CN114621425B - Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition - Google Patents

Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition Download PDF

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CN114621425B
CN114621425B CN202210257661.7A CN202210257661A CN114621425B CN 114621425 B CN114621425 B CN 114621425B CN 202210257661 A CN202210257661 A CN 202210257661A CN 114621425 B CN114621425 B CN 114621425B
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CN114621425A (en
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臧国强
张宝忠
张志全
杨雨强
肖刚
杨力芳
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China Petroleum and Chemical Corp
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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
    • C08G63/78—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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a titanium composition for synthesizing polybutylene succinate-co-terephthalic acid butanediol ester and a PBST synthesizing method. The titanium composition is white solid prepared through the reaction of titanate and phosphate in isopropanol or absolute ethyl alcohol solvent at 50-90 deg.c for 1-3 hr to obtain intermediate, the one-step addition of one metal compound from magnesium, aluminum and zinc compounds into the intermediate, the dropping deionized water to react for 1-3 hr, cooling the reaction product to room temperature, filtering and vacuum drying. Is suitable for preparing PBST with the mole number ratio of aliphatic-aromatic groups of 70/30-30/70, and the weight average molecular weight (Mw) after direct polycondensation reaction is up to 110000g/mol. The catalyst composition reduces the generation of tetrahydrofuran side reaction, and the hue b value of the synthesized PBST product is less than 8.

Description

Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition
Technical Field
The invention belongs to the technical field of synthesis of biodegradable materials, and particularly relates to a titanium composition for synthesizing poly (butylene succinate) -co-terephthalate (PBST for short) and a method for synthesizing poly (butylene succinate) -co-terephthalate.
Background
In recent years, various plastic products bring convenience to the life of people, and a large amount of used wastes cause non-negligible negative influence on the environment, so that a new pollution source is formed. Development and application of biodegradable polyester materials is one of the main approaches to replace non-degradable plastics and to solve the problem of "white pollution". The aliphatic-aromatic copolyester is a material which is very actively researched in the prior biodegradable polyester, and has the characteristics of high melting point, high crystallization speed, excellent mechanical property and the like of the aromatic polyester (for example, polybutylene terephthalate (for short, PBT) on the basis of good biodegradability of the aliphatic polyester (for example, polybutylene succinate (PBS)) and the like, and has very good application prospect. Wherein, refined terephthalic acid (PTA for short) and succinic acid (SA for short) are reacted together with 1, 4-butanediol, and the synthesized aliphatic-aromatic copolyester is called poly terephthalic acid-co-butanediol succinate (PBST for short).
The synthesis process of PBST is mainly divided into a transesterification method and a direct esterification method, wherein the direct esterification method takes refined terephthalic acid (PTA for short), succinic acid (SA for short) and 1, 4-butanediol (BDO for short) as raw materials, and the transesterification method takes dimethyl terephthalate (DMT for short), dimethyl succinate and BDO as raw materials, and both the raw materials generate tetrahydrofuran due to side reaction of 1, 4-butanediol in the production process. In recent years, because raw material DMT is rarely produced and sold, a direct esterification method is adopted in large-scale PBST preparation and production. Catalysts are needed in the esterification and polycondensation reaction stages of PBST synthesis, and the performance of the catalysts has great influence on the preparation process and the product quality; the good catalyst is convenient to use and difficult to inactivate, has good catalytic activity for esterification and polymerization reaction processes, and has the advantages of less amount of tetrahydrofuran generated by side reaction, less side reaction of decarboxylation, cyclization and thermal degradation, high molecular weight of the final synthesized PBST product and white color of the sliced piece.
The single-component titanium catalyst, such as tetrabutyl titanate, isopropyl titanate and other titanate catalysts, is commonly used in PBST synthesis, is easy to hydrolyze when meeting water in the reaction process, causes deactivation, and generates tetrahydrofuran by side reaction; meanwhile, the prepared slice has lower molecular weight, and usually, a chain extender is also required to be added for chain extension reaction. It is therefore desirable to provide a highly efficient catalyst system that overcomes the above disadvantages and drawbacks of the synthetic process when preparing PBST. There are known catalysts for synthesizing PBST and processes thereof, and patent nos. CN 103910858, CN101525425, CN 111116874, CN 100360581, CN 101328260, CN 107674188, etc., wherein one single component titanate, organotin compound, organozinc compound, etc. are used or two or more compounds are used in combination as catalysts. When the single-component titanium catalyst is used, the catalytic activity and the speed are not ideal, the aliphatic-aromatic copolyester with higher molecular weight is difficult to obtain, and the hue of the prepared product is yellow; when the rare earth catalyst is singly used, a better PBST product can be obtained, but the rare earth catalyst has the advantages of limited raw material sources, high price, complex preparation process and no contribution to large-scale use. How to prepare and use a composite catalyst system with high catalytic activity, small side reaction, safety and environmental protection and how to synthesize PBST products with high molecular weight and good hue become research hot spots in the field.
Patent CN 103910858 discloses a method for synthesizing biodegradable copolyester, the adopted catalyst is a type a+b composite catalyst, a is one of benzenesulfonic acid and p-toluenesulfonic acid, B is one of stannous octoate, dibutyltin oxide, stannous chloride and stannous oxalate, no antioxidant and chain extender are needed in the synthesis, and the molecular weight of PBST is synthesized to be higher. However, benzenesulfonic acid compounds have strong corrosiveness, have great influence on corrosion of equipment and pipelines during use, have strong toxicity of organic tin compounds, and do not meet the requirements of safety and environmental protection.
Patent CN 101525425 discloses a method for preparing biodegradable polyester by direct esterification polycondensation, which adopts one of an organic aluminum compound, an organic tin compound and an organic zinc compound, obtains PBST by direct polycondensation without chain extension, uses terephthalic acid PTA and succinic acid SA with a molar ratio of 7:3, obtains PBST by synthesis, has a melting point of about 180 ℃, has higher aromatic chain segment content in the synthesized PBST, and has a biodegradability test result which is inconsistent with the biodegradability of the copolyester reported in general literature.
Patent CN 111116874 discloses a biodegradable PBST copolyester and a synthesis method thereof, which adopts BDO, dimethyl succinate and DMT as raw materials, titanate as a catalyst, and the PBST product is synthesized by transesterification, polymerization and solid-phase tackifying. The single titanate is used as a catalyst, the substance is easy to hydrolyze and deactivate when meeting water, the molecular weight of PBST obtained after polymerization reaction is not high, and further solid phase tackifying is needed to improve the molecular weight of the product.
Patent CN 100360581 discloses a catalyst system for synthesizing degradable polyester and its application, in which one of tetrabutyl titanate, titanium isopropoxide, antimony trioxide, antimony acetate and zinc acetate is selected as esterification catalyst, and one rare earth of lanthanum La, cerium Ce, neodymium Nd, praseodymium Pr and scandium Sc is selected as polycondensation catalyst, and PBST is synthesized. The method can be used for synthesizing a better PBST product, but the source of the rare earth compound raw material is limited, chlorine ions need to be treated in the preparation process, the preparation process is very complex, and the method is not beneficial to large-scale use.
Patent CN 101328260 discloses a binary composite catalyst containing lanthanide bidentate complex, its preparation method and use, and its application in the synthesis of PBS and PBST, the synthesized PBST has low molecular weight. The lanthanide bidentate complex is prepared by taking a rare earth compound as a raw material, the preparation process is complex, the influence on the reaction is only reduced in reaction temperature and reaction time, and the influence on the reaction process and the PBST product performance is not deeply studied.
Patent CN 107674188 discloses a process method for synthesizing PBST by catalyzing organic guanidine, which adopts a bi-component high-activity catalyst system, wherein a main catalyst nontoxic biomass organic guanidine compound is one of creatine or guanidinoacetic acid, a cocatalyst is one of zinc lactate, zinc glycolate and zinc acetate, and PBST with higher molecular weight and white color is obtained through direct melting and solid phase polycondensation. The catalyst contains less organic guanidine compound source, is complex to prepare, has smaller molecular weight of PBST products obtained by direct melt polycondensation, and also needs subsequent solid-phase tackifying to improve the molecular weight of the products.
Disclosure of Invention
The invention aims to provide a titanium composition for synthesizing PBST, which has high reaction activity and small side reaction, and synthesized PBST slices have good color phase and high molecular weight.
The invention provides a titanium composition, which can be used for synthesizing copolyester PBST, can catalyze esterification reaction and polycondensation reaction at the same time, and can improve the polycondensation reaction rate and the product molecular weight compared with the single titanate used as a catalyst for synthesizing PBST; the prepared PBST product has high molecular weight, the highest weight average molecular weight (Mw) can reach 110000g/mol after direct melt polycondensation, the generation of tetrahydrofuran side reaction is reduced, and the defect of yellow hue of the PBST product synthesized by using a single titanate catalyst is overcome.
The invention provides a preparation method of a titanium composition and a preparation method for synthesizing PBST by using the titanium composition.
The aim of the invention is achieved by the following technical scheme:
Titanium-based composition for poly (butylene succinate) -co-terephthalate synthesis: reacting titanate and phosphate in isopropanol or absolute ethanol solvent at 50-90 deg.c for 1-3 hr to obtain intermediate, adding one metal compound from magnesium, aluminum or zinc compound into the intermediate, dropping deionized water, reacting for 1-3 hr, cooling the reaction product to room temperature, filtering and vacuum drying to obtain white solid.
In the above-mentioned titanium composition, the titanate is one of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, and the phosphate is one of trimethyl phosphate and triethyl phosphate.
The magnesium compound is one selected from anhydrous magnesium acetate or tetrahydrate magnesium acetate, the aluminum compound is one selected from aluminum acetate, ethylene glycol aluminum or aluminum isopropoxide, and the zinc compound is one selected from zinc oxide, zinc acetate or zinc acetate dihydrate.
In the above-mentioned scheme of titanium-based composition, the molar ratio of titanium compound to phosphate is 10:1-1:1, and the molar ratio of titanium compound to metal compound is 1:1-1:10.
In the above-mentioned scheme of titanium-based composition, the molar ratio of the solvent isopropanol or absolute ethanol to the titanium compound is 10: 1-20:1.
The specific preparation process of the titanium composition comprises the following steps: reacting titanate and phosphate in isopropanol or absolute ethanol solvent at 50-90 deg.c for 1-3 hr to obtain intermediate, adding one metal compound from magnesium, aluminum or zinc compound into the intermediate, dropping deionized water, reacting for 1-3 hr, cooling the reaction product to room temperature, filtering and vacuum drying to obtain white solid.
The titanium composition can be used as a catalyst for synthesizing PBST, and the ratio of the added titanium composition before the reaction to the total mole number of the reaction monomers PTA and SA is 1: (1X 10 3～10×103) the amount of the titanium-based composition was calculated based on the titanium element contained.
The prepared titanium composition can be applied to the synthesis of aliphatic-aromatic copolyester PBST, and a preparation method of the synthetic PBST comprises the following preparation processes: the PBST is prepared by adding reaction monomers of refined terephthalic acid PTA, succinic acid SA and 1, 4-butanediol BDO into a titanium composition catalyst, performing esterification reaction to obtain an esterification intermediate product, and continuing polycondensation reaction.
In the technical scheme for preparing PBST, the molar ratio of the reaction monomer PTA to SA is 30/70-70/30, and the ratio of the sum of the molar ratio of PTA to SA to the molar ratio of BDO is 1: (1.1-2.0).
In the technical scheme for preparing PBST, the ratio of the amount of the titanium composition added before the reaction to the total mole number of the reaction monomers PTA and SA is 1: (1X 10 3～10×103) the amount of the titanium-based composition was calculated based on the titanium element contained.
In the technical scheme for preparing PBST, the esterification reaction condition is that the pressure (gauge pressure) is between 0.05 and 0.3MPa, and the temperature is between 180 and 230 ℃; the polycondensation reaction conditions are: the vacuum degree is 50-300 Pa, and the temperature is 220-270 ℃.
The color phase b value of the synthesized PBST copolyester product is smaller than 8, the defect that the synthesized product is yellow when a single-component titanium catalyst is used is overcome, the synthesized PBST has higher molecular weight and good biodegradability, can be finally degraded into harmless small molecules in nature, and can be widely used in various fields of express packages, cutlery boxes, film bags, foaming materials, disposable products and the like.
The molecular weight and distribution of PBST in the present invention are determined by gel chromatography (GPC), the molecular weight Mw is the weight average, the instrument specification is Waters 1515, the test conditions are: the mobile phase is chloroform with the flow rate of 1ml/min and the temperature of 35 ℃. The hue b value of PBST was measured using a TC-PIIG full-automatic color difference meter.
Tetrahydrofuran THF content in the esterification distillate was determined using gas chromatography.
The beneficial effects of the invention are as follows:
the titanium composition of the invention does not contain heavy metal antimony, organic tin compound and rare earth element, is a nontoxic or low-toxicity catalyst system, and has no influence on human health and ecological environment.
The preparation method using the titanium composition as the catalyst is suitable for preparing PBST products with the molar ratio of aliphatic/aromatic being 30/70-70/30, and the polycondensation reaction can be directly carried out only by adding the catalyst once before the esterification reaction to generate the intermediate product of the esterification reaction without adding the catalyst again.
The catalyst system of the invention has excellent catalytic activity, obviously increases the reaction speed, and reduces the polycondensation reaction time from 6 hours to 3-4 hours compared with a single-component titanium catalyst; the average molecular weight of the product is obviously increased, and compared with a single-component titanium catalyst, the weight average molecular weight Mw of the obtained copolyester product is increased from 1 ten thousand to 4 ten thousand and can be increased to 3 ten thousand to 11 ten thousand.
The catalyst has stable reaction process, no need of adding other stabilizers, small side reaction, and the amount of tetrahydrofuran THF generated by side reaction in the esterification reaction stage is reduced to 5-8% by 10% of the single-component titanium catalyst in the catalytic reaction, based on the amount of BDO of the raw material.
The PBST product synthesized by the method has good color phase, the value b of the PBST color phase obtained by the catalytic synthesis of the single-component titanium catalyst is 10-15, and the value b is reduced to 5-8.
The preparation method of the synthetic PBST of the invention can lead the molecular weight of the PBST product to be continuously increased under the condition of only prolonging the polycondensation reaction time without adding a chain extender, a stabilizer and the like.
Detailed Description
Examples 1 to 8 preparation of titanium-based compositions
Example 1
The molar ratio of titanium compound to phosphate is 10:1, and the molar ratio of titanium compound to metal compound is 1:1.
34G (0.2 mol) of tetramethyl titanate, 2.8g (0.02 mol) of trimethyl phosphate and 120g (2 mol) of isopropanol are firstly weighed and placed in a reactor with a reflux device, stirred and reacted for 3 hours at 50 ℃ to obtain an intermediate product, 28.0g (0.2 mol) of anhydrous magnesium acetate is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 3 hours, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain the white solid titanium composition C 1.
Example 2
The molar ratio of titanium compound to phosphate is 10:1, and the molar ratio of titanium compound to metal compound is 1:5.
45.6G (0.2 mol) of tetraethyl titanate, 2.8g (0.02 mol) of trimethyl phosphate and 240g (4 mol) of isopropanol are weighed and placed in a reactor with a reflux device, stirred and reacted for 1 hour at 90 ℃ to obtain an intermediate product, 214g (1 mol) of magnesium acetate tetrahydrate is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 1 hour, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain a white solid titanium composition C 2.
Example 3
The molar ratio of titanium compound to phosphate is 1:1, and the molar ratio of titanium compound to metal compound is 1:10.
Firstly, 57g (0.2 mol) of tetraisopropyl titanate, 36g (0.2 mol) of triethyl phosphate and 184g (4 mol) of absolute ethyl alcohol are weighed and placed in a reactor with a reflux device, the reaction is stirred at 60 ℃ for 2.5 hours to obtain an intermediate product, 408g (2 mol) of aluminum acetate is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 2.5 hours, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain a white solid titanium composition C 3.
Example 4
The molar ratio of titanium compound to phosphate is 1:1, and the molar ratio of titanium compound to metal compound is 1:5.
68G (0.2 mol) of tetrabutyl titanate, 36g (0.2 mol) of triethyl phosphate and 184g (4 mol) of absolute ethyl alcohol are firstly weighed and placed in a reactor with a reflux device, stirred and reacted for 2 hours at 70 ℃ to obtain an intermediate product, 73g (1 mol) of ethylene glycol aluminum is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 2 hours, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain the white solid titanium composition C 4.
Example 5
The molar ratio of titanium compound to phosphate is 5:1 and the molar ratio of titanium compound to metal compound is 1:2.
34G (0.2 mol) of tetramethyl titanate, 5.6g (0.04 mol) of trimethyl phosphate and 120g (2 mol) of isopropanol are weighed, placed in a reactor with a reflux device, stirred and reacted for 1.5 hours at 80 ℃ to obtain an intermediate product, 82g (0.4 mol) of aluminum isopropoxide is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 1.5 hours, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain the white solid titanium composition C 5.
Example 6
The molar ratio of titanium compound to phosphate is 2:1 and the molar ratio of titanium compound to metal compound is 1:5.
45.6G (0.2 mol) of tetraethyl titanate, 18g (0.1 mol) of triethyl phosphate and 92g (2 mol) of absolute ethyl alcohol are firstly weighed and placed in a reactor with a reflux device to react for 3 hours under stirring at 50 ℃ to obtain an intermediate product, 81g (1 mol) of zinc oxide is added, deionized water is slowly added into the intermediate product in a dropwise manner, the reaction is continued for 3 hours, the reaction product is cooled to room temperature, and then filtered and dried in vacuum to obtain the white solid titanium composition C 6.
Example 7
The molar ratio of titanium compound to phosphate is 10:1, and the molar ratio of titanium compound to metal compound is 1:1.
Firstly, 57g (0.2 mol) of tetraisopropyl titanate, 2.8g (0.02 mol) of trimethyl phosphate and 184g (4 mol) of absolute ethyl alcohol are weighed and placed in a reactor with a reflux device, the mixture is stirred and reacted for 1 hour at 90 ℃ to obtain an intermediate product, 36.6g (0.2 mol) of zinc acetate is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 1 hour, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain the white solid titanium composition C 7.
Example 8
The molar ratio of titanium compound to phosphate is 1:1, and the molar ratio of titanium compound to metal compound is 1:10.
68G (0.2 mol) of tetrabutyl titanate, 36g (0.2 mol) of triethyl phosphate and 240g (4 mol) of isopropanol are firstly weighed and placed in a reactor with a reflux device, stirred and reacted for 2 hours at 70 ℃ to obtain an intermediate product, 438g (2 mol) of zinc acetate dihydrate is added into the intermediate product, deionized water is slowly added dropwise, the reaction is continued for 2 hours, and the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain the white solid titanium composition C 8.
EXAMPLES 9-16 preparation of PBST
Example 9
199G (1.2 mol) of PTA, 330g (2.8 mol) of SA, 396g (4.4 mol) of BDO and 4X 10 -3 mol of titanium composition C 1 were charged into a polymerization reactor, and the amount of the catalyst was as follows: c 1/(PTA+SA)＝1:(1×103), the titanium-based composition C 1 has a total mole number of PTA and SA (pta+sa) (hereinafter, referred to as the mole number of titanium-containing element) (hereinafter). Carrying out esterification reaction at 180 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of theoretical value, ending the esterification reaction to obtain an intermediate product, wherein the total amount of the distillate is L 1, and the tetrahydrofuran content in the distillate is H 1 by using gas chromatography analysis; gradually decompressing and heating the reaction system, performing polycondensation reaction at 220 ℃ under the condition of 50Pa of vacuum degree, stopping the reaction after the polycondensation product reaches the required stirring power, and synthesizing the material liquid by water cooling and granulating to obtain the PBST product with the aliphatic/aromatic ratio of 70/30.
Example 10
465G (2.8 mol) of PTA, 142g (1.2 mol) of SA, 720g (8 mol) of 1, 4-butanediol and titanium-based composition C 2 were charged into the polymerization vessel in an amount of 4X 10 -4 mol, and the catalyst was used in the following conditions: c 2/(PTA+SA)＝1:(10×103). Carrying out esterification reaction under the conditions of 230 ℃ and 0.3MPa (gauge pressure), when the distillate reaches more than 95% of theoretical value, ending the esterification reaction to obtain an intermediate product, wherein the total amount of the distillate is L 2, and the tetrahydrofuran content in the distillate is H 2 by using gas chromatography analysis; gradually decompressing and heating the reaction system, performing polycondensation reaction at 270 ℃ and under the vacuum degree of 300Pa, stopping the reaction after the polycondensation product reaches the required stirring power, and obtaining the PBST polyester product with the aliphatic/aromatic ratio of 30/70 through water cooling and granulating of the feed liquid.
Example 11
266G (1.6 mol) of PTA, 283g (2.4 mol) of SA, 540g (6 mol) of 1, 4-butanediol and the titanium composition C 3 were charged into the polymerization vessel in an amount of 8X 10 -4 mol, and the catalyst was used in the following conditions: c 3/(PTA+SA)＝1:(5×103). Carrying out esterification reaction under 230 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of theoretical value, ending the esterification reaction to obtain an intermediate product, wherein the total amount of the distillate is L 3, and the tetrahydrofuran content in the distillate is H 3 by using gas chromatography analysis; gradually decompressing and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ under the condition of 50Pa of vacuum degree, stopping the reaction after the polycondensation product reaches the required stirring power, and carrying out water cooling and granulating on the feed liquid to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 60/40.
Example 12
332G (2 mol) of PTA, 236g (2 mol) of SA, 540g (6 mol) of 1, 4-butanediol and a catalyst titanium composition C 4 were added into a polymerization reactor in an amount of 8X 10 -4 mol, and the catalyst was used in the following conditions: c 4/(PTA+SA)＝1:(5×103). Carrying out esterification reaction under the conditions of 200 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of theoretical value, obtaining an intermediate product after the esterification reaction, wherein the total amount of the distillate is L 4, and analyzing the tetrahydrofuran content H 4 in the distillate by using gas chromatography; gradually decompressing and heating the intermediate product, performing polycondensation reaction at 240 ℃ and a vacuum degree of 100Pa, stopping the reaction after the polycondensation product reaches the required stirring power, and cooling the feed liquid by water and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 50/50.
Example 13
332G (2 mol) of PTA, 236g (2 mol) of SA, 540g (6 mol) of 1, 4-butanediol and a catalyst titanium composition C 5 were added into a polymerization reactor in an amount of 8X 10 -4 mol, and the catalyst was used in the following conditions: c 5/(PTA+SA)＝1:(5×103). The esterification reaction is carried out under the conditions of 200 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of the theoretical value, the esterification reaction is finished to obtain an intermediate product, the total amount of the distillate is L 5, and the tetrahydrofuran content H 5 in the distillate is analyzed by using gas chromatography. Gradually decompressing and heating the intermediate product, performing polycondensation reaction at 250 ℃ under the condition of 100Pa of vacuum degree, stopping the reaction after the polycondensation product reaches the required stirring power, and synthesizing the PBST copolyester product with the aliphatic/aromatic ratio of 50/50 by water cooling and granulating the feed liquid.
Example 14
266G (1.6 mol) of PTA, 284g (2.4 mol) of SA, 540g (6 mol) of 1, 4-butanediol and 4X 10 -4 mol of catalyst titanium composition C 6 were charged into a polymerization reactor, and the conditions of the catalyst amount were: c 6/(PTA+SA)＝1:(10×103). The esterification reaction is carried out under the conditions of 230 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of the theoretical value, the esterification reaction is finished to obtain an intermediate product, the total amount of the distillate is L 6, and the tetrahydrofuran content H 6 in the distillate is analyzed by using gas chromatography. Gradually decompressing and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ under the condition of 50Pa of vacuum degree, stopping the reaction after the polycondensation product reaches the required stirring power, and carrying out water cooling and granulating on the feed liquid to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 60/40.
Example 15
332G (2 mol) of PTA, 236g (2 mol) of SA, 540g (6 mol) of 1, 4-butanediol and 4X 10 -3 mol of catalyst titanium composition C 7 were added into a polymerization reactor, and the conditions of the catalyst dosage were: c 1/(PTA+SA)＝1:(1×103). The esterification reaction was carried out at 210℃and-0.05 MPa (gauge pressure), and when the distillate reached 95% or more of the theoretical value, the esterification reaction was ended to obtain an intermediate product, the total amount of the distillate was L 7, and the tetrahydrofuran content H 7 in the distillate was analyzed by gas chromatography. Gradually decompressing and heating the intermediate product, performing polycondensation reaction at 240 ℃ and a vacuum degree of 100Pa, stopping the reaction after the polycondensation product reaches the required stirring power, and cooling the feed liquid by water and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 50/50.
Example 16
199G (1.2 mol) of PTA, 330g (2.8 mol) of SA, 540g (6 mol) of 1, 4-butanediol and 2X 10 -3 mol of catalyst titanium composition C 8 were charged into a polymerization reactor, and the catalyst was used in the following conditions: c 1/(PTA+SA)＝1:(2×103). And (3) carrying out esterification reaction at 220 ℃ and-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of theoretical value, ending the esterification reaction to obtain an intermediate product, analyzing the tetrahydrofuran content H 8 in the distillate by using gas chromatography, gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ under the condition of the vacuum degree of 200Pa, stopping the reaction after the polycondensation product reaches the required stirring power, and carrying out water cooling and granulating on the feed liquid to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 70/30.
In examples 9 to 16, the titanium-based composition used and the experimental results of the esterification and polycondensation reactions are shown in Table 1, and the mole number of the titanium-based composition is calculated on the titanium element contained.
Comparative example 1
PBST having an aliphatic/aromatic ratio of 50/50 was prepared in the same manner as in example 12, except that 4X 10 -4 mol of tetrabutyl titanate (TBT) was added before the esterification, and after the completion of the esterification, a polycondensation reaction was conducted by adding 2X 10 -3 mol of TBT to the intermediate product again, the mole number of TBT being calculated as the titanium element contained, and the results are shown in Table 1.
Comparative example 2
PBST having an aliphatic/aromatic ratio of 70/30 was prepared in the same manner as in example 16 except that 8X 10 -4 mol of tetraisopropyl titanate (TPT) was added before the esterification, and after the completion of the esterification, 1X 10 -3 mol of TPT was added again to the intermediate product to carry out the polycondensation, the mole number of TPT based on the titanium element contained was used, and the results are shown in Table 1.
TABLE 1 Experimental results for PBST Synthesis
As can be seen from Table 1, in examples 9 to 16, compared with comparative examples 1 and 2, the amount of tetrahydrofuran THF produced by side reaction in the esterification reaction stage was reduced to 5% to 8% from 10% in the single titanate catalytic reaction; when the molecular weight is similar, compared with the single titanate serving as a catalyst, the polycondensation time is reduced; the weight average molecular weight Mw of PBST can reach 11 ten thousand by using the titanium composition, and the color phase b value is better and is reduced to 5 to 8 from 10 to 15 when single titanate is used for catalytic reaction.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.

Claims (7)

1. A titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester is characterized in that titanate and phosphate react in a solvent of isopropanol or absolute ethyl alcohol at 50-90 ℃ for 1-3 hours to obtain an intermediate product, one metal compound selected from magnesium, aluminum or zinc compounds is added into the intermediate product at one time, the reaction is continued for 1-3 hours under the condition of dropwise adding deionized water, and the reaction product is filtered and dried in vacuum after being cooled to room temperature to obtain a white solid;
Wherein, the mol ratio of titanate to phosphate is 10: 1-1:1, wherein the mol ratio of titanate to metal compound is 1:1-1:10, and the mol ratio of the dosage of solvent isopropanol or absolute ethanol to titanate is 10: 1-20: 1.
2. The titanium-based composition according to claim 1, wherein the titanate is one of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, or tetrabutyl titanate; the phosphate is one of trimethyl phosphate or triethyl phosphate.
3. The titanium-based composition according to claim 1, wherein the magnesium compound is one selected from the group consisting of anhydrous magnesium acetate and magnesium acetate tetrahydrate; the aluminum compound is one selected from aluminum acetate, ethylene glycol aluminum or aluminum isopropoxide; the zinc compound is one of zinc oxide, zinc acetate or zinc acetate dihydrate.
4. The method for synthesizing PBST by using the titanium composition of claim 1, which is characterized in that the reaction monomers of refined terephthalic acid PTA, succinic acid SA and 1, 4-butanediol BDO are subjected to esterification reaction after the titanium composition is added with a catalyst, and after an esterification intermediate product is obtained, the polycondensation reaction is continued, and finally PBST is prepared; wherein:
the mole number ratio of the reaction monomer PTA to SA is 30/70-70/30; the ratio of the sum of the mole numbers of PTA and SA to the mole number of BDO is 1: (1.1-2.0); the ratio of the amount of the titanium-based composition added to the total mole number of both the reaction monomers PTA and SA was 1: (1X 10 3～10×103) the amount of the titanium-based composition was calculated based on the titanium element contained.
5. The method according to claim 4, wherein the esterification reaction condition is that the pressure gauge pressure is-0.05-0.3 MPa and the temperature is 180-230 ℃; the polycondensation reaction conditions are: the vacuum degree is 50-300 Pa, and the temperature is 220-270 ℃.
6. The process according to claim 4, wherein the esterification reaction stage produces tetrahydrofuran THF in an amount of 5 to 8% based on BDO of the starting material, based on 10% of the reaction catalyzed by the one-component titanium catalyst.
7. The process according to claim 4, wherein the polycondensation reaction produces PBST having a weight average molecular weight of 6000 to 110000g/mol and a hue b value of less than 8.
CN202210257661.7A 2022-03-16 2022-03-16 Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition Active CN114621425B (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB877834A (en) * 1959-07-16 1961-09-20 Du Pont Improvements in or relating to polymers of thiocarbonyl difluoride
CN102225994A (en) * 2011-05-10 2011-10-26 浙江比例包装股份有限公司 Nanometer composite catalyst for synthesis of polyester and copolyester, and synthetic method for polyester and copolyester
CN102382287A (en) * 2010-08-30 2012-03-21 中国石油化工股份有限公司 Liquid titanium catalyst for polyester and copolyester and preparation method thereof
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
CN106366298A (en) * 2016-11-02 2017-02-01 安庆和兴化工有限责任公司 Preparation method of polybutylene terephthalate succinate
CN106634277A (en) * 2016-12-16 2017-05-10 江海涛 Titanium-pyrophosphate-containing anti-ultraviolet strippable macromolecular antirust film
CN107868238A (en) * 2017-11-29 2018-04-03 中国石油化工股份有限公司 A kind of preparation method and application of heavy metal free polyester polycondensation catalyst
KR102069509B1 (en) * 2019-07-05 2020-01-23 변종구 Biodegradable poly(butylene tetramethyleneglutarate-co-butylene terephthalate) aliphatic and aromatic polyester resin and the manufacturing method thereof
CN112794996A (en) * 2020-12-29 2021-05-14 中国纺织科学研究院有限公司 Preparation system and preparation method of biodegradable copolyester and copolyester thereof
CN113388100A (en) * 2021-05-28 2021-09-14 中国石油化工股份有限公司 Catalyst system for synthesis of aliphatic-aromatic copolyester and application thereof
KR20210147334A (en) * 2020-05-28 2021-12-07 에스케이씨 주식회사 Method for preparing biodegradable polyester resin and bioderadable polyester resin therefrom

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB877834A (en) * 1959-07-16 1961-09-20 Du Pont Improvements in or relating to polymers of thiocarbonyl difluoride
CN102382287A (en) * 2010-08-30 2012-03-21 中国石油化工股份有限公司 Liquid titanium catalyst for polyester and copolyester and preparation method thereof
CN102225994A (en) * 2011-05-10 2011-10-26 浙江比例包装股份有限公司 Nanometer composite catalyst for synthesis of polyester and copolyester, and synthetic method for polyester and copolyester
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
CN106366298A (en) * 2016-11-02 2017-02-01 安庆和兴化工有限责任公司 Preparation method of polybutylene terephthalate succinate
CN106634277A (en) * 2016-12-16 2017-05-10 江海涛 Titanium-pyrophosphate-containing anti-ultraviolet strippable macromolecular antirust film
CN107868238A (en) * 2017-11-29 2018-04-03 中国石油化工股份有限公司 A kind of preparation method and application of heavy metal free polyester polycondensation catalyst
KR102069509B1 (en) * 2019-07-05 2020-01-23 변종구 Biodegradable poly(butylene tetramethyleneglutarate-co-butylene terephthalate) aliphatic and aromatic polyester resin and the manufacturing method thereof
KR20210147334A (en) * 2020-05-28 2021-12-07 에스케이씨 주식회사 Method for preparing biodegradable polyester resin and bioderadable polyester resin therefrom
CN112794996A (en) * 2020-12-29 2021-05-14 中国纺织科学研究院有限公司 Preparation system and preparation method of biodegradable copolyester and copolyester thereof
CN113388100A (en) * 2021-05-28 2021-09-14 中国石油化工股份有限公司 Catalyst system for synthesis of aliphatic-aromatic copolyester and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Studies on the optimal conditions for synthesizing poly(butylene succinate-co-terephthalate) copolyesters with targeted properties;Tsai, Ping-Hsun et al.;《ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING》;20120418;第7卷;第S88-S94页 *
原位聚合制备PBT/nano-ZnO复合材料及其结晶性能研究;陈延明;贾鹏月;王立岩;吴全才;;中国塑料;20160326;第30卷(第03期);第33-37页 *

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