CN114920917A - Low-melting-index high-crystallization-temperature branched poly (butylene terephthalate-adipate) and preparation method thereof - Google Patents

Low-melting-index high-crystallization-temperature branched poly (butylene terephthalate-adipate) and preparation method thereof Download PDF

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CN114920917A
CN114920917A CN202111663095.1A CN202111663095A CN114920917A CN 114920917 A CN114920917 A CN 114920917A CN 202111663095 A CN202111663095 A CN 202111663095A CN 114920917 A CN114920917 A CN 114920917A
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刘建
魏志勇
涂著
李平
桑琳
张伟
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Dalian University of Technology
Kanghui New Material Technology Co Ltd
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Abstract

The invention relates to a preparation method of branched poly (butylene terephthalate) -adipate with low melting index and high crystallization temperature, which is prepared by adopting an alpha-hydroxy acid in-situ polymerization catalyst and a trifunctional aminocarboxylic acid branching agent. The preparation method of the in-situ polymerization catalyst comprises the following steps: (1) adding metal carboxylate with certain mass into a mixed solution of an alcohol compound with a molecular structure only provided with one hydroxyl and distilled water for reaction; (2) after the alpha-hydroxy acid is added, the system is refluxed and reacted for a period of time to prepare the in-situ polymerization catalyst. The prepared in-situ polymerization catalyst has small particle size, good dispersibility, high activity, deliquescence resistance, heat resistance and illumination resistance, and can be stored for a long time in a natural environment. Under the action of catalyst and branching agent, the branched polybutylene terephthalate-adipate with low melting temperature can be obtained.

Description

Low-melting-index high-crystallization-temperature branched poly (butylene terephthalate-adipate) and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of biodegradable aliphatic polyester high polymer materials, and relates to low-melting-index high-crystallization-temperature branched poly (butylene terephthalate-adipate) and a preparation method thereof.
Background
In the increasing exhaustion of fossil resources, CO 2 Under the background of global warming and serious environmental pollution caused by excessive emission and the like, the global consensus is achieved by turning to low-carbon circular economy, policies such as carbon peaking and carbon neutralization are brought into the overall layout of ecological civilization construction, people's fortune is continuously developed and a human fortune community is constructed in the event of China, and a new energy source and a new material are searched to replace petrochemical products, so that the global common mission is achieved.
Compared with the traditional biodegradable polyester, the main chain of the poly (butylene adipate-terephthalate) (PBAT) is formed by connecting an aliphatic structural unit and an aromatic structural unit through an ester bond which is easy to hydrolyze, is easy to be decomposed and metabolized by a plurality of microorganisms or animal and plant in nature, and is finally converted into CO2 and H2O. The PBAT has higher melting point, good mechanical ductility, processability and physical and mechanical properties, can be processed by injection molding, blow molding, film blowing and other forming methods, has extremely wide application, can be applied to the field of packaging, medicine and health, agriculture and the like, and meets the requirements of environmental protection and sustainable development strategy.
Patent CN 108384201A relates to a PBAT material with high crystallization speed and a preparation method thereof, and xylylene dialkyl urea is used as a nucleating agent to promote crystallization of PBAT, so that the crystallization speed and mechanical properties of PBAT can be improved. But the PBAT matrix and the nucleating agent are from commercial products, and the nucleating agent contains a benzene ring structure with toxicity, so that the application of biodegradable PBAT is greatly limited.
Patent CN 100528929 discloses a process for preparing aliphatic polyester, which adopts a composite catalyst system of metal alkoxide and titanium silicon oxide to compound with phosphoric acid compounds, so as to synthesize aliphatic dibasic acid glycol ester with high molecular weight and good chromaticity. However, the preparation steps of the catalyst are complicated, and the production energy consumption is greatly increased.
Patent CN 110105555B mentions a preparation method of branched biodegradable polyester, which utilizes triethanolamine and trifunctional aziridine group compound to introduce a branched structure on polyester molecules, and also inhibits the generation of terminal carboxyl, thereby obtaining a polyester material with high melt strength and small longitudinal and transverse differences of tensile strength and right-angle tearing strength;
patent CN 107189043A relates to a polyester with high molecular weight and weak crystallinity, and a preparation method and application thereof, the polyester is prepared by polycondensation of 1, 5-pentanediol, dibasic acid, glycerol or trimethylolpropane and other branching agents, and the application field of the polyester is too narrow due to poor mechanical property of the polyester material with weak crystallinity;
patent CN 110684180a relates to a method for improving the crystallization performance of biodegradable aliphatic aromatic copolyester, which comprises subjecting an aliphatic aromatic copolyester melt obtained by esterification and polycondensation to shearing and cooling directly, or subjecting the obtained aliphatic aromatic copolyester melt to cooling granulation, melting, shearing and cooling to obtain the aliphatic aromatic copolyester with high crystallization performance. The method needs to melt the polyester twice, has large energy consumption, greatly reduces the performance of the material after melting for many times, and is not advisable in practical application;
patent CN 104974337a relates to a degradable branched polyester and a preparation method thereof, wherein monoglyceride is used as a branching agent to be introduced into linear molecules of the polyester to obtain a polyester product with low crystallinity.
It can be seen that the existing research can only increase the branching degree of PBAT or increase the crystallization rate of the commercialized PBAT in a single way, but cannot make PBAT have high crystallization rate and crystallization temperature while having high molecular weight and a certain branching degree. Therefore, it is of great importance to develop a method for rapidly increasing the molecular weight and crystallization temperature and decreasing the melt index of PBAT having a certain degree of branching.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method of low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate.
The nanoparticle in-situ polymerization catalyst provided by the invention is prepared by using alpha-hydroxy acid of biological origin as a raw material, the provided branching agent is trifunctional aminocarboxylic acid of full biological origin, is green and nontoxic, and can accelerate the crystallization rate and improve the crystallization temperature of the branched PBAT while catalytically synthesizing high molecular weight.
The invention provides a low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate, which comprises the following steps: using adipic acid, terephthalic acid and 1, 4-butanediol as raw materials, carrying out esterification reaction under the action of an in-situ polymerization catalyst, and carrying out pre-polycondensation reaction and final polycondensation reaction under the action of a branching agent to prepare branched poly (butylene adipate-terephthalate) with low melting index and high crystallization temperature; the branching agent is an aminocarboxylic acid with three functional groups.
Wherein the branching agent is an amino acid compound having two amino groups and one carboxyl group, or two carboxyl groups and one amino group, or one amino group, one carboxyl group and one hydroxyl group.
Wherein the branching agent is serine, threonine, glutamine, asparagine, tyrosine, aspartic acid, glutamic acid, lysine.
The preparation method of the in-situ polymerization catalyst comprises the following specific steps:
(1) adding metal carboxylate with certain mass into a mixed solution of alcohol compounds with a certain proportion of molecular structures and distilled water, starting mechanical stirring, and stirring at a certain speed for 10 min;
(2) adding alpha-hydroxy acid, stirring for 10-30min, slowly heating to 10 deg.C above the boiling point of low-boiling monohydric alcohol, and refluxing for 2-5 hr;
(3) and after the reaction is finished, the mechanical stirring is closed, the reaction product is cooled to the room temperature of 25 ℃, the reaction product is filtered under reduced pressure, the filter cake is washed three times by using absolute ethyl alcohol, and the in-situ polymerization catalyst is obtained after the reaction product is dried in vacuum at the room temperature.
Wherein the low temperature is-5-5 ℃, preferably 0 ℃, and the mechanical stirring speed is 300 r/min; the mass ratio of the alcohol compound with only one hydroxyl group in the molecular structure to the distilled water is 20-40, preferably 30.
Wherein, the mass ratio of the alpha-hydroxy acid to the metal acetate is 1.6-2.8, preferably 2.1;
wherein the metal carboxylate with certain mass is 0.01-0.03 time of the mass of the mixed solution, and preferably 0.02; the metal carboxylate is at least one of acetate, oxalate, malonate, succinate, glutarate and adipate of metal calcium, magnesium, zinc, aluminum, iron, cobalt, nickel and copper;
wherein the alcohol compound with only one hydroxyl in the molecular structure is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol; the alpha-hydroxy acid is at least one of glycolic acid, lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid.
Wherein, the dosage of the nanometer microparticle in-situ polymerization catalyst is 0.5-1.5 per mill of the total mass of the system, and is preferably 1 per mill; the dosage of the branching agent is 0.2-0.6 per mill of the total mass of the system, preferably 0.5 per mill;
wherein the molar ratio of the alkyd to the system is 1.4, and the mass ratio of adipic acid to terephthalic acid is 1: 1; the esterification temperature is 200-; the pre-polycondensation temperature is 230 ℃ and 250 ℃, the pre-polycondensation pressure is 1k-2kPa absolute, and the pre-polycondensation time is 30-50 min; the polycondensation temperature is 230-250 ℃, the polycondensation pressure is 5-30Pa absolute, and the polycondensation time is 120-180 min.
The preparation method of the poly (butylene terephthalate-adipate) nano microparticle in-situ polymerization catalyst has the advantages that the particle size of the in-situ polymerization catalyst is 50-100 nm; the prepared polybutylene adipate-terephthalate has the melt index of 1.0-2.7g/10 min; the crystallization temperature is above 85 ℃.
The nanoparticle in-situ polymerization catalyst provided by the invention is prepared by adopting alpha-hydroxy acid of biological origin as a raw material, and the branching agent is trifunctional aminocarboxylic acid of full biological origin, so that the catalyst is green and nontoxic, the preparation process is simple and convenient, the operation is easy, and the catalyst is free from environmental pollution. The in situ polymerization catalysts and branching agents used in the present invention have the following advantages over other catalysts:
(1) the in-situ polymerization catalyst has simple synthesis steps and low energy consumption;
(2) the used alpha-hydroxy acid and trifunctional aminocarboxylic acid are environment-friendly, and the application range of biodegradable PBAT is not influenced;
(3) the synthesized in-situ polymerization catalyst is nano-micro particles, the particle size is small, the nano-scale is realized, the addition amount is small, and the dispersibility is good;
(4) meanwhile, the branched PBAT with low melt index and high crystallization temperature can be synthesized by catalysis.
Drawings
FIG. 1 is a DSC thermogram of PBAT synthesized by adding zinc mandelate and glutamic acid branching agent as in-situ catalysts to PBAT and using the method of the embodiment I. The branched PBAT in FIG. 1 refers to PBAT after in situ catalyst zinc mandelate and branching agent glutamic acid were added, and the pure PBAT refers to PBAT synthesized by the method of the first embodiment.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the drawings.
The invention provides a low-melting-index high-crystallization-temperature polybutylene terephthalate-adipate, which comprises the following steps: using adipic acid, terephthalic acid and 1, 4-butanediol as raw materials, carrying out esterification reaction under the action of an in-situ polymerization catalyst, and carrying out pre-polycondensation reaction and final polycondensation reaction under the action of a branching agent to prepare low-melting-index high-crystallization-temperature branched poly (butylene adipate-terephthalate); the branching agent is an aminocarboxylic acid with three functional groups.
The dosage of the in-situ polymerization catalyst is 0.5-1.5 per mill of the total mass of the system, and is preferably 1 per mill; the dosage of the branching agent is 0.2-0.6 per mill of the total mass of the system, preferably 0.5 per mill;
the molar ratio of the alkyd of the system is 1.4, wherein the mass ratio of adipic acid to terephthalic acid is 1: 1; the esterification temperature is 200-220 ℃, and the esterification time is 150-200 min; the pre-polycondensation temperature is 230-; the polycondensation temperature is 230-.
The branching agent is an amino acid compound with two amino groups and one carboxyl group or two carboxyl groups and one amino group or one amino group, one carboxyl group and one hydroxyl group.
The branching agent is at least one of serine, threonine, glutamine, asparagine, tyrosine, aspartic acid, glutamic acid and lysine.
The preparation equation of the in-situ polymerization catalyst is as follows:
Figure BDA0003447360070000061
wherein, with R 1 The alpha-hydroxy carboxylic acid of the group is of the formula
Figure BDA0003447360070000062
Figure BDA0003447360070000063
M is metal atoms such as Ca, Zn, Mg, Mn, Co, Fe and the like;
the branching agent has the structural formula:
Figure BDA0003447360070000065
Figure BDA0003447360070000064
the preparation method of the in-situ polymerization catalyst comprises the following specific steps:
(1) adding metal carboxylate with certain mass into a mixed solution of alcohol compounds with a certain proportion of molecular structures and distilled water, starting mechanical stirring, and stirring at a certain speed for 10 min;
(2) adding alpha-hydroxy acid, stirring for 10-30min, slowly heating to 10 deg.C above the boiling point of low-boiling monohydric alcohol, and refluxing for 2-5 hr;
(3) and after the reaction is finished, closing the mechanical stirring, cooling to room temperature of 25 ℃, carrying out suction filtration under a reduced pressure condition, washing a filter cake for three times by using absolute ethyl alcohol, and carrying out vacuum drying at room temperature to obtain the in-situ polymerization catalyst.
The low temperature is-5-5 ℃, preferably 0 ℃, and the mechanical stirring speed is 300 r/min; the mass ratio of the alcohol compound having only one hydroxyl group in the molecular structure to distilled water is 20 to 40, preferably 30; the mass ratio of the alpha-hydroxy acid to the metal acetate is 1.6-2.8, preferably 2.1; the metal carboxylate with a certain mass is 0.01-0.03 time of the mass of the mixed solution, and preferably 0.02; the metal carboxylate is at least one of acetate, oxalate, malonate, succinate, glutarate and adipate of metal calcium, magnesium, zinc, aluminum, iron, cobalt, nickel and copper; the alcohol compound with only one hydroxyl in the molecular structure is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol; the alpha-hydroxy acid is at least one of glycolic acid, lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid.
Embodiment 1
Preparation of in-situ polymerization catalyst:
(1) adding 20g of calcium acetate into a mixed solution of 2kg of methanol and distilled water at the temperature of-5 ℃, wherein the mass ratio of the methanol to the distilled water is 20, and stirring at the stirring speed of 300r/min for 10 min;
(2) adding 32g of glycolic acid into the system, stirring for 10min, and then heating to 80 ℃ to enable the system to perform reflux reaction for 2 h;
(3) after the reflux is finished, the mechanical stirring is stopped, the system is cooled to room temperature, the suction filtration is carried out under the reduced pressure condition, the filter cake is washed by absolute ethyl alcohol for three times, and the in-situ polymerization catalyst calcium glycolate is obtained after the vacuum drying at room temperature, the particle size of the catalyst calcium glycolate is 69nm, and the structural formula of the catalyst calcium glycolate is
Figure BDA0003447360070000081
Example II
Preparation of in-situ polymerization catalyst:
(1) adding 15g of zinc acetate into a mixed solution of 3kg of ethanol and distilled water at the temperature of-0 ℃, wherein the mass ratio of the ethanol to the distilled water is 30, and stirring at the stirring speed of 300r/min for 10 min;
(2) adding 33g of mandelic acid into the system, stirring for 10min, heating to 75 ℃, and carrying out reflux reaction on the system for 3 h;
(3) after the reflux is finished, the mechanical stirring is closed, the system is cooled to room temperature, the pumping filtration is carried out under the reduced pressure condition, the filter cake is washed three times by absolute ethyl alcohol, and the in-situ polymerization catalyst zinc mandelate is obtained after the vacuum drying at room temperature, the particle size of the zinc mandelate is 57nm, and the structural formula of the zinc mandelate is shown in the specification
Figure BDA0003447360070000082
Example three
Preparation of in-situ polymerization catalyst:
(1) adding 30g of magnesium adipate into a mixed solution of 4kg of n-propanol and distilled water at the temperature of 5 ℃, wherein the mass ratio of the n-propanol to the distilled water is 40, and stirring at the stirring speed of 300r/min for 10 min;
(2) adding 84g of 6-hydroxycaproic acid into the system, stirring for 10min, heating to 75 ℃, and carrying out reflux reaction on the system for 4 h;
(3) after the reflux is finished, the mechanical stirring is closed, the system is cooled to the room temperature, the suction filtration is carried out under the reduced pressure condition, the filter cake is washed three times by absolute ethyl alcohol, and the vacuum drying is carried out at the room temperature to obtain the productThe particle size of the in-situ polymerization catalyst, namely the magnesium hydroxycaproate, is 81nm, and the structural formula of the catalyst is shown in the specification
Figure BDA0003447360070000091
Example four
Preparation of polybutylene terephthalate-adipate:
(1) respectively adding 900g of terephthalic acid (5.4mol), 900g of adipic acid (6.2mol) and 1464g of butanediol (16.2mol) into a 5L reaction kettle, then adding 1.63g of a self-made zinc mandelate in-situ polymerization catalyst (0.5 per thousand of the total mass of the system), heating the system to 200 ℃ for esterification reaction, wherein the reaction time is 150 minutes;
(2) adding 1.63g of serine (0.5 per mill of the total mass of the system) into the system after the esterification reaction is finished, heating the system to 230 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1kPa for 30 min;
(3) after the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 230 ℃ and under the absolute pressure of 5Pa, and the polycondensation time is 120 min. Thus obtaining the polybutylene terephthalate-adipate melt. The intrinsic viscosity was found to be 1.1g/10min, and the crystallization temperature was 89 ℃.
Example five
Preparation of polybutylene terephthalate-adipate:
(1) respectively adding 900g of terephthalic acid (5.4mol), 900g of adipic acid (6.2mol) and 1464g of butanediol (16.2mol) into a 5L reaction kettle, then adding 3.26g of a home-made calcium glycolate in-situ polymerization catalyst (1 per mill of the total mass of the system), heating the system to 210 ℃ for esterification reaction, wherein the reaction time is 180 minutes;
(2) after the esterification reaction is finished, adding 1.63g of aspartic acid (0.5 per mill of the total mass of the system) into the system, heating the system to 230 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1.4kPa for 40 min;
(3) after the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 240 ℃ under the absolute pressure of 25Pa, and the polycondensation time is 130 min. Thus obtaining the polybutylene terephthalate-adipate melt. It was found to have a melt index of 1.9g/10min and a crystallization temperature of 87 ℃.
Comparative example 1
Preparation of polybutylene terephthalate-adipate:
(1) respectively adding 900g of terephthalic acid (5.4mol), 900g of adipic acid (6.2mol) and 1464g of butanediol (16.2mol) into a 5L reaction kettle, then adding 3g of tetrabutyl titanate, heating the system to 200 ℃ for esterification reaction, wherein the reaction time is 200 minutes;
(2) after the esterification reaction is finished, heating the system to 220 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1.9kPa for 20 min;
(3) after the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 250 ℃ and under the absolute pressure of 49Pa, and the polycondensation time is 180 min. Thus obtaining the polybutylene terephthalate-adipate melt under the catalysis of tetrabutyl titanate. It was found to have a melt index of 12.4g/10min and a crystallization temperature of 69 ℃.
The nano-microparticle in-situ polymerization catalyst and polybutylene terephthalate-adipate prepared in the above examples were detected according to the following methods:
the particle size measuring instrument is a QUANTA450 tungsten filament scanning electron microscope manufactured by FEI corporation, USA.
The method for testing the melt index is as follows: the method is carried out according to the regulation of GB/T3682-2000A. The test conditions were D (temperature: 190 ℃ C., load: 2.16 kg).
Crystallization temperature DSC measurement was performed using DSC25 with an instrument model TA corporation, usa, and the polymer crystallization temperature and melting point were calculated from the measurement results. During testing, the adopted procedure is as follows: under the nitrogen atmosphere (the flow rate is 50ml/min), the temperature rising and falling speed is 10 ℃/min.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.

Claims (10)

1. A low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate is characterized in that the preparation method of the low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate comprises the following steps: using adipic acid, terephthalic acid and 1, 4-butanediol as raw materials, carrying out esterification reaction under the action of an in-situ polymerization catalyst, and carrying out pre-polycondensation reaction and final polycondensation reaction under the action of a branching agent to prepare low-melting-index high-crystallization-temperature branched poly (butylene adipate-terephthalate); the branching agent is an aminocarboxylic acid with three functional groups.
2. The low melting-index branched polybutylene terephthalate-adipate as claimed in claim 1, wherein the branching agent is an amino acid compound with two amino groups and one carboxyl group, or two carboxyl groups and one amino group, or one amino group, one carboxyl group and one hydroxyl group.
3. The low melting point branched polybutylene terephthalate-adipate as claimed in claim 2, wherein the branching agent is at least one of serine, threonine, glutamine, asparagine, tyrosine, aspartic acid, glutamic acid, and lysine.
4. The low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate as claimed in claim 3, wherein the in-situ polymerization catalyst is prepared by the following specific steps:
(1) adding a certain mass of metal carboxylate into a mixed solution of an alcohol compound with a certain proportion of molecular structure and only one hydroxyl and distilled water at a low temperature, starting mechanical stirring, and stirring at a certain speed for 10 min;
(2) adding alpha-hydroxy acid, stirring for 10-30min, slowly heating to 10 deg.C above the boiling point of low-boiling monohydric alcohol, and refluxing for 2-5 hr;
(3) and after the reaction is finished, closing the mechanical stirring, cooling to room temperature of 25 ℃, carrying out suction filtration under a reduced pressure condition, washing a filter cake for three times by using absolute ethyl alcohol, and carrying out vacuum drying at room temperature to obtain the in-situ polymerization catalyst.
5. The low melt index high crystallization temperature branched poly (butylene terephthalate-adipate) according to claim 4, wherein the low temperature conditions are-5-5 ℃, preferably 0 ℃, and the mechanical stirring rate is 300 r/min; the mass ratio of the alcohol compound having only one hydroxyl group in the molecular structure to distilled water is 20 to 40, preferably 30.
6. The low melt index high crystallization temperature branched polybutylene terephthalate-adipate of claim 4, characterized in that the mass ratio of the alpha-hydroxy acid to the metal acetate is 1.6-2.8, preferably 2.1.
7. The low-melting-index high-crystallization-temperature branched polybutylene terephthalate-adipate as claimed in claim 4, wherein the certain mass of the metal carboxylate is 0.01-0.03 times, preferably 0.02 times of the mass of the mixed solution; the metal carboxylate is at least one of acetate, oxalate, malonate, succinate, glutarate and adipate of calcium, magnesium, zinc, aluminum, iron, cobalt, nickel and copper.
8. The low melting-index high crystallization-temperature branched polybutylene terephthalate-adipate as claimed in claim 4, wherein the alcohol compound having only one hydroxyl group in the molecular structure is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol; the alpha-hydroxy acid is at least one of glycolic acid, lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid.
9. The low melting index high crystallization temperature branched poly (butylene terephthalate-adipate) according to any one of claims 1 to 8, wherein the amount of the in situ polymerization catalyst is 0.5 to 1.5%, preferably 1%, by mass of the total system; the amount of the branching agent is 0.2 to 0.6 per mill, preferably 0.5 per mill of the total mass of the system.
10. The low melting point high crystallization temperature branched polybutylene terephthalate-adipate as claimed in any one of claims 1-8, wherein the molar ratio of the alkyd in the system is 1.4, and the mass ratio of adipic acid to terephthalic acid is 1: 1; the esterification temperature is 200-; the pre-polycondensation temperature is 230 ℃ and 250 ℃, the pre-polycondensation pressure is 1k-2kPa absolute, and the pre-polycondensation time is 30-50 min; the polycondensation temperature is 230-250 ℃, the polycondensation pressure is 5-30Pa absolute, and the polycondensation time is 120-180 min.
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