CN114874424A - Preparation method of fast-crystallization type polyester - Google Patents
Preparation method of fast-crystallization type polyester Download PDFInfo
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- CN114874424A CN114874424A CN202110167114.5A CN202110167114A CN114874424A CN 114874424 A CN114874424 A CN 114874424A CN 202110167114 A CN202110167114 A CN 202110167114A CN 114874424 A CN114874424 A CN 114874424A
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- titanium catalyst
- titanium
- fast
- catalyst composition
- polyol
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- 229920000728 polyester Polymers 0.000 title claims abstract description 49
- 238000002425 crystallisation Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000010936 titanium Substances 0.000 claims abstract description 68
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 238000005886 esterification reaction Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 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 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- -1 polyol ether compound Chemical class 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 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 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- VMKMZRBPOSNUMX-UHFFFAOYSA-N 2-(1-hydroxypropan-2-yloxy)propan-1-ol Chemical compound OCC(C)OC(C)CO VMKMZRBPOSNUMX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 12
- 230000008018 melting Effects 0.000 abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 11
- 239000002667 nucleating agent Substances 0.000 abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 4
- 239000004299 sodium benzoate Substances 0.000 description 4
- 235000010234 sodium benzoate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
-
- 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
Abstract
The invention discloses a preparation method of fast-crystallization polyester, which comprises the steps of preparing raw materials into slurry, carrying out first esterification reaction, second esterification reaction, pre-polycondensation reaction and final polycondensation reaction, and adding a titanium catalyst or a titanium catalyst composition containing the titanium catalyst into the slurry or the second esterification reaction, wherein the titanium catalyst has the following structural formula, wherein R1 ═ CH 2 OH，R2＝H、‑CH 2 CH 3 、‑CH 3 or-NH 2 . On the premise of not adding a nucleating agent, the titanium catalyst or the titanium catalyst composition is used to prepare the fast crystallization type PET polyester with the melting crystallization peak temperature of 210-; at a lower viscosity in the range of 0.65-0.68dL/g, the carboxyl end group content can be kept in the range of less than 10mol/t, and the thermal stability is improved.
Description
Technical Field
The invention relates to a preparation method of polyester, in particular to a preparation method of fast crystallization type polyester.
Background
The melting crystallization peak temperature of the conventional PET is generally 170-180 ℃, the crystallization speed is relatively slow, the injection mold temperature reaches 120-140 ℃, and the economical efficiency is poor. The slow crystallization rate at typical molding processing temperatures prevents their use in the engineering plastic field. One of the key points for the successful use of PET as an engineering plastic is to accelerate the crystallization rate of PET. For many years, a great deal of research has been conducted on the modification of the crystallization of polyesters, such as the addition of various types of crystallization nucleating agents and crystallization promoters. The prior art is added with organic montmorillonite, sodium benzoate and polyethylene glycol, which is a more researched and effective method at present. However, the addition amount is limited by adding the nucleating agent, extra preparation is needed during production, the cost is increased, the post-processing performance is affected after the nucleating agent is added too much, and the like, and the melting crystallization peak temperature of the PET polyester can only be increased to 200 ℃ to 210 ℃ by adding the nucleating agent, so that the continuous increase has certain difficulty and still cannot meet the application requirement of engineering plastics.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of fast crystallization type polyester, which can realize fast crystallization without adding nucleating agent.
The technical scheme is as follows: the preparation method of the crystalline polyester comprises the steps of preparing raw materials into slurry, and adding a titanium catalyst or a titanium catalyst composition containing the titanium catalyst into the slurry or in the second esterification reaction through a first esterification reaction, a second esterification reaction, a pre-polycondensation reaction and a final polycondensation reaction, wherein the titanium catalyst has the following structural formula:
wherein, R1 ═ CH 2 OH，R2＝H、-CH 2 CH 3 、-CH 3 or-NH 2 。
Preferably, a titanium catalyst is added to the slurry or to the second esterification reaction, said titanium catalyst being prepared by: dissolving a titanium compound in an inert solvent, then dropwise adding a polyol or polyol ether compound into the inert solvent, and reacting under a heating condition after dropwise adding; and after the reaction is finished, filtering and separating to obtain the titanium catalyst.
Preferably, a titanium catalyst composition containing a titanium catalyst is added in the slurry or in the second esterification reaction, and the raw materials for preparing the titanium catalyst composition comprise the titanium catalyst, a phosphorus source, a sodium source and a magnesium source or a zinc source; preferably, the mass ratio of Ti to P to Na to Mg or Zn in the titanium catalyst composition is 1 (0.2-0.5) to (0.1-0.3) to (1-3).
Preferably, the phosphorus compound comprises at least one of phosphoric acid, phosphorous acid, phosphate esters or phosphite esters; the sodium compound comprises at least one of sodium acetate, sodium carbonate or sodium bicarbonate; the magnesium compound comprises magnesium acetate and/or magnesium chloride; the zinc compound comprises zinc acetate and/or zinc aluminate.
Preferably, the titanium catalyst composition is added in an amount of 10 to 20ppm in terms of titanium atom based on the mass of the polyester.
Preferably, a titanium catalyst composition comprising a titanium catalyst is added in the slurry or in the second esterification reaction, the titanium catalyst composition being prepared by: dissolving a titanium compound in an inert solvent, dropwise adding a polyol or polyol ether compound into the inert solvent, reacting under a heating condition after dropwise adding is finished, then adding a phosphorus source, a sodium source and a magnesium source or a zinc source, and filtering and separating after the reaction is finished to obtain the titanium catalyst composition.
Preferably, the mass ratio of the titanium compound to the polyol or polyol ether compound is 1:1 to 2.
Preferably, the titanium compound is at least one of tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate.
Preferably, the polyol or polyol ether compound is at least one of glycerol ether, bis (1-methyl-2-hydroxyethyl) ether, trimethylolpropane, trimethylolethane, glycerol, or tris (hydroxymethyl) aminomethane.
Preferably, in the process of dripping the polyhydric alcohol, the reaction temperature is controlled to be 40-140 ℃, and the dripping time is 60-120 min.
Preferably, after the dropwise addition is finished, stirring and reacting for 2-6h at the temperature of 40-140 ℃.
Preferably, the inert solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, petroleum ether, heptane, cyclohexane, n-hexane or ethyl acetate.
Preferably, the filtered and separated product is distilled under reduced pressure to obtain a retention product, and the retention product is dried under vacuum to obtain the titanium catalyst solid powder.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: 1. on the premise of not adding a nucleating agent, by using the titanium catalyst or the titanium catalyst composition, the fast crystallization type PET polyester with the melting crystallization peak temperature of 210-230 ℃ is prepared on a ten thousand ton/year five-kettle flow production device, and the higher the temperature is, the higher the melting crystallization speed is, so that the prepared fast crystallization type polyester is; 2. the PET polyester prepared by using the catalyst or the titanium catalyst composition has lower viscosity in the range of 0.65-0.68dL/g, the carboxyl end group content can be kept in the range of less than 10mol/t, and the thermal stability is improved.
Detailed Description
The present invention is described in further detail below.
Example 1
The invention discloses a preparation method of fast crystallization type polyester, which comprises the following steps:
the production device is a five-kettle flow, the capacity is 1 ten thousand tons/year, the production device comprises a first esterification reaction kettle, a second esterification reaction kettle, a first pre-polycondensation reaction kettle, a second pre-polycondensation reaction kettle and a final polycondensation reaction kettle, and the alcohol-acid ratio of ethylene glycol to purified terephthalic acid is 1.13 when slurry is prepared. Wherein the temperature of the first esterification reaction kettle is 245 ℃, the temperature of the second esterification reaction kettle is 245 ℃, the temperature of the first pre-polymerization reaction kettle is 265 ℃, the pressure is 5kpa, the temperature of the second pre-polymerization reaction kettle is 270 ℃, the pressure is 1kpa, the temperature of the final pre-polymerization reaction kettle is 275 ℃, and the pressure is 10 pa. The titanium catalyst composition of the present invention was added to the slurry in an amount of 10ppm by mass relative to PET in terms of Ti atom. The intrinsic viscosity of the obtained PET polyester is 0.66dL/g, the melting crystallization peak temperature Tmc of the polyester: 210 ℃ and the content of terminal carboxyl groups is less than 10 mol/t.
