CN115449059A - Preparation method and application of degradable polybutylene adipate terephthalate - Google Patents

Preparation method and application of degradable polybutylene adipate terephthalate Download PDF

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CN115449059A
CN115449059A CN202211020850.9A CN202211020850A CN115449059A CN 115449059 A CN115449059 A CN 115449059A CN 202211020850 A CN202211020850 A CN 202211020850A CN 115449059 A CN115449059 A CN 115449059A
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degradable
prepolymer
polybutylene adipate
stabilizer
graphene
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CN115449059B (en
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饶建国
刘文伟
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Zhongshan Hongyi Film Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a preparation method and application of degradable polybutylene adipate terephthalate, which comprises the following steps: preparing zinc oxide @ graphene, mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer with the zinc oxide @ graphene, and reacting to obtain a first prepolymer; mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and reacting to obtain a second prepolymer; and mixing the first prepolymer and the second prepolymer, and reacting to obtain the degradable polybutylene adipate terephthalate chip. The prepared degradable polybutylene adipate-terephthalate slice has the characteristics of high strength, high toughness, high water resistance, degradability and the like, and can be used for preparing film products or injection-molded products.

Description

Preparation method and application of degradable polybutylene adipate terephthalate
Technical Field
The invention relates to the technical field of polyester materials, in particular to a preparation method and application of degradable polybutylene adipate terephthalate.
Background
Poly (butylene adipate terephthalate) (PBAT) is prepared by copolymerizing adipic acid, terephthalic acid and 1,4-butanediol, and a molecular chain of the poly (butylene adipate terephthalate) (PBAT) contains aromatic rings and aliphatic chain segments, so that the poly (butylene terephthalate) (PBAT) has good ductility and elongation at break, and can be used as a film material.
PBAT is degradable, but the degree of degradation is greatly affected by the composition of the segment. Relevant studies have shown that complete biodegradation can only be achieved when terephthalic acid accounts for less than 55% of the total molar amount of diacid monomers, but the mechanical properties are not easily improved due to the low proportion of terephthalic acid. In addition, the existing PBAT has poor barrier property, water vapor is easy to permeate, the use requirements in the fields of food preservation, agricultural mulching films and the like are difficult to meet, the PBAT preparation process is complex, the cost is high, and the PBAT preparation process is also a great factor for limiting the application of the PBAT.
By adding the layered fillers such as montmorillonite and mica powder, the permeation path of water vapor can be prolonged to a certain extent, so that the purpose of blocking water vapor permeation is achieved to a certain extent, but the improvement of the blocking property is still limited, a certain amount of fillers are required to be added to realize the effect, and the mechanical property is easily influenced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of degradable polybutylene adipate terephthalate (PBAT), and the prepared PBAT has the characteristics of high strength, high toughness, high water resistance, degradability and the like.
The invention also provides the degradable polybutylene adipate terephthalate slice prepared by the preparation method.
The invention also provides application of the degradable polybutylene adipate terephthalate slice.
The preparation method of the degradable polybutylene adipate terephthalate according to the first aspect of the invention comprises the following steps:
dispersing graphene oxide in a first solvent to prepare a dispersion liquid;
adding zinc acetate into the dispersion liquid, adjusting the pH value to be neutral, carrying out hydrothermal treatment, adding a reducing agent for reaction, separating a solid phase, and calcining in an inert atmosphere to obtain zinc oxide @ graphene;
mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer with the zinc oxide @ graphene, and carrying out a first esterification reaction to obtain a first prepolymer;
mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction to obtain a second prepolymer;
and mixing the first prepolymer and the second prepolymer, and carrying out a third esterification reaction to obtain the degradable polybutylene adipate-terephthalate chip.
The preparation method of the degradable polybutylene adipate terephthalate provided by the embodiment of the invention has at least the following beneficial effects:
the surface of the graphene oxide has rich functional groups, zinc acetate can be adsorbed, the zinc acetate is hydrolyzed to generate zinc hydroxide to be attached to the surface of the graphene oxide through pH adjustment and hydrothermal treatment, a reducing agent is added to reduce the graphene oxide to obtain zinc hydroxide @ graphene, and the zinc hydroxide @ graphene is obtained through calcination in an inert atmosphere. By the method, the zinc oxide can be uniformly loaded on the surface of the graphene, and the agglomeration of the zinc oxide and the graphene is reduced.
The zinc oxide can absorb ultraviolet rays, the graphene has a barrier effect, and the zinc oxide and the graphene can reduce the absorption of the polyester matrix to the ultraviolet rays and reduce the transmittance of the ultraviolet rays by matching use, so that the aging resistance is improved. On the other hand, although the invention can inhibit the photoaging degradation of the PBAT, the PBAT is still inevitably degraded in the use process to generate degradation free radicals, and the exposed electrons are easily transmitted to the surface of the graphene from the valence band of the zinc oxide along with the accumulation of the degradation free radicals, so that the electron transfer is realized, and the effect of accelerating the degradation can be further achieved when the degradation products are accumulated to a certain degree. Therefore, the zinc oxide @ graphene is utilized, so that the effect of inhibiting the photo-aging degradation of PBAT is achieved, the obvious reduction of the service performance caused by too fast degradation in the early stage of use is avoided, the durability is improved, and the effect of accelerating degradation is achieved when degradation products are accumulated in the later stage of use, so that the durability and the degradability are both achieved. Based on the photocatalytic degradation effect of zinc oxide @ graphene, complete degradation can be realized at a higher terephthalic acid ratio, and the mechanical property is improved.
The zinc oxide @ graphene improves the dispersibility of graphene, can avoid the agglomeration of graphene sheet layers, improves the mechanical property, is beneficial to constructing a circuitous channel, prolongs the transmission path of water vapor and further improves the water blocking performance.
The two-step prepolymerization is carried out in the esterification reaction process, so that the esterification rate can be improved, a butanediol adipate chain segment with a certain length can be obtained, a microcrystalline region is provided by utilizing the excellent crystallinity of the butanediol adipate chain segment, and the butanediol adipate chain segment plays a role of a physical anchor point, so that the mechanical property is further improved, the compactness of a molecular chain can be improved, and the water resistance is improved.
According to some embodiments of the invention, the first solvent comprises an alcohol and water.
According to some embodiments of the invention, the alcohol is selected from ethanol.
According to some embodiments of the invention, the volume ratio of the alcohol to the water in the first solvent is from 0.5 to 2:1.
According to some embodiments of the invention, the ultrasound treatment is performed during the preparation of the dispersion.
According to some embodiments of the invention, the power of the sonication is 50-100W, the frequency is 25-40kHz, and further the time of the sonication is 0.5-3h.
According to some embodiments of the invention, the mass ratio of zinc in the zinc acetate to the graphene oxide is 1-10, further 2-6:1.
According to some embodiments of the invention, the temperature of the hydrothermal treatment is 60-95 ℃.
According to some embodiments of the invention, the hydrothermal treatment is carried out for a time of 5 to 20 hours.
The hydrothermal treatment is used for fully generating zinc hydroxide from zinc acetate and loading the zinc hydroxide on the surface of graphene.
According to some embodiments of the invention, the reducing agent is selected from sodium citrate, hydrazine hydrate.
According to some embodiments of the invention, the weight ratio of the reducing agent to the graphene oxide is 0.5-0.8.
According to some embodiments of the invention, the temperature at which the reducing agent is added to carry out the reaction is between 80 and 100 ℃.
According to some embodiments of the invention, the reducing agent is added for a reaction time of 1 to 3 hours.
According to some embodiments of the invention, the temperature of the calcination is 200 to 300 ℃, and further, the calcination time is 1 to 5 hours. The residual functional groups on the surface of the graphene can be further eliminated by calcination, so that the forbidden bandwidth is reduced, and the photocatalytic activity is improved.
According to some embodiments of the invention, the first catalyst and the second catalyst are independently selected from the group consisting of tetrabutyl titanate, tetra-n-ethyl titanate, and tetra-isopropyl titanate.
According to some embodiments of the invention, the first stabilizer and the second stabilizer are independently selected from the group consisting of triphenyl phosphate, pentaerythritol phosphate, and ethyl phosphate.
According to some embodiments of the invention, the first stabilizer is triphenyl phosphate and the second stabilizer is pentaerythritol phosphate. The triphenyl phosphate and the terephthalic acid have good compatibility, can play a good stabilizing role, and reduce the occurrence of side reactions; in addition, triphenyl phosphate has a polyphenyl ring structure, can generate conjugate interaction with graphene, and improves the dispersibility of the graphene and the interface effect between the graphene and polyester, so that the reinforcing effect and the blocking effect of the graphene can be better exerted. The pentaerythritol phosphate has better stabilizing effect on adipic acid, and the two stabilizers are matched, so that a high-molecular-weight final product can be obtained more favorably.
According to some embodiments of the invention, the molar ratio of terephthalic acid to butanediol in the first esterification reaction is 1.2 to 2.
According to some embodiments of the invention, the zinc oxide @ graphene is used in the first esterification reaction in an amount of 1 to 10% by mass of the terephthalic acid. Further, the usage amount of the zinc oxide @ graphene is 3-8% of the mass of the terephthalic acid.
According to some embodiments of the invention, the first esterification reaction is carried out at a temperature of 200 to 250 ℃ and at a pressure of 0.5 to 1MPa.
According to some embodiments of the invention, the first catalyst is used in an amount of 5 to 50ppm in the first esterification reaction.
According to some embodiments of the invention, the first stabilizer is used in an amount of 50 to 300ppm in the first esterification reaction.
According to some embodiments of the invention, the degree of polymerization of the first prepolymer is 3 to 8. Wherein, the polymerization degree can be calculated by detecting the water yield of the reaction, and when the actually measured water yield is close to the theoretical water yield, the reaction is regarded as reaching the end point. It is also possible to use gas or liquid chromatography for the determination of the ester content or gel permeation chromatography for the determination of the degree of polymerization, but these procedures are more inconvenient and do not facilitate monitoring of the reaction progress.
According to some embodiments of the invention, the molar ratio of adipic acid to butanediol in the second esterification reaction is 1.2 to 2.
According to some embodiments of the invention, the temperature of the second esterification reaction is 200 to 250 ℃ and the pressure is 0.5 to 1MPa.
According to some embodiments of the invention, the second catalyst is used in an amount of 5 to 50ppm in the second esterification reaction.
According to some embodiments of the invention, the second stabilizer is used in an amount of 60 to 400ppm in the second esterification reaction.
According to some embodiments of the invention, the degree of polymerization of the second prepolymer is 3 to 8. Further, the degree of polymerization of the second prepolymer is 3 to 5.
According to some embodiments of the invention, the molar ratio of terephthalic acid in the first prepolymer to adipic acid in the second prepolymer used in the third esterification reaction is from 1.3 to 1.5, further from 1.3 to 1.4.
According to some embodiments of the invention, the temperature of the third esterification reaction is 235 to 250 ℃ and the pressure is 0.4 to 0.6MPa. Further, the time of the third esterification reaction is 1.5-3h. Further, the measured water yield at the end of the third esterification reaction reached 97.5% or more of the theoretical water yield.
According to another aspect of the present invention, there is provided a degradable polybutylene adipate terephthalate pellet prepared by the above-mentioned preparation method.
According to some embodiments of the present invention, the degradable polybutylene adipate terephthalate chip has a molar ratio of terephthalic acid to adipic acid monomer of 1.3 to 1.5, further 1.3 to 1.4. It has the advantages of high strength, high toughness, complete degradation, etc.
The invention also provides application of the degradable polybutylene adipate terephthalate slice prepared by the preparation method in preparing a film product or an injection molding product. The film product includes but is not limited to agricultural mulching film, packaging film and plastic bag. The injection molded article may be disposable tableware.
According to some embodiments of the invention, the film article is made using an extrusion blow molding process.
According to some embodiments of the invention, further comprising stretching the film obtained by extrusion blow molding. In the stretching process, the graphene sheet layer and the microcrystal region are oriented, so that the tensile strength and the barrier property are improved.
According to some embodiments of the invention, the stretching comprises machine direction stretching at a stretch ratio of 2:1 or greater.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, which are illustrated by way of example only and not by way of limitation.
In the following examples, graphene oxide is a single layer of graphene oxide, which is available from Nanjing Xiancheng nanomaterial science and technology Co., ltd., and has a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2nm. The first catalyst and the second catalyst are tetrabutyl titanate. The first stabilizer is triphenyl phosphate and the second stabilizer is pentaerythritol phosphate. The raw materials used are all conventional products on the market, unless otherwise specified.
Example 1
The embodiment provides a preparation method of degradable polybutylene adipate terephthalate, which comprises the following specific steps:
adding graphene oxide into 50% V/V ethanol water solution, and performing ultrasonic treatment at 100W and 25Hz for 2h to obtain dispersion.
And adding zinc acetate into the dispersion liquid to ensure that the mass ratio of zinc in the zinc acetate to the graphene oxide is 5:1.
Adjusting the pH value to be neutral, heating to 90 ℃, keeping the temperature constant for 12h, adding hydrazine hydrate (the weight ratio of hydrazine hydrate: graphene = 0.6;
mixing terephthalic acid, butanediol, a first catalyst, a first stabilizer and zinc oxide @ graphene, and performing a first esterification reaction at 240 ℃ and 0.8MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.4, the dosage of the first catalyst is 30ppm, the dosage of the first stabilizer is 150ppm, and the mass of zinc oxide @ graphene is 6% of that of terephthalic acid; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butylene terephthalate), the water yield is monitored by a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and the reaction is regarded as reaching the end point.
Mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction at 245 ℃ and 0.9MPa to obtain a second prepolymer; wherein the molar ratio of adipic acid to butanediol is 1.2, the dosage of the second catalyst is 30ppm, and the dosage of the second stabilizer is 200ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of butanediol adipate), monitoring the water yield by using a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and regarding the reaction as reaching the end point.
And (2) mixing the first prepolymer with the second prepolymer, wherein the molar ratio of the used terephthalic acid to the used adipic acid is 1.35.
Example 2
The embodiment provides a preparation method of degradable polybutylene terephthalate adipate, which comprises the following specific steps:
adding graphene oxide into 50% V/V ethanol water solution, and performing ultrasonic treatment at 100W and 25Hz for 2h to obtain dispersion.
And adding zinc acetate into the dispersion liquid, so that the mass ratio of zinc in the zinc acetate to the graphene oxide is 3:1.
Adjusting the pH value to be neutral, heating to 90 ℃, keeping the temperature constant for 12h, adding hydrazine hydrate (the weight ratio of hydrazine hydrate: graphene = 0.8;
mixing terephthalic acid, butanediol, a first catalyst, a first stabilizer and zinc oxide @ graphene, and performing a first esterification reaction at 220 ℃ and 0.8MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.4, the dosage of the first catalyst is 30ppm, the dosage of the first stabilizer is 150ppm, and the mass of zinc oxide @ graphene is 6% of that of terephthalic acid; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butylene terephthalate), the water yield is monitored by a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and the reaction is regarded as reaching the end point.
Mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction at 235 ℃ and 0.7MPa to obtain a second prepolymer; wherein the molar ratio of adipic acid to butanediol is 1.2, the dosage of the second catalyst is 30ppm, and the dosage of the second stabilizer is 200ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of butanediol adipate), monitoring the water yield by using a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and regarding the reaction as reaching the end point.
And mixing the first prepolymer with the second prepolymer, wherein the molar ratio of the used terephthalic acid to the used adipic acid is 1.35, reacting for more than 2 hours at 250 ℃ and under 0.6MPa, and actually measuring the water yield to be more than 97.5 percent of the theoretical water yield to obtain the degradable polybutylene adipate-terephthalate chip.
Comparative example 1 (without addition of graphene oxide)
The comparative example provides a preparation method of degradable polybutylene terephthalate adipate, which comprises the following specific steps:
adding zinc acetate into 50% V/V ethanol water solution, adjusting pH to neutral, heating to 90 deg.C, maintaining the temperature for 12h, separating solid phase, and calcining at 250 deg.C under nitrogen atmosphere for 3h to obtain zinc oxide;
mixing terephthalic acid, butanediol, a first catalyst, a first stabilizer and zinc oxide, and performing a first esterification reaction at 240 ℃ and 0.8MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.4, the dosage of the first catalyst is 30ppm, the dosage of the first stabilizer is 150ppm, and the mass of zinc oxide is 5.2% of that of terephthalic acid; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butylene terephthalate), the water yield is monitored by a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and the reaction is regarded as reaching the end point.
Mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction at 245 ℃ and 0.9MPa to obtain a second prepolymer; wherein the molar ratio of adipic acid to butanediol is 1.2, the dosage of the second catalyst is 30ppm, and the dosage of the second stabilizer is 200ppm; when the reaction reaches the target polymerization degree of 3 (the number of chain links of butanediol adipate), monitoring the water yield by using a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and regarding that the reaction reaches the end point.
And mixing the first prepolymer with the second prepolymer, wherein the molar ratio of the used terephthalic acid to the used adipic acid is 1.35, reacting for more than 2 hours at 240 ℃ and 0.4MPa, and actually measuring the water yield to be more than 97.5 percent of the theoretical water yield to obtain the degradable polybutylene adipate terephthalate chip.
COMPARATIVE EXAMPLE 2 (without zinc oxide)
The comparative example provides a preparation method of degradable polybutylene adipate terephthalate, which comprises the following specific steps:
adding graphene oxide into 50% V/V ethanol water solution, and performing ultrasonic treatment at 100W and 25Hz for 2h to obtain dispersion.
Adding hydrazine hydrate (the weight ratio of hydrazine hydrate: graphene = 0.6).
Mixing terephthalic acid, butanediol, a first catalyst, a first stabilizer and graphene, and performing a first esterification reaction at 240 ℃ and 0.8MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.4, the dosage of the first catalyst is 30ppm, the dosage of the first stabilizer is 150ppm, and the mass of graphene is 0.8% of that of terephthalic acid; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butylene terephthalate), the water yield is monitored by a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and the reaction is regarded as reaching the end point.
Mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction at 245 ℃ and 0.9MPa to obtain a second prepolymer; wherein the molar ratio of adipic acid to butanediol is 1.2, the dosage of the second catalyst is 30ppm, and the dosage of the second stabilizer is 200ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of butanediol adipate), monitoring the water yield by using a Karl Fischer moisture tester until the actually measured water yield reaches more than 99 percent of the theoretical water yield, and regarding the reaction as reaching the end point.
And mixing the first prepolymer with the second prepolymer, wherein the molar ratio of the used terephthalic acid to the used adipic acid is 1.35, reacting for more than 2 hours at 240 ℃ and 0.4MPa, and actually measuring the water yield to be more than 97.5 percent of the theoretical water yield to obtain the degradable polybutylene adipate terephthalate chip.
Comparative example 3 (one-step polymerization)
Compared with the example 1, the difference is that the stepwise esterification is changed into the following one-step esterification, and the rest is unchanged: mixing terephthalic acid, adipic acid, butanediol, a first catalyst, a second catalyst, a first stabilizer, a second stabilizer and zinc oxide @ graphene, and reacting at 240 ℃ and 0.4MPa for 2.5 hours to obtain degradable polybutylene adipate terephthalate chips, wherein the total using amount of all the components is the same as that in example 1.
Test example
The test paper is used for testing tensile property, water vapor transmission rate and degradation property.
1. Tensile Properties
The final products of each example and comparative example were dried to constant weight at 90 ℃ and subjected to single screw extrusion film blowing at a draw ratio of 3:1 to produce a film having a thickness of 0.04 mm. The samples were taken in the longitudinal direction (tensile direction, MD) and specimens were prepared from type II specimens as specified in GB/T1040 at a tensile speed of 50mm/min. The test was repeated for 5 splines and the average was taken. Among them, in comparative example 2, since graphene is seriously agglomerated,
2. water vapor transmission rate
The final products of example 1, example 2, comparative example 1 and comparative example 3 were tested and the sample preparation methods refer to tensile property testing. The water vapor transmission capacity is tested according to GB/T1037-2021, the test method is a weight increasing method, and the test conditions are as follows: 23 ℃ plus or minus 0.5 ℃ and relative humidity of 50 percent plus or minus 2 percent.
3. Degradation Properties
The final products of example 1, example 2, comparative example 1 and comparative example 3 were tested and the sample preparation methods refer to tensile property testing. Carrying out accelerated aging in an aging box: UVA-340 irradiation, 0.8W/m 2 And stopping for 2h every time the irradiation is carried out for 2h, and circulating in such a way, and accumulating the irradiation for 50h. And then natural degradation is carried out: the film samples after accelerated aging were spread on the wet soil surface and left open for 45 days at the beginning of 6 months. Weighing an initial mass M 0 And mass after accelerated aging and natural aging, respectively, is M 1 、M 2 Calculate M 1 、M 2 Occupy M 0 The mass percent of (A) is the mass retention rate of the corresponding aging stage. Continuing natural aging, the samples of example 1, example 2, comparative example 3 were all able to be aged for a total of three monthsThe film of comparative example 1 is degraded into fragments in a natural aging period, and degradation holes or cracks appear in the film, but the main body of the film still has a continuous structure because the content of terephthalic acid is relatively high, and zinc oxide which mainly plays a role of an ultraviolet absorber is added alone, so that sufficient degradation is difficult to realize.
The relevant test results are shown in tables 1 and 2.
TABLE 1
Figure BDA0003814143350000081
TABLE 2
Figure BDA0003814143350000082
It can be seen that the PBAT prepared in the embodiment has excellent mechanical properties and low water vapor transmission rate, shows more excellent aging resistance in an accelerated aging stage, and shows more excellent degradability in a subsequent natural aging stage, so that the phenomenon that the service performance is reduced too fast due to too fast degradation in the initial use stage of the material is avoided, the material can be degraded sufficiently and quickly in the later use stage, the service performance and the environmental friendliness are well considered, and the daily use requirement can be well met.
The tensile strength (MD) of the synthesized PBAT material reaches 29.7MPa, while the tensile strength of the commercially available PBAT is generally below 20MPa, and the breaking elongation of the PBAT material is close to that of the commercially available PBAT. Therefore, the PBAT material with excellent comprehensive performance is prepared by the in-situ method, and compared with the method for directly purchasing PBAT raw materials for modification, the PBAT material has the advantages of lower material cost, excellent comprehensive performance and simple preparation process, and is beneficial to expanding the industrial application range of PBAT.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.

Claims (10)

1. A preparation method of degradable polybutylene adipate terephthalate is characterized by comprising the following steps: the method comprises the following steps:
dispersing graphene oxide in a first solