CN108976398B - Process for producing polyester - Google Patents

Process for producing polyester Download PDF

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Publication number
CN108976398B
CN108976398B CN201810895668.5A CN201810895668A CN108976398B CN 108976398 B CN108976398 B CN 108976398B CN 201810895668 A CN201810895668 A CN 201810895668A CN 108976398 B CN108976398 B CN 108976398B
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polyester
phosphate
integer
acid
titanium
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CN108976398A (en
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曹善文
李朝晖
孟刚
曹晓晴
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Zhejiang Lixing Technology Co ltd
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Zhejiang Shangyu Lixing Chemical Co ltd
Jinan Zhaohui Technology Co ltd
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    • 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
    • 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

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  • 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 process for preparing polyester from terephthalic acid and ethanediol includes such steps as preparing the mixture of (A) Ti (C)nH2n+1O)4Titanate (wherein n is an integer of 1 to 8), (B) phosphorus compound, (C) complex and (D) selected from the group consisting ofnH2n+1The Li, Na, K, Mg and AI salts of the monoacid of COOH (wherein n is an integer of 0 and 1-3) are used as catalysts to prepare the polyester, and the catalysts have good catalytic activity and low b value of the catalytically synthesized PET polyester.

Description

Process for producing polyester
Technical Field
The invention relates to the field of a preparation method of polyester, in particular to the field of directly using titanate, phosphorus compounds, complexes and alkali metal salts of monobasic acids as catalysts for synthesizing polyethylene terephthalate.
Background
At present, more than 95 percent of Polyester (PET) in the world is produced by using antimony catalysts including antimony trioxide, antimony acetate or ethylene glycol antimony, the content of antimony metal in the polyester is generally 150-350 ug/g, but antimony compounds are toxic and heavy metal-containing compounds, which pollute the environment, can precipitate toxic antimony in the use process of polyester products and are harmful to human health, so that the Polyester (PET) is always concerned all the time, and people continuously research substitute products of the antimony catalysts or reduce the antimony to be used as the polyester catalysts from the initial development stage of the polyester industry, such as research on the use of germanium compounds, titanium compounds and the like. Germanium compounds are limited in their application due to their low resources and high prices; the titanium catalyst is favored by polyester manufacturers at home and abroad because of high activity and no heavy metal, and has become a research hotspot at home and abroad for many times, the synthesis and application of the titanium catalyst are also reported frequently, the components of the titanium catalyst are researched and reported in a large amount from easily hydrolyzed titanate to modified titanate, titanium-containing metal salt, composite titanium catalyst and the like, but the defects of unstable activity, remarkable catalytic side reaction, easy yellowing of polyester and the like are not solved so far, and the application of the titanium catalyst is limited. In a recent report, DuPont patent CN1402653A states that "organic titanates such as tetraisopropyl and tetra-n-butyl titanate are known to be effective polycondensation catalysts for the production of polyalkylene terephthalate in general, and are often selected for use as catalysts. However, these catalysts, when contacted with water, tend to hydrolyze to form diol-insoluble oligomers which lose their catalytic activity. These organotitanates also produce a significant amount of yellowing when used as polyester catalysts. In addition, many organotitanate catalysts are also substantially insoluble in the polymerization mixture, thereby resulting in a non-uniform distribution of the catalyst in the mixture. ", it thus provides a titanium composition as a catalyst, but the titanium activity at the time of application is only 12 times that of Sb (in terms of metal content), and the b value of the polyester is at least 4.94, and the yellow color is still evident.
Disclosure of Invention
The invention aims to realize the direct use of titanate as a polyester catalyst, overcome the defects that titanate is easy to deactivate and causes the yellowing of polyester in the application in the prior art, and realize the application in the polyester by adopting new technical characteristics.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme: a preparation method of polyester comprises the steps of taking terephthalic acid and ethylene glycol as raw materials, adding a titanium catalyst, carrying out esterification under the conditions of normal pressure to 0.3MPa and temperature of 220 to 280 ℃, removing water generated in the reaction through a distillation or rectification device to obtain a prepolymer, then reducing the pressure to be below 100Pa within 60min, controlling the temperature to be 250 to 300 ℃ for polycondensation, stopping the reaction when the viscosity of a polycondensate is reached in the polycondensation reaction, and carrying out continuous extrusion, cooling and grain cutting to obtain the PET polyester, wherein the used titanium catalyst comprises the following substances:
(A) the general formula is Ti (C)nH2n+1O)4(wherein n is an integer of 1 to 8);
(B) a phosphorus compound;
(C) a complex;
(D) selected from the general formula CnH2n+1Li, Na, K, Mg, AI salts of COOH (where n is 0 and an integer from 1 to 3) carboxylic acids;
wherein the dosage of titanate is 5-20 mg/kgPTA calculated by titanium, the molar ratio of titanium to phosphorus is 1: 0.49-5.32, and the dosage of the complex is 30-300mg/kgPTA, formula CnH2n+1The amount of Li, Na, K, Mg, AI salts of COOH (wherein n is an integer of 0 and 1 to 3) carboxylic acids is 30 to 400 Mg/kgPTA.
In the technical scheme of the invention, the general formula is Ti (C)nH2n+1O)4Titanates (wherein n is an integer of 1 to 8) are used for the catalyst for polyester, and are not limited to these titanates, but tetrapropyl titanate and tetrabutyl titanate are preferable in the present invention in view of commercial properties and cost control.
The phosphorus compound used in the technical scheme of the invention comprises phosphate, phosphite, alkali metal phosphate, alkali metal phosphite and alkali metal hypophosphite, wherein the phosphate is selected from (C)nH2n+1O）3Phosphate of PO (wherein n is an integer of 1 to 8), triphenyl phosphate, trihydroxyethyl phosphate, trihydroxypropyl phosphate, trihydroxybutyl phosphate, 2-ethylhexyl diphenyl phosphate, pentaerythritol phosphate; the phosphite is selected from the group consisting of compounds of the formula (C)nH2n+1O）3P (wherein n is an integer of 1 to 8) phosphite, triphenyl phosphite, trimethylol phosphite, trimethylolpropane phosphite, and tributyl phosphite; the invention researches and discovers that phosphorus atoms in the phosphorus compounds can form a coordination structure with titanium atoms and can adjust the activity of titanium atoms in catalyzing polyester, and the phosphorus compounds with different structures or carbon chain lengths prove the unique action of phosphorus in the phosphorus compounds, and the invention is only based on convenient application, commodity availability and price, in addition, the phosphorus compounds can be used independently or randomly mixed, wherein the molar ratio of titanium to total phosphorus is controlled within the range of 1: 0.49-5.32, when the molar ratio of titanium to phosphorus is more than 1: 0.49, the activity adjusting action of phosphorus on titanium is obviously reduced, and the polyester can turn yellow due to thermal degradation; when the molar ratio of titanium to phosphorus is less than 1: 5.32, the inhibition of the activity of phosphorus on titanium starts to be obvious along with the reduction of the molar ratio, and the polymerization reaction speed is inhibited; to facilitateIn application, the invention selects at least 1 and at most 3 of the above.
The complex used in the technical scheme of the invention is shown as a general formula CnH2n（COOH）2(wherein n is an integer of 0 and 1 to 8) dibasic acids and alkali metal salts thereof, general formula of HOCnH2nThe coordination compound has the advantages that the coordination compound has obvious synergistic effect with titanium and phosphorus compounds, the synergistic effect is that the activity and the selectivity of titanium are improved, the yellowing of polyester is avoided, the content of aggregated particles and diethylene glycol in the polyester is not increased, in addition, the coordination compound can be used independently or can be used in any mixture mode, the excellent coordination effect is shown, and for convenient application, at least 1 of the coordination compound is selected, and at most 3 of the coordination compound are selected, wherein the dosage of the coordination compound is preferably 30-300 mg/kgPTA.
General formula C used in the technical scheme of the inventionnH2n+1The Li, Na, K, Mg and Al salts of COOH (wherein n is an integer of 0 and 1-3) carboxylic acid can be further cooperated with titanium and the like in the preparation process of polyester, so that more excellent catalytic performance is shown, and the polyester can be tackified further, the Li, Na, K, Mg and Al salts can be used in the polyester alone or in a mixture, for convenient application, at least 1 and at most 3 of the Li, Na, K, Mg and Al salts are selected from the group consisting of COOH (wherein n is an integer of 0 and 1-3), and the total dosage of the Li, Na, K, Mg and Al salts in the polyester is 30-400 Mg.
The specific implementation mode is as follows:
example 1:
adding 1.0kg of terephthalic acid, 465g of ethylene glycol, 0.0357g of tetrabutyl titanate serving as a catalyst component, 0.0156g of trimethyl phosphate serving as a phosphorus compound, 0.03g of glycolic acid and 0.05g of sodium potassium tartrate serving as a complex, and 0.3g of lithium formate serving as a carboxylate into a 2.5-liter stainless steel reaction kettle, wherein the molar ratio of titanium to phosphorus is 1: 1.06, carrying out esterification under the condition of 0.05-0.3 MPa, removing water generated in the reaction by a rectification device, reducing the pressure to normal pressure when the temperature is increased to 255 ℃, then continuing to increase the temperature to 260-270 ℃ until no water is discharged, vacuumizing and reducing the pressure gradually to below 100Pa within 60min, controlling the temperature to be 285-300 ℃, judging the end point of the polymerization reaction according to the rotating speed of a stirrer or the power of a motor, relieving the vacuum by using nitrogen when the viscosity of the corresponding polymer is 0.650dl/g (allowable error is 0.01), stopping the polycondensation reaction, and recording the total time, the polymer was extruded in the form of a strand, cooled, and pelletized to obtain polyester chips, which were tested for b, melting point, and agglomerated particles, and the test results are shown in Table 1.
Example 2:
a polyester was prepared in the same manner as in example 1, except that the catalyst was 0.018g of tetramethyl titanate, the phosphorus compound was 0.0301g of trimethyl phosphite, the complex was 0.12g of sebacic acid and 0.05g of malic acid, and the carboxylate was 0.4g of magnesium acetate in which the molar ratio of titanium to phosphorus was 1: 2.32, and the test results were shown in Table 1.
Example 3:
a polyester was prepared in the same manner as in example 1, except that 0.0476g of isopropyl titanate as a catalyst, 0.0219g of tributyl phosphate as a phosphorus compound, 0.02g of sodium oxalate and 0.02g of tartaric acid as a complex, 0.15g of lithium formate and 0.15g of magnesium acetate as a carboxylate, and the molar ratio of titanium to phosphorus was 1: 0.49, and the test results were shown in Table 1.
Example 4:
a polyester was prepared in the same manner as in example 1, except that 0.0357g of tetraisopropyl titanate as a catalyst, 0.0246g of triphenyl phosphate and 0.0118g of trisodium phosphate as a phosphorus compound, 0.03g of potassium citrate monohydrate, 0.02g of 1-hydroxyhexanoic acid and 0.10g of ascorbic acid as a complex, 0.10g of sodium butyrate as a carboxylate and 0.10g of magnesium acetate as a complex, and the molar ratio of titanium to total phosphorus was 1: 1.17, and the results of the tests are shown in Table 1.
Example 5:
a polyester was prepared in the same manner as in example 1, except that the catalyst composition was 0.05g of tetrabutyltitanate, the phosphorus compound was 0.0242g of sodium hypophosphite monohydrate, the complex was 0.01g of sodium adipate and 0.03g of ascorbic acid, the carboxylate was 0.1g of potassium acetate and 0.1g of lithium acetate, and the molar ratio of titanium to phosphorus was 1: 1.56, and the test results are shown in Table 1.
Example 6:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0714g of tetraoctyl titanate, 0.015g of a phosphorus compound, and 0.010g of sodium phosphite pentahydrate; the complex was 0.02g oxalic acid and 0.01g sodium oxalate, the carboxylate was 0.40g lithium butyrate with a molar ratio of titanium to phosphorus of 1: 0.88, and the results are shown in Table 1.
Example 7:
polyester was prepared in the same manner as in example 1, wherein the catalyst composition was 0.0429g of titanate tetrabutyl titanate and 0.0318g of phosphorus compound was pentaerythritol phosphate; the complex was 0.10g citric acid and 0.10g sodium sebacate, the carboxylate was sodium formate 0.10g, potassium acetate 0.10g and sodium butyrate 0.10g, with a molar ratio of titanium to phosphorus of 1: 1.4, and the results are shown in Table 1.
Example 8:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0446g of tetraisopropyl titanate and the phosphorus compound was 0.209g of tributyl phosphite; the complex was 0.05g of pentaerythritol and 0.05g of malic acid, the carboxylate was 0.30g of aluminum acetate, the molar ratio of titanium to total phosphorus was 1: 5.32, and the results are shown in Table 1.
Example 9:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0718g of tetraethyl titanate, the phosphorus compound was 0.035g of tributyl phosphate, 0.01g of potassium phosphate and 0.01g of potassium phosphite; the complex is 0.05g of pentaerythritol, 0.03g of 1-hydroxypropionic acid and 0.08g of potassium hydrogen tartrate; the carboxylate was 0.04g of lithium formate and the molar ratio of titanium to phosphorus was 1: 0.77, and the results are shown in Table 1.
Example 10:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0571g of tetrabutyltitanate, the phosphorus compound was 0.045g of triphenyl phosphite, 0.005g of lithium phosphite and 0.01g of trioctyl phosphate; the complex is 0.30g of isophthalic acid-5-sodium sulfonate; the carboxylate was 0.01g lithium formate, 0.01g potassium acetate, 0.01g magnesium acetate, and the molar ratio of titanium to phosphorus was 1: 1.24, and the test results are shown in Table 1.
Example 11:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0476g of tetraisopropyl titanate and the phosphorus compound was 0.04g of potassium hypophosphite; the complex is 0.15g of isophthalic acid-5-sodium sulfonate and 0.05g of sodium hydrogen tartrate; the carboxylate was 0.20g of potassium acetate and the molar ratio of titanium to phosphorus was 1: 2.3, with the results shown in Table 1.
Example 12:
a polyester was prepared in the same manner as in example 1, except that the catalyst composition was 0.1191g of tetraisopropyl titanate, the phosphorus compound was 0.18g of pentaerythritol phosphate and 0.035g of trimethyl phosphate; the complex is 0.10g of succinic acid and 0.20g of isophthalic acid-5-sodium sulfonate; the carboxylate was 0.04g lithium acetate and the molar ratio of titanium to phosphorus was 1: 2.98, and the results are shown in Table 1.
Example 13:
a polyester was produced in the same manner as in example 1, except that the catalyst composition was 0.0446g of tetraisopropyl titanate, the phosphorus compound was 0.02g of triphenyl phosphate, and 0.01g of sodium hypophosphite monohydrate; the complex is 0.05g of sodium oxalate and 0.05g of 3-hydroxycaproic acid; the carboxylate was 0.25g of lithium acetate and the molar ratio of titanium to phosphorus was 1: 0.99, with the results shown in Table 1.
Comparative example: a polyester was prepared in the same manner as in example 1, using 0.35g of ethylene glycol antimony as a catalyst, and the test results are shown in Table 1.
The invention uses the symbols: MPa is MPa; pa: handkerchief; h: hours; min: the method comprises the following steps of (1) taking minutes; g: g; mg: mg; kg: kilogram; percent: and (4) percent by mass.
As can be seen from examples 1 to 13 and comparative examples, the present invention has the following advantages:
1. the synthesized titanium composition shows remarkable catalytic activity in catalyzing Polyester (PET) reaction;
2. the titanium composition catalyst synthesized by the method is used as a polyester catalyst, so that a high-temperature modulation process using an antimony catalyst can be omitted, the production cost of polyester is reduced, and environmental pollution in the production and post-processing processes of polyester is eliminated.
Table 1:
Figure 371685DEST_PATH_IMAGE001

Claims (3)

1. a preparation method of polyester takes terephthalic acid and ethylene glycol as raw materials, esterification is carried out under the conditions of normal pressure to 0.3MPa and temperature of 220 to 280 ℃ in the presence of a titanium catalyst, water generated in the reaction is removed through a distillation or rectification device to obtain a prepolymer, then the pressure is reduced to be below 100Pa, the temperature is controlled to be 250 to 300 ℃ for polycondensation, the reaction is stopped when the viscosity of a polycondensate is reached in the polycondensation reaction, and PET polyester is obtained through continuous extrusion, cooling and grain cutting, and the preparation method is characterized in that the titanium catalyst comprises the following components:
(A) the general formula is Ti (C)nH2n+1O)4Wherein n is an integer of 1-8;
(B) phosphorus compound: selected from the group consisting of those of the formula (C)nH2n+1O）3Phosphate of PO, triphenyl phosphate, trihydroxyethyl phosphate, trihydroxypropyl phosphate, trihydroxybutyl phosphate, 2-ethylhexyl diphenyl phosphate, pentaerythritol phosphate, the general formula (C)nH2n+ 1O）3P phosphite ester, triphenyl phosphite, alkali metal phosphate, alkali metal phosphite and alkali metal hypophosphite, wherein n is an integer of 1-8;
(C) the complex is as follows: selected from the group consisting of those of the formula CmH2m（COOH）2A dibasic acid of the general formula CmH2m（COOH）2Alkali metal salt of dibasic acid of the formula HOCnH2nCOOH hydroxy acid, malic acid, tartaric acid, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, citric acid, potassium citrate, sodium citrate, ascorbic acid, pentaerythritol and 5-sodium sulfoisophthalate, wherein m is 0 and an integer of 1-8, and n is an integer of 1-5;
(D) selected from the general formula CnH2n+1Li, Na, K, Mg, Al salts of COOH carboxylic acids, wherein n is 0 and an integer of 1 to 3;
wherein the dosage of titanate is 5-20 mg/kgPTA calculated by titanium, the molar ratio of titanium to phosphorus is 1: 0.49-5.32,The dosage of the complex is 30-300 mg/kgPTA, and the general formula is CnH2n+1The amount of Li, Na, K, Mg and Al salts of COOH carboxylic acid is 30-400 Mg/kgPTA, wherein n is 0 and an integer of 1-3;
the components (A), (B), (C) and (D) in the titanium catalyst are directly added into a reaction system.
2. The method for preparing polyester according to claim 1, wherein the alkali metal phosphates, alkali metal phosphites and alkali metal hypophosphites are phosphates, phosphites and hypophosphites of sodium, potassium and lithium.
3. The process for preparing a polyester as claimed in claim 1, wherein (D) is selected from the group consisting of those of the formula CnH2n+11 to 3 kinds of Li, Na, K, Mg and Al salts of COOH carboxylic acid, wherein n is an integer of 0 and 1 to 3.
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CN111607074B (en) * 2020-06-19 2022-08-12 海宁澜钛新材料有限公司 Method for preparing terephthalic acid-ethylene glycol-isosorbide copolyester by antimony-titanium bimetallic catalysis
CN112280012B (en) * 2020-11-13 2021-09-07 康辉新材料科技有限公司 Preparation method of poly (butylene succinate)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402653A (en) * 1999-12-02 2003-03-12 纳幕尔杜邦公司 Esterification catalyst compositions and use thereof
CN1962723A (en) * 2005-11-11 2007-05-16 中国石油化工股份有限公司 Preparation method of titanium series catalyst for polyester
CN101942076A (en) * 2009-07-06 2011-01-12 中国石油化工股份有限公司上海石油化工研究院 Preparation method of polyester
CN102477151A (en) * 2010-11-25 2012-05-30 东丽纤维研究所（中国）有限公司 Catalyst for preparation of polyester, its preparation method, and production method of polyester
CN104629033A (en) * 2013-11-06 2015-05-20 中国石油化工股份有限公司 Production method of low acetaldehyde titanium system polyester

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402653A (en) * 1999-12-02 2003-03-12 纳幕尔杜邦公司 Esterification catalyst compositions and use thereof
CN1962723A (en) * 2005-11-11 2007-05-16 中国石油化工股份有限公司 Preparation method of titanium series catalyst for polyester
CN101942076A (en) * 2009-07-06 2011-01-12 中国石油化工股份有限公司上海石油化工研究院 Preparation method of polyester
CN102477151A (en) * 2010-11-25 2012-05-30 东丽纤维研究所（中国）有限公司 Catalyst for preparation of polyester, its preparation method, and production method of polyester
CN104629033A (en) * 2013-11-06 2015-05-20 中国石油化工股份有限公司 Production method of low acetaldehyde titanium system polyester

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