The preparation method of the titanium catalyst composition comprises the following steps:
firstly, tetrabutyl titanate is added into a heptane solvent, the mass ratio of tetrabutyl titanate to heptane is 1:3, then glycerol ether is slowly dripped into the system under the stirring of 40 ℃ and 50Hz, the dripping speed is controlled, the temperature is controlled to be 40 ℃, the time is controlled to be 120min, the mass ratio of the total weight of the glycerol ether to tetrabutyl titanate is 1:1.5, after the dripping is finished, the stirring reaction is continuously carried out for 6 hours at 40 ℃, then a certain amount of trimethyl phosphate, magnesium acetate and sodium acetate are added, the mass ratio of titanium element to phosphorus element is controlled to be 1:0.2, the mass ratio of titanium element to sodium element is controlled to be 1:0.3, the mass ratio of titanium element to magnesium element is controlled to be 1:1, and the stirring is continuously carried out for 2 hours. And after the reaction is finished, filtering and separating a solid product generated in the reaction process, and drying the solid product in vacuum drying equipment at 60 ℃ for 10 hours to obtain the titanium catalyst composition, wherein the mass ratio of Ti to P to Na to Mg in the obtained titanium catalyst composition is 1:0.2:0.3: 1.
Example 2
The invention discloses a preparation method of fast crystallization type polyester, which comprises the following steps:
the production device is a five-kettle flow, the capacity is 1 ten thousand tons/year, the production device comprises a first esterification reaction kettle, a second esterification reaction kettle, a first pre-polycondensation reaction kettle, a second pre-polycondensation reaction kettle and a final polycondensation reaction kettle, and the alcohol-acid ratio of ethylene glycol to purified terephthalic acid is 1.1 when slurry is prepared. Wherein the temperature of the first esterification reaction kettle is 265 ℃, the temperature of the second esterification reaction kettle is 265 ℃, the temperature of the first pre-polymerization reaction kettle is 275 ℃, the pressure is 10kpa, the temperature of the second pre-polymerization reaction kettle is 280 ℃, the pressure is 1.5kpa, the temperature of the final polymerization reaction kettle is 285 ℃, and the pressure is 100 pa. The titanium catalyst composition of the present invention was added to the second esterification reaction vessel in an amount of 20ppm by mass relative to PET in terms of Ti atom. The intrinsic viscosity of the obtained PET polyester is 0.68dL/g, the melting crystallization peak temperature Tmc of the polyester: 230 ℃ and the content of terminal carboxyl groups is less than 10 mol/t.
The preparation method of the titanium catalyst composition comprises the following steps:
firstly adding tetraethyl titanate into a heptane solvent, wherein the mass ratio of tetrabutyl titanate to heptane is 1:3, then slowly dripping trimethylolpropane into the system at the temperature of 90 ℃ under the stirring of 50Hz, controlling the dripping speed, controlling the temperature of 140 ℃ and the time to be within 60min, controlling the mass ratio of the total weight of trimethylolpropane to tetrabutyl titanate to be 1:1.5, continuously stirring and reacting at the temperature of 140 ℃ for 2 hours after finishing dripping, then adding a certain amount of trimethyl phosphate, zinc acetate and sodium acetate, controlling the mass ratio of titanium element to phosphorus element to be 1:0.5, controlling the mass ratio of titanium element to sodium element to be 1:0.1 and controlling the mass ratio of titanium element to zinc element to be 1:3, and continuously stirring for 2 hours. And after the reaction is finished, filtering and separating a solid product generated in the reaction process, and drying the solid product in a vacuum drying device at 100 ℃ for 5 hours to obtain the titanium catalyst composition, wherein the mass ratio of Ti to P to Na to Zn in the obtained titanium catalyst composition is 1:0.5:0.1: 3.
Example 3
The invention discloses a preparation method of fast crystallization type polyester, which comprises the following steps:
the production device is a five-kettle flow, the capacity is 1 ten thousand tons/year, the production device comprises a first esterification reaction kettle, a second esterification reaction kettle, a first pre-polycondensation reaction kettle, a second pre-polycondensation reaction kettle and a final polycondensation reaction kettle, and the alcohol-acid ratio of ethylene glycol to purified terephthalic acid is 1.2 when slurry is prepared. Wherein the temperature of the first esterification reaction kettle is 255 ℃, the temperature of the second esterification reaction kettle is 255 ℃, the temperature of the first pre-polycondensation reaction kettle is 270 ℃, the pressure is 8kpa, the temperature of the second pre-polycondensation reaction kettle is 275 ℃, the pressure is 1.3kpa, the temperature of the final polycondensation reaction kettle is 280 ℃, and the pressure is 50 pa. The titanium catalyst composition of the present invention was added to the slurry in an amount of 15ppm by mass relative to PET in terms of Ti atom. The intrinsic viscosity of the obtained PET polyester is 0.67dL/g, the melting crystallization peak temperature Tmc of the polyester: 220 ℃ and the content of terminal carboxyl groups is less than 10 mol/t.
