CN114621425A - Titanium composition for synthesizing poly (butylene succinate-co-terephthalate) and PBST (Poly-p-phenylene Benzene-succinate) synthesis method - Google Patents

Titanium composition for synthesizing poly (butylene succinate-co-terephthalate) and PBST (Poly-p-phenylene Benzene-succinate) synthesis method Download PDF

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CN114621425A
CN114621425A CN202210257661.7A CN202210257661A CN114621425A CN 114621425 A CN114621425 A CN 114621425A CN 202210257661 A CN202210257661 A CN 202210257661A CN 114621425 A CN114621425 A CN 114621425A
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titanium
reaction
pbst
titanate
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CN114621425B (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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention discloses a titanium composition for synthesizing poly (butylene succinate-co-terephthalate) and a method for synthesizing PBST (poly (butylene succinate-co-terephthalate)). The titanium composition is a white solid prepared by reacting titanate and phosphate in a solvent of isopropanol or absolute ethyl alcohol for 1-3 hours at 50-90 ℃ to obtain an intermediate product, adding one metal compound selected from magnesium, aluminum and zinc compounds into the intermediate product at one time, continuously reacting for 1-3 hours under the condition of dropwise adding deionized water, cooling the reaction product to room temperature, filtering and drying in vacuum. The method is suitable for preparing PBST with the mole ratio of aliphatic-aromatic groups of 70/30-30/70, and the weight average molecular weight (Mw) after direct polycondensation reaches 110000g/mol to the maximum. 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-terephthalate) and PBST (Poly-p-phenylene Benzene-succinate) synthesis method
Technical Field
The invention belongs to the technical field of biodegradable material synthesis, and particularly relates to a titanium composition for synthesizing polybutylene succinate-co-terephthalate (PBST) and a method for synthesizing polybutylene succinate-co-terephthalate.
Background
In recent years, various plastic products bring convenience to people's life, and a large amount of used waste has a considerable negative effect on the environment, so that a new pollution source is formed. The development and application of biodegradable polyester materials are one of the main approaches to replace non-degradable plastics and solve the problem of 'white pollution'. The aliphatic-aromatic copolyester is a material which is actively researched in the current biodegradable polyester, has the characteristics of high melting point, high crystallization speed, excellent mechanical property and the like of the aromatic polyester (such as polybutylene terephthalate, PBT for short) on the basis of good biodegradability of the aliphatic polyester (such as polybutylene succinate, PBS for short), and has a very good application prospect. Wherein, the Purified Terephthalic Acid (PTA) and Succinic Acid (SA) are reacted with 1, 4-butanediol, and the synthesized aliphatic-aromatic copolyester is called poly terephthalic acid-co-butylene succinate (PBST).
The synthesis process of PBST mainly comprises an ester exchange method and a direct esterification method, wherein the direct esterification method takes Purified Terephthalic Acid (PTA), Succinic Acid (SA) and 1, 4-Butanediol (BDO) as raw materials, the ester exchange method takes dimethyl terephthalate (DMT), dimethyl succinate and BDO as raw materials, and the two are subjected to side reaction of 1, 4-butanediol to generate tetrahydrofuran in the production process. In recent years, because DMT as a raw material is rarely produced and sold, the direct esterification method is adopted for large-scale PBST preparation production. Catalysts are needed in esterification and polycondensation reaction stages for synthesizing PBST, 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 not easy to inactivate, has good catalytic activity in the esterification and polymerization reaction processes, has less tetrahydrofuran generated by side reactions, has less side reactions of decarboxylation, cyclization and thermal degradation, and finally obtains a PBST product with high molecular weight and white slice color.
In the synthesis of PBST, single-component titanium catalysts are generally applied at present, such as titanate catalysts like tetrabutyl titanate and isopropyl titanate, which are easy to hydrolyze in water during the reaction process to cause inactivation and generate tetrahydrofuran by side reaction; meanwhile, the prepared slices have low molecular weight, and a chain extender is usually added for chain extension reaction. There is therefore a need to provide a highly efficient catalyst system for the preparation of PBST that overcomes the above drawbacks and deficiencies of the synthetic process. There are known catalysts for PBST synthesis and processes thereof, and patent Nos. CN 103910858, CN101525425, CN 111116874, CN 100360581, CN 101328260, and CN 107674188, in which one kind of single-component titanate, organic tin compound, organic zinc compound, etc. or two or more kinds of compounds are used in combination as a catalyst. When the single-component titanium catalyst is used, the catalytic activity and the speed are not ideal, aliphatic-aromatic copolyester with higher molecular weight is difficult to obtain, and the prepared product has yellow hue; better PBST products can be obtained when the rare earth catalyst is singly used, but the rare earth catalyst has limited raw material sources, high price and complex preparation process, and is not beneficial 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 a PBST product with high molecular weight and good hue becomes a research hotspot in the field.
Patent CN 103910858 discloses a method for synthesizing biodegradable copolyester, the catalyst used is a + B type composite catalyst, a is one of benzene sulfonic acid, p-toluene sulfonic acid, etc., B is one of stannous octoate, dibutyl tin oxide, stannous chloride, stannous oxalate, no antioxidant and chain extender are needed in the synthesis, and the molecular weight of the synthesized PBST is high. However, the benzenesulfonic acid compounds have strong corrosivity, have great influence on corrosion of equipment and pipelines in use, and the organotin compounds have strong toxicity and do not meet the requirements of safety and environmental protection.
Patent CN101525425 discloses a method for preparing biodegradable polyester by direct esterification polycondensation, which adopts one of organic aluminum compound, organic tin compound and organic zinc compound, and synthesizes PBST through direct polycondensation without chain extension step, the molar ratio of terephthalic acid PTA and succinic acid SA used is 7:3, the melting point of the synthesized PBST is about 180 ℃, the content of aromatic chain segment in the synthesized PBST is high, and the test result of biodegradability is not consistent 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 and titanates as catalysts to synthesize a PBST product by ester exchange, polymerization and solid-phase tackifying methods. The single titanate is used as a catalyst, the titanate is easy to hydrolyze and deactivate when meeting water, the molecular weight of PBST obtained after polymerization reaction is not high, and subsequent further solid-phase tackifying is needed to improve the molecular weight of the product.
Patent CN 100360581 discloses a catalyst system for degradable polyester synthesis and application thereof, wherein one of tetrabutyl titanate, titanium isopropoxide, antimony trioxide, antimony acetate and zinc acetate is selected as an esterification catalyst, and one of rare earths of lanthanum La, cerium Ce, neodymium Nd, praseodymium Pr and scandium Sc is selected as a polycondensation catalyst, and PBST is synthesized. The method can be used for synthesizing better PBST products, but the rare earth compound has limited raw material sources, needs to treat chloride ions in the preparation process, has very complex preparation process and is not beneficial to large-scale use.
Patent CN 101328260 discloses a binary composite catalyst containing lanthanide series bidentate complex, a preparation method and application thereof, and the binary composite catalyst is applied to the synthesis of PBS and PBST, and the synthesized PBST has low molecular weight. The lanthanide series bidentate complex is also prepared by taking a rare earth compound as a raw material, the preparation process is complex, the influence on the reaction is only to reduce the reaction temperature and shorten the reaction time, and the influence on the reaction process and the PBST product performance is not deeply researched.
Patent CN 107674188 discloses a process for synthesizing PBST by organic guanidine catalysis, which adopts a bi-component high-activity catalyst system, wherein the main catalyst nontoxic biomass organic guanidine compound is one of creatine or guanidinoacetic acid, the cocatalyst is one of zinc lactate, zinc glycolate and zinc acetate, and PBST with higher molecular weight and snow white hue is obtained by direct melting and solid phase polycondensation. The catalyst contains few organic guanidine compounds, is complex to prepare, and the PBST product obtained by direct melt polycondensation has smaller molecular weight, and needs subsequent solid-phase tackifying to improve the molecular weight of the product.
Disclosure of Invention
The technical problems to be solved by the invention are a titanium composition for synthesizing polybutylene succinate-co-terephthalate and a method for synthesizing polybutylene succinate-co-terephthalate, aiming at providing a titanium composition for preparing synthetic PBST, which has high reaction activity and small side reaction, and the synthesized PBST slice has good hue and high molecular weight.
The invention provides a titanium composition, which can be used for synthesizing copolyester PBST, can simultaneously play a role in catalyzing esterification reaction and polycondensation reaction, and can improve the polycondensation reaction rate and the product molecular weight compared with the synthesis of PBST by taking single titanate as a catalyst; the prepared PBST product has high molecular weight, the weight-average molecular weight (Mw) can reach 110000g/mol after direct melt polycondensation, the generation of tetrahydrofuran side reaction is reduced, and the defect that the PBST product synthesized by using a single titanate catalyst has yellow hue is overcome.
The invention provides a preparation method of a titanium composition and a preparation method for synthesizing PBST by applying the titanium composition.
The purpose of the invention is achieved by the following technical scheme:
the titanium composition for synthesizing the poly (butylene succinate-co-terephthalate): titanate and phosphate react in isopropanol or absolute ethyl alcohol solvent, an intermediate product is obtained after the reaction is carried out for 1-3 hours at 50-90 ℃, a 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 white solid is prepared after the reaction product is cooled to room temperature, filtered and dried in vacuum.
In the 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 magnesium acetate tetrahydrate, the aluminum compound is one selected from aluminum acetate, aluminum glycol or aluminum isopropoxide, and the zinc compound is one selected from zinc oxide, zinc acetate or zinc acetate dihydrate.
In the titanium composition, the molar ratio of the titanium compound to the phosphate is 10:1 to 1:1, and the molar ratio of the titanium compound to the metal compound is 1:1 to 1: 10.
In the scheme of the titanium composition, the molar ratio of the dosage of the solvent isopropanol or absolute ethyl alcohol to the titanium compound is 10: 1-20: 1.
The specific preparation process of the titanium composition comprises the following steps: titanate and phosphate react in isopropanol or absolute ethyl alcohol solvent, an intermediate product is obtained after the reaction is carried out for 1-3 hours at 50-90 ℃, a 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 white solid is prepared after the reaction product is cooled to room temperature, filtered and dried in vacuum.
The titanium composition can be used as a catalyst for synthesizing PBST, and the ratio of the amount of the titanium composition added before reaction to the total molar number of the reaction monomers PTA and SA is 1: (1X 10)3～10×103) The amount of the titanium-based composition is based on the titanium element contained.
The prepared titanium composition can be applied to synthesis of aliphatic-aromatic copolyester PBST, and the preparation method of the synthesized PBST comprises the following steps: the method comprises the steps of adding reaction monomers of Pure Terephthalic Acid (PTA), Succinic Acid (SA) and 1, 4-Butanediol (BDO) into a catalyst titanium composition, carrying out esterification reaction to obtain an esterification intermediate product, and then continuing polycondensation reaction to finally prepare PBST.
In the above 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 ratios of PTA to SA to the molar ratio of BDO is 1: (1.1-2.0).
In the above technical scheme for preparing PBST, the ratio of the amount of the titanium composition added before the reaction to the total moles of the reaction monomers PTA and SA is 1: (1X 10)3～10×103) The amount of the titanium-based composition is based on the titanium element contained.
In the technical scheme for preparing the PBST, the esterification reaction conditions are that the pressure (gauge pressure) -0.05-0.3 MPa and the temperature is 180-230 ℃; the polycondensation reaction conditions are as follows: 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 less 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 micromolecules in the nature, and can be widely used in various fields such as express packaging, lunch boxes, film bags, foaming materials, disposable products and the like.
The molecular weight and distribution of the PBST in the invention are determined by gel chromatography (GPC), the molecular weight Mw is weight average component, the instrument specification is Waters 1515, and the test conditions are as follows: the mobile phase is trichloromethane, the flow rate is 1ml/min, and the temperature is 35 ℃. The b value of the PBST hue is measured by using a TC-PIIG full-automatic colorimeter.
The THF content of the esterification distillate was determined by gas chromatography.
The invention has the beneficial effects that:
the titanium composition does not contain heavy metal antimony, organic tin compound and rare earth element, is a non-toxic 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 groups to aromatic groups of 30/70-70/30, only the catalyst needs to be added once before the esterification reaction, and the catalyst does not need to be added again after the esterification reaction intermediate product is generated, so that the polycondensation reaction can be directly carried out.
The catalyst system has excellent catalytic activity, the reaction speed is obviously increased, and the polycondensation reaction time is reduced 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 from 1 to 4 ten thousand, and can be increased to 3 to 11 ten thousand.
The catalyst has stable reaction process, does not need to add other stabilizers, has small side reaction, and reduces the amount of tetrahydrofuran THF (tetrahydrofuran) generated by the side reaction in the esterification reaction stage to 5-8 percent from 10 percent in the single-component titanium catalyst catalytic reaction, calculated by the amount of BDO (boron-doped oxygen) serving as a raw material.
The PBST product synthesized by the method has good hue, and the b value of the hue of the PBST obtained by catalytic synthesis of a single-component titanium catalyst is reduced to 5-8, wherein the b value of the hue of the PBST is 10-15.
The preparation method for synthesizing PBST can continuously increase the molecular weight of PBST products without adding chain extenders under the condition of only prolonging the polycondensation reaction time, and the products do not contain chain extenders, stabilizers and the like.
Detailed Description
EXAMPLES 1-8 preparation of titanium-based compositions
Example 1
The molar ratio of the titanium compound to the phosphate ester was 10:1, and the molar ratio of the titanium compound to the metal compound was 1: 1.
Firstly weighing 34g (0.2mol) of tetramethyl titanate, 2.8g (0.02mol) of trimethyl phosphate and 120g (2mol) of isopropanol, placing the materials into a reactor with a reflux device, stirring and reacting for 3 hours at 50 ℃ to obtain an intermediate product, adding 28.0g (0.2mol) of anhydrous magnesium acetate into the intermediate product, slowly dropwise adding deionized water, continuing to react for 3 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composition C1。
Example 2
The molar ratio of titanium compound to phosphate was 10:1 and the molar ratio of titanium compound to metal compound was 1: 5.
Firstly weighing 45.6g (0.2mol) of tetraethyl titanate, 2.8g (0.02mol) of trimethyl phosphate and 240g (4mol) of isopropanol, placing the weighed materials into a reactor with a reflux device, stirring and reacting for 1 hour at 90 ℃ to obtain an intermediate product, adding 214g (1mol) of magnesium acetate tetrahydrate into the intermediate product, slowly dropwise adding deionized water, continuing to react for 1 hour, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composition C2。
Example 3
The molar ratio of the titanium compound to the phosphate ester is 1:1 and the molar ratio of the titanium compound to the metal compound is 1: 10.
Firstly, 57g (0.2mol) of tetraisopropyl titanate, 36g (0.2mol) of triethyl phosphate and 184g (4mol) of absolute ethyl alcohol are weighed and placed in a reactor with a reflux device, stirring and reacting are carried out for 2.5 hours at the temperature of 60 ℃ to obtain an intermediate product, 408g (2mol) of aluminum acetate is added into the intermediate product, then deionized water is slowly dripped, the reaction is continued for 2.5 hours, and the white solid titanium composition C is obtained after the reaction product is cooled to room temperature, filtered and dried in vacuum3。
Example 4
The molar ratio of the titanium compound to the phosphate ester is 1:1 and the molar ratio of the titanium compound to the metal compound is 1: 5.
Firstly weighing 68g (0.2mol) of tetrabutyl titanate, 36g (0.2mol) of triethyl phosphate and 184g (4mol) of absolute ethyl alcohol, placing the weighed materials into a reactor with a reflux device, stirring and reacting for 2 hours at 70 ℃ to obtain an intermediate product, adding 73g (1mol) of ethylene glycol aluminum into the intermediate product, slowly dropwise adding deionized water, continuing to react for 2 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composition C4。
Example 5
The molar ratio of the titanium compound to the phosphate ester is 5:1 and the molar ratio of the titanium compound to the metal compound is 1: 2.
Firstly 34g (0.2mol) of tetramethyl titanate, 5.6g (0.04mol) of trimethyl phosphate and 120g (2mol) of isopropanol are weighed and put into a reactor with a reflux device to be stirred and reacted for 1.5 hours at the temperature of 80 DEG CAdding 82g (0.4mol) of aluminum isopropoxide into the intermediate product, slowly dropwise adding deionized water, continuously reacting for 1.5 hours, cooling the reaction product to room temperature, filtering, and drying in vacuum to obtain a white solid titanium composition C5。
Example 6
The molar ratio of the titanium compound to the phosphate ester is 2:1 and the molar ratio of the titanium compound to the metal compound is 1: 5.
Firstly weighing 45.6g (0.2mol) of tetraethyl titanate, 18g (0.1mol) of triethyl phosphate and 92g (2mol) of absolute ethyl alcohol, placing the materials into a reactor with a reflux device, stirring and reacting for 3 hours at 50 ℃ to obtain an intermediate product, adding 81g (1mol) of zinc oxide into the intermediate product, slowly dripping deionized water into the intermediate product, continuing the reaction for 3 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composition C6。
Example 7
The molar ratio of the titanium compound to the phosphate ester was 10:1, and the molar ratio of the titanium compound to the metal compound was 1: 1.
Firstly, 57g (0.2mol) of tetraisopropyl titanate, 2.8g (0.02mol) of trimethyl phosphate and 184g (4mol) of absolute ethyl alcohol are weighed and placed in a reactor with a reflux device, stirring and reacting are carried out for 1 hour at the temperature of 90 ℃ to obtain an intermediate product, 36.6g (0.2mol) of zinc acetate is added into the intermediate product, then deionized water is slowly dripped into the intermediate product, the reaction is continuously carried out for 1 hour, the reaction product is cooled to room temperature, filtered and dried in vacuum to obtain a white solid titanium composition C7。
Example 8
The molar ratio of the titanium compound to the phosphate ester is 1:1 and the molar ratio of the titanium compound to the metal compound is 1: 10.
Firstly weighing 68g (0.2mol) of tetrabutyl titanate, 36g (0.2mol) of triethyl phosphate and 240g (4mol) of isopropanol, placing the weighed materials in a reactor with a reflux device, stirring and reacting for 2 hours at 70 ℃ to obtain an intermediate product, adding 438g (2mol) of zinc acetate dihydrate into the intermediate product, slowly dropwise adding deionized water, continuing to react for 2 hours, cooling the reaction product to room temperature, filtering and drying in vacuum to obtain a white solid titanium composition C8。
Examples 9-16 preparation of PBST
Example 9
199g (1.2mol) of PTA, 330g (2.8mol) of SA, 396g (4.4mol) of BDO and the titanium composition C were charged into the polymerization reactor1In an amount of 4X 10-3mol, and the dosage condition of the catalyst is as follows: c1/(PTA+SA)＝1:(1×103) Titanium-based composition C1The total mole number of PTA and SA, based on the mole number of the titanium-containing element (the same applies below), is (PTA + SA) (the same applies below). Performing esterification reaction at 180 deg.C under-0.05 MPa (gauge pressure), and finishing esterification reaction when distillate reaches over 95% of theoretical value to obtain intermediate product with total distillate L1And analyzing the tetrahydrofuran content in the distillate to H by gas chromatography1(ii) a And gradually reducing the pressure and raising the temperature of a reaction system, carrying out polycondensation reaction at 220 ℃ and under the vacuum degree of 50Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST product with the aliphatic/aromatic ratio of 70/30.
Example 10
465g (2.8mol) of PTA, 142g (1.2mol) of SA, 720g (8mol) of 1, 4-butanediol and the titanium composition C were charged into a polymerization reactor2In an amount of 4X 10-4mol, and the dosage condition of the catalyst is as follows: c2/(PTA+SA)＝1:(10×103). Performing esterification reaction at 230 deg.C and 0.3MPa (gauge pressure), and finishing esterification reaction when distillate reaches over 95% of theoretical value to obtain intermediate product with total distillate L2And analyzing the tetrahydrofuran content in the distillate to be H by gas chromatography2(ii) a And gradually reducing the pressure and raising the temperature of a reaction system, carrying out polycondensation reaction at 270 ℃ and under the vacuum degree of 300Pa, stopping the reaction when the polycondensation product reaches the required stirring power, cooling feed liquid by water, granulating, and synthesizing to obtain the PBST polyester product with the aliphatic/aromatic ratio of 30/70.
Example 11
266g (1.6mol) of PTA, 283g (2.4mol) of SA, 540g (6mol) of 1, 4-butanediol and the titanium composition C are added into a polymerization reaction kettle3In an amount of 8X 10-4mol, and the dosage condition of the catalyst is as follows: c3/(PTA+SA)＝1:(5×103). At 230 ℃ andcarrying out esterification reaction under the condition of-0.05 MPa (gauge pressure), when the distillate reaches more than 95% of the theoretical value, finishing the esterification reaction to obtain an intermediate product, wherein the total amount of the distillate is L3And analyzing the tetrahydrofuran content in the distillate to H by gas chromatography3A step of,; and gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 50Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 60/40.
Example 12
332g (2mol) of PTA, 236g (2mol) of SA, 540g (6mol) of 1, 4-butanediol and a titanium-based composition C as a catalyst were charged into a polymerization reactor4In an amount of 8X 10-4mol, and the dosage condition of the catalyst is as follows: c4/(PTA+SA)＝1:(5×103). Performing esterification reaction at 200 deg.C under-0.05 MPa (gauge pressure), and when the distillate reaches over 95% of theoretical value, finishing esterification reaction to obtain intermediate product with total distillate L4And the tetrahydrofuran content H in the distillate was analyzed by gas chromatography4(ii) a And gradually reducing the pressure and raising the temperature of the intermediate product, carrying out polycondensation reaction at 240 ℃ under the vacuum degree of 100Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 50/50.
Example 13
332g (2mol) of PTA, 236g (2mol) of SA, 540g (6mol) of 1, 4-butanediol and a titanium-based composition C as a catalyst were charged into a polymerization reactor5In an amount of 8X 10-4mol, and the dosage condition of the catalyst is as follows: c5/(PTA+SA)＝1:(5×103). Performing esterification reaction at 200 deg.C under-0.05 MPa (gauge pressure), and finishing esterification reaction when distillate reaches over 95% of theoretical value to obtain intermediate product with total distillate L5And the tetrahydrofuran content H in the distillate was analyzed by gas chromatography5. Gradually reducing pressure and heating the intermediate product, performing polycondensation reaction at 250 deg.C and vacuum degree of 100Pa, stopping reaction until the polycondensation product reaches required stirring power, and passing the feed liquid throughWater cooling and pelletizing to obtain PBST copolyester with aliphatic/aromatic ratio of 50/50.
Example 14
266g (1.6mol) of PTA, 284g (2.4mol) of SA, 540g (6mol) of 1, 4-butanediol and a titanium composition C as a catalyst were charged into a polymerization reactor6The amount is 4X 10-4mol, and the dosage condition of the catalyst is as follows: c6/(PTA+SA)＝1:(10×103). Performing esterification reaction at 230 deg.C and-0.05 MPa (gauge pressure), and finishing esterification reaction when distillate reaches over 95% of theoretical value to obtain intermediate product with total distillate L6And the tetrahydrofuran content H in the distillate was analyzed by gas chromatography6. And gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 50Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 60/40.
Example 15
332g (2mol) of PTA, 236g (2mol) of SA, 540g (6mol) of 1, 4-butanediol and a titanium-based composition C as a catalyst were charged into a polymerization reactor7In an amount of 4X 10-3mol, and the dosage condition of the catalyst is as follows: c1/(PTA+SA)＝1:(1×103). Performing esterification reaction at 210 deg.C and-0.05 MPa (gauge pressure), and finishing esterification reaction when the distillate reaches above 95% of theoretical value to obtain intermediate product with total distillate L7And the tetrahydrofuran content H in the distillate was analyzed by gas chromatography7. And gradually reducing the pressure and heating the intermediate product, carrying out polycondensation reaction at the temperature of 240 ℃ and the vacuum degree of 100Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 50/50.
Example 16
199g (1.2mol) of PTA, 330g (2.8mol) of SA, 540g (6mol) of 1, 4-butanediol and a titanium composition C as a catalyst were charged into a polymerization reactor8In an amount of 2X 10-3mol, and the dosage condition of the catalyst is as follows: c1/(PTA+SA)＝1:(2×103). In thatCarrying out esterification reaction at 220 deg.C under-0.05 MPa (gauge pressure), and finishing esterification reaction when distillate reaches over 95% of theoretical value to obtain intermediate product with total distillate L8And the tetrahydrofuran content H in the distillate was analyzed by gas chromatography8Gradually reducing the pressure and raising the temperature of the intermediate product, carrying out polycondensation reaction at 250 ℃ and under the vacuum degree of 200Pa, stopping the reaction after the polycondensation product reaches the required stirring power, cooling feed liquid by water, and granulating to synthesize the PBST copolyester product with the aliphatic/aromatic ratio of 70/30.
The titanium-based compositions used in examples 9 to 16 and the results of the esterification and polycondensation reactions are shown in Table 1, respectively, and the number of moles of the titanium-based composition is based 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 tetrabutyl titanate (TBT for short) as a one-component catalyst was added in an amount of 4X 10 before the esterification-4mol, adding TBT into the intermediate product again after the esterification reaction is finished, wherein the TBT is 2 multiplied by 10-3After mol, the polycondensation reaction is carried out, and the mole number of the TBT is calculated by the contained titanium element, and the result is 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 tetraisopropyl titanate (TPT), a one-component titanium-based catalyst, was added before esterification in an amount of 8X 10-4mol, adding TPT into the intermediate product again after the esterification reaction is finished, wherein the TPT is 1 multiplied by 10-3After mol, the polycondensation reaction was carried out, and the results are shown in Table 1, wherein TPT is used in mol based on the contained titanium element.
TABLE 1 Experimental results for the synthesis of PBST
Figure BDA0003549414960000081
As can be seen from Table 1, in examples 9 to 16, compared with comparative examples 1 and 2, the amount of THF produced by the side reaction in the esterification stage was reduced to 5% to 8% from 10% in the case of the single titanate-catalyzed reaction; when similar molecular weights are achieved, polycondensation times are reduced compared to a single titanate catalyst; by using the titanium composition, the weight average molecular weight Mw of PBST can reach 11 ten thousand, and the hue b value is better, and is reduced to 5-8 from 10-15 in the single titanate catalytic reaction.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the 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 within the spirit, scope and content of the invention.

Claims (9)

1. A titanium composition for synthesizing poly (butylene succinate-co-terephthalate) is characterized in that titanate and phosphate ester react in a solvent of isopropanol or absolute ethyl alcohol, an intermediate product is obtained after the reaction is carried out for 1-3 hours at the temperature of 50-90 ℃, a 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 white solid is prepared after the reaction product is cooled to room temperature, filtered and dried in vacuum.
2. The titanium-based composition according to claim 1, wherein the titanate is one of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, and 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 tetrahydrate magnesium acetate; the aluminum compound is one selected from aluminum acetate, aluminum ethylene glycol or aluminum isopropoxide; the zinc compound is one of zinc oxide, zinc acetate or zinc acetate dihydrate.
4. The titanium composition according to claim 1, wherein the molar ratio of the titanium compound to the phosphoric ester is 10:1 to 1:1, and the molar ratio of the titanium compound to the metal compound is 1:1 to 1: 10.
5. The titanium composition according to claim 1, wherein the molar ratio of the solvent isopropanol or absolute ethanol to the titanium compound is 10: 1-20: 1.
6. the method for synthesizing PBST by applying the titanium composition of claim 1 is characterized in that reaction monomers of PTA, SA and BDO are subjected to esterification reaction after adding the catalyst titanium composition to obtain an esterification intermediate product, and then the polycondensation reaction is continued to prepare PBST finally; wherein:
the molar 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 added titanium composition to the total molar number of the reaction monomers PTA and SA is 1: (1X 10)3～10×103) The amount of the titanium-based composition is based on the titanium element contained.
7. The method according to claim 6, wherein the esterification reaction is carried out under conditions of a pressure gauge of-0.05 to 0.3MPa and a temperature of 180 to 230 ℃; the polycondensation reaction conditions are as follows: the vacuum degree is 50-300 Pa, and the temperature is 220-270 ℃.
8. The process according to claim 6, wherein the esterification reaction stage is accompanied by side reactions, and THF is produced in an amount of 5 to 8% as compared with the amount of BDO as the starting material, which is 10% of the amount of THF produced in the reaction catalyzed by the single-component titanium-based catalyst.
9. The method of claim 6, wherein the weight average molecular weight of the condensation polymerization prepared PBST is 6000 to 110000g/mol, and the hue b value of PBST is 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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