphorus composition solution J, wherein the molar ratio of titanium and phosphorus be 1: 1.2, titanium with
The molar ratio of 1.3- propylene glycol is 1: 18.9.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution J is
0.400g；Complex is 5-sodium sulfo isophthalate 0.30g；Carboxylate is lithium formate 0.1g, 0.1g potassium acetate, 0.2g vinegar
The solid-phase tack producing time of sour magnesium, polyester is 4h, and test result is shown in Table 1.
Embodiment 11:
14.4g tetramethoxy titanate ester is added in the reactor with stirring and 150g butanediol, normal heating to boiling point obtain
1.4- butanediol titanium light yellow liquid product stops heating, and when being cooled to 50 DEG C, 15.7g tricresyl phosphate hydroxyl butyl ester, 9.8g is added
Phosphoric acid, 13.3g tributyl phosphate, are heated to boiling, are passed through CO2And adjust CO2Flow is 0.01L/minL reactor, is passed through
Distilling apparatus collect generate distillate, when no low molecule distillate and it is fully transparent after, be cooled to room temperature, pass through addition
1.4- butanediol is adjusted to 400g to get the titanium phosphorus composition solution K of titaniferous 1.0% is arrived, and wherein the molar ratio of titanium and phosphorus is 1:
2.4, the molar ratio of titanium and 1.4- butanediol is 1: 20.
The preparation of polyester: 8ppm prepares polyester using method similarly to Example 1, and wherein titanium phosphorus composition solution K is
0.800g；Complex is 5-sodium sulfo isophthalate 0.15g and sodium hydrogen tartrate 0.05g；Carboxylate is potassium acetate 0.20g,
The solid-phase tack producing time of polyester is 12h, and test result is shown in Table 1.
Embodiment 12:
4.78g tetraisopropyl titanate, 9g pentaerythritol phosphate and 180g ethylene glycol are added in the reactor with stirring, adds
Heat collects the distillate generated by distilling apparatus to boiling, when no low molecule distillate and it is fully transparent after, be cooled to normal
Temperature is adjusted to 400g by the way that ethylene glycol is added to get arriving the titanium phosphorus composition solution L of titaniferous 0.2%, wherein mole of titanium and phosphorus
It is 1: 174 than the molar ratio for 1: 2.97, titanium and ethylene glycol.
The preparation of polyester: 20ppm prepares polyester using method similarly to Example 1, and wherein titanium phosphorus composition solution L is
10.0g；Complex is succinic acid 0.10g and 5-sodium sulfo isophthalate 0.20g；Carboxylate is lithium acetate 0.05g, polyester
The solid-phase tack producing time be 12h, test result is shown in Table 1.
Embodiment 13:
With stirring reactor in be added 59.6g tetraisopropyl titanate, 48.9g triphenyl phosphate, 3.9g hypophosphorous acid and
140g ethylene glycol, being evacuated to system pressure is 0 ~ 100Pa, heats and controls reaction temperature at 105 ~ 110 DEG C, is heated to boiling
Rise, when no low molecule distillate and it is fully transparent after, be cooled to room temperature, be adjusted to 400g by the way that ethylene glycol is added to get to containing
The titanium phosphorus composition solution M of titanium 2.5%, it is 1: 10.8 that wherein the molar ratio of titanium and phosphorus, which is the molar ratio of 1: 1.0, titanium and ethylene glycol,.
The preparation of polyester: polyester is prepared using method similarly to Example 1, wherein titanium phosphorus composition solution M is
0.300g；Complex is sodium oxalate 0.05g and 3- hydroxycaproic acid 0.05g；Carboxylate is lithium acetate 0.25g, and the solid phase of polyester increases
The viscous time is 6h, and test result is shown in Table 1.
Comparative example:
Polyester is prepared using method similarly to Example 1, catalyst is 0.35g antimony glycol, the solid-phase tack producing time of polyester
For 6h, test result is shown in Table 1.
Symbol: MPa: megapascal is used in the present invention；Pa: pa；H: hour；Min: minute；L: it rises；Mg: milligram；G: gram；Kg:
Kilogram；%: mass percent.
Polyester inherent viscosity (shorthand of unit dl/g, deciliters/grams) is viscous by Ubbelohde in the present invention
Degree meter measurement；B value is measured by colour difference meter.
It can be seen that the present invention from embodiment 1~13 and comparative example to have the advantage that
1, the titanium composition that the present invention synthesizes shows significant catalytic activity in catalyst, polyester (PET) reaction；
2, the titanium composition catalyst synthesized using the present invention can eliminate the need for the tune of antimony-based catalyst as polyester catalyst
Process processed reduces production of polyester cost, eliminates existing environmental pollution during production of polyester and post-processing.
Table 1:
Claims (10)
1. a kind of preparation method of polyester, using terephthalic acid (TPA) and dihydric alcohol as raw material, in the presence of Titanium series catalyst, in normal pressure
~ 0.5MPa, it is esterified under the conditions of 210 ~ 280 DEG C of temperature, and the low molecule that reaction generates is sloughed by distillation or rectifier unit
Compound, obtains prepolymer, is then decompressed to 100 Pa hereinafter, working as polycondensation reaction controlled at 230 ~ 300 DEG C of progress polycondensations
Stop reaction when reaching condensation polymer viscosity, continuously squeezed out, cooling, pelletizing obtains polyester；Obtained PET polyester slice is put
Enter drying in vacuum drum, controlled at 175 ~ 180 DEG C, is kept for 5 hours, then in 220 ~ 245 DEG C, 0 ~ 100Pa of vacuum degree
Under the conditions of, 4 ~ 20h of solid-phase tack producing obtains solid-phase tack producing polyester slice (SSP)；It is characterized in that Titanium series catalyst used forms
It is as follows:
(A) titanium phosphorus composition；
(B) complex；
(C) it is selected from general formula CnH2n+1COOH(wherein n be 0 and 1 ~ 3 integer) monoacid Li, Na, K, Mg, AI salt；
Wherein, titanium phosphorus composition is prepared by titanium compound, dihydric alcohol and phosphorus-containing compound hybrid reaction, it is characterised in that is being reacted
Titanium compound, dihydric alcohol and phosphorus-containing compound are added in device, in 105 DEG C to dihydric alcohol boiling spread, passes through decompression or normal pressure
Or be passed through inert gas and react and deviate from the low molecular compound generated in system, when no low molecular compound distillates, stop
Reaction, is down to room temperature, the colourless or light yellow liquid product obtained in the reactor is titanium catalyst, and wherein Ti content is
0.1 ± 6.0%, the molar ratio of titanium and phosphorus is 1: 0.49 ~ 5.33, and the molar ratio of titanium and dihydric alcohol is 1:5.99 ~ 251；For gathering
When prepared by ester, titanium phosphorus composition dosage is calculated as 5 ~ 85.5mg/kgPTA with titanium, the dosage of complex is 13 ~ 300mg/kgPTA, logical
Formula is CnH2n+1The COOH(integer that wherein n is 0 and 1 ~ 3) dosage of Li, Na, K, Mg salt of monoacid is 40 ~ 602 mg/
kgPTA。
2. the preparation method of a kind of polyester according to claim 1, wherein it is Ti that the titanium compound, which is selected from general formula,
(CnH2n+1O)4Reaction product, the general formula of (the wherein integer that n is 1~8) titanate esters and its hydrolysate, titanate esters and dihydric alcohol
It is CI, Br for TiX4(X) at least one of halogenated titanium and the hydrolysate of titanium sulfate.
3. the preparation method of a kind of polyester according to claim 1, wherein it is HO(CH that the dihydric alcohol, which is selected from general formula,2)nThe OH(integer that wherein n is 2 ~ 4) one of dihydric alcohol.
4. the preparation method of a kind of polyester according to claim 1, wherein the phosphorus-containing compound is to be selected from general formula
(CnH2n+1O)3The PO(integer that wherein n is 1 ~ 8) phosphate, general formula be (CnH2n+1O)3The P(integer that wherein n is 1 ~ 8) phosphorous
Acid esters, triphenyl phosphate, triphenyl phosphite, tricresyl phosphate hydroxyethyl ester, tricresyl phosphate hydroxypropyl ester, tricresyl phosphate hydroxyl butyl ester, 2-
At least one of ethylhexyl diphenyl phosphate, pentaerythritol phosphate.
5. the preparation method of a kind of polyester according to claim 1, wherein the complex is selected from general formula CnH2n
(COOH)2Binary acid, the general formula C of (the wherein integer that n is 0 and 1 ~ 8)nH2n(COOH)2The two of (the wherein integer that n is 0 and 1 ~ 8)
Alkali metal salt, the general formula HOC of first acidnH2nThe COOH(integer that wherein n is 1-5) carboxylic acid, malic acid, tartaric acid, tartaric acid
Hydrogen potassium, sodium hydrogen tartrate, sodium potassium tartrate tetrahydrate, citric acid, potassium citrate, sodium citrate, ascorbic acid, pentaerythrite, isophthalic two
At least one of formic acid -5- sodium sulfonate.
6. the preparation method of a kind of polyester according to claim 1, wherein described is selected from general formula CnH2n+1COOH(wherein n
Integer for 0 and 1 ~ 3) Li, Na, K, Mg, Al salt of monoacid at least selects one kind.
7. the preparation method of a kind of polyester according to claim 1, wherein the titanium phosphorus compound is prepared when reacting
Decompression refers to that system pressure control is 0 ~ 105Pa。
8. the preparation method of a kind of polyester according to claim 1, wherein the titanium phosphorus compound leads to when preparing reaction
The inert gas entered is N2Or He or carbon dioxide.
9. a kind of preparation method of polyester according to claim 1 and it is according to any one of claims 8 be passed through inert gas, it is special
Sign is that being passed through inert gas flow is 0.01~1.0 L/minL reactor.
10. a kind of preparation method of polyester according to claim 1, it is characterised in that polyethylene terephthalate
(PET), the preparation of poly terephthalic acid -1.3- propylene glycol ester (PTT) and poly terephthalic acid -1.4- butanediol ester (PBT).
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