The preparation method of the titanium catalyst composition comprises the following steps:
firstly, tetrabutyl titanate is added into a heptane solvent, the mass ratio of tetrabutyl titanate to heptane is 1:3, then glycerol is slowly dripped into a system under the stirring of 50Hz within the temperature range of 50 ℃, the dripping speed is controlled, the temperature is controlled to be 90 ℃, the time is controlled to be within the range of 90min, the mass ratio of the total weight of the glycerol to the tetrabutyl titanate is 1:1.5, after the dripping is finished, the stirring and the reaction are continuously carried out for 4 hours within the temperature range of 90 ℃, then a certain amount of trimethyl phosphate, magnesium chloride and sodium carbonate are added, the mass ratio of titanium element to phosphorus element is controlled to be 1:0.3, the mass ratio of titanium element to sodium element is controlled to be 1:0.2, the mass ratio of titanium element to magnesium element is controlled to be 1:2, and the stirring is continuously carried out for 2 hours. And after the reaction is finished, filtering and separating a solid product generated in the reaction process, and drying the solid product in vacuum drying equipment at the temperature of 80 ℃ for 8 hours to obtain the titanium catalyst composition, wherein the mass ratio of Ti to P to Na to Mg in the obtained titanium catalyst composition is 1:0.3:0.2: 2.
Example 4
The production process was the same as in example 1 except that the titanium catalyst of the present invention was added to the slurry. The intrinsic viscosity of the obtained PET polyester is 0.65dL/g, the melting crystallization peak temperature Tmc of the polyester: 210 ℃ and the content of terminal carboxyl groups is less than 10 mol/t.
The preparation method of the titanium catalyst comprises the following steps:
firstly, tetrabutyl titanate is added into a heptane solvent, the mass ratio of tetrabutyl titanate to heptane is 1:3, then glycerol is slowly dripped into the system under the stirring of 50Hz within the temperature range of 40 ℃, the dripping speed is controlled, the temperature is 40 ℃, the time is controlled to be 120min, the mass ratio of the total weight of the glycerol to the tetrabutyl titanate is 1:1.5, the stirring reaction is continued within the temperature range of 40 ℃ for 6 hours after the dripping is finished, the solid product generated in the reaction process is filtered and separated after the dripping is finished, and the titanium catalyst is obtained after the solid product is dried in vacuum drying equipment at 80 ℃ for 8 hours.
Comparative example 1
The conventional polyester PET production process was the same as in example 1 except that the catalyst was tetrabutyl titanate, a titanium catalyst commonly used at present. The intrinsic viscosity of the obtained PET polyester is 0.65dL/g, the melting crystallization peak temperature Tmc of the polyester: the carboxyl end group content was 20mol/t at 175 ℃.
Comparative example 2
The conventional polyester PET production process was the same as comparative example 1 except that 0.3% by mass of the matting agent titanium dioxide compared to PET was added to the second esterification solution. The intrinsic viscosity of the obtained PET polyester is 0.65dL/g, the melting crystallization peak temperature Tmc of the polyester: the carboxyl end group content is 22mol/t at 185 ℃.
Comparative example 3
The production process of the modified polyester PET is the same as that of the comparative example 1, except that the second esterification reaction kettle is added with 0.3 percent of delustering agent titanium dioxide and 0.2 percent of nucleating agent sodium benzoate by mass percent compared with the PET. The intrinsic viscosity of the obtained PET polyester is 0.65dL/g, the peak temperature of melt crystallization of the polyester is 200 ℃, and the content of terminal carboxyl is 21 mol/t.
Comparative example 4
The production process of the modified polyester PET is the same as that of the comparative example 1, except that the second esterification reaction kettle is added with 0.3 percent of delustering agent titanium dioxide and 0.3 percent of nucleating agent sodium benzoate by mass percent compared with the PET. The intrinsic viscosity of the obtained PET polyester is 0.66dL/g, the melting crystallization peak temperature of the polyester is 210 ℃, and the carboxyl end group content is 20 mol/t.
Comparative example 5
The production process of the modified polyester PET is the same as that of the comparative example 1, except that the second esterification reaction kettle is added with 0.3 percent of delustering agent titanium dioxide and 0.4 percent of nucleating agent sodium benzoate by mass percent compared with the PET. The intrinsic viscosity of the obtained PET polyester is 0.65dL/g, the peak temperature of melt crystallization of the polyester is 208 ℃, and the content of carboxyl end groups is 21 mol/t.
Claims (10)
1. A preparation method of fast crystallization type polyester comprises the steps of preparing raw materials into slurry, and carrying out first esterification reaction, second esterification reaction, pre-polycondensation reaction and final polycondensation reaction, wherein a titanium catalyst or a titanium catalyst composition containing the titanium catalyst is added into the slurry or the second esterification reaction, and the titanium catalyst has the following structural formula:
wherein, R1 ═ CH 2 OH，R2＝H、-CH 2 CH 3 、-CH 3 or-NH 2 。
2. The method for preparing a fast-crystallizing polyester according to claim 1, wherein a titanium catalyst is added to the slurry or the second esterification reaction, and the titanium catalyst is prepared by the steps of: dissolving a titanium compound in an inert solvent, then dropwise adding a polyol or polyol ether compound into the inert solvent, and reacting under a heating condition after dropwise adding; and after the reaction is finished, filtering and separating to obtain the titanium catalyst.
3. The method for preparing a fast crystalline polyester according to claim 1, wherein a titanium catalyst composition comprising a titanium catalyst is added to the slurry or the second esterification reaction, and the raw materials for preparing the titanium catalyst composition comprise a titanium catalyst, a phosphorus source, a sodium source, and a magnesium source or a zinc source; the mass ratio of Ti to P to Na to Mg or Zn in the titanium catalyst composition is 1 (0.2-0.5) to (0.1-0.3) to (1-3).
4. The process for producing a fast-crystallizing polyester according to claim 3, wherein the titanium catalyst composition is added in an amount of 10 to 20ppm by mass in terms of titanium atom based on the polyester.
5. The method of preparing a fast crystalline polyester according to claim 1, wherein a titanium catalyst composition comprising a titanium catalyst is added to the slurry or the second esterification reaction, and the titanium catalyst composition is prepared by the steps of: dissolving a titanium compound in an inert solvent, dropwise adding a polyol or polyol ether compound into the inert solvent, reacting under a heating condition after dropwise adding is finished, then adding a phosphorus source, a sodium source and a magnesium source or a zinc source, and filtering and separating after the reaction is finished to obtain the titanium catalyst composition.
6. The process for producing a fast-crystallizing polyester as claimed in claim 5, wherein the mass ratio of the titanium compound to the polyol or polyol ether compound is 1:1 to 2.
7. The method for producing a fast-crystallizing polyester according to claim 5, wherein the titanium compound is at least one of tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate.
8. The method of claim 5, wherein the polyol or polyol ether compound is at least one of glycerol ether, bis (1-methyl-2-hydroxyethyl) ether, trimethylolpropane, trimethylolethane, glycerol, or tris (hydroxymethyl) aminomethane.
9. The method for preparing a fast-crystallizing polyester as claimed in claim 5, wherein the reaction temperature is 40-140 ℃ and the dropping time is 60-120min during the dropping of the polyol; after the dropwise addition is finished, stirring and reacting for 2-6h at the temperature of 40-140 ℃.
10. The method of claim 5, wherein the inert solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, petroleum ether, heptane, cyclohexane, n-hexane or ethyl acetate.
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| WO2002016467A1 (en) * | 2000-08-22 | 2002-02-28 | Mitsui Chemicals, Inc. | Catalysts for polyester production, process for producing polyester, and polyester |
| CN1962720A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing polyester |
| CN101104678A (en) * | 2007-08-15 | 2008-01-16 | 华润聚酯（常州）有限公司 | Method for preparing titanium catalyst polyester |
| CN102924698A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate |
| CN103073712A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Preparation method for polyester by using liquid titanium catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016467A1 (en) * | 2000-08-22 | 2002-02-28 | Mitsui Chemicals, Inc. | Catalysts for polyester production, process for producing polyester, and polyester |
| CN1962720A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing polyester |
| CN101104678A (en) * | 2007-08-15 | 2008-01-16 | 华润聚酯（常州）有限公司 | Method for preparing titanium catalyst polyester |
| CN103073712A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Preparation method for polyester by using liquid titanium catalyst |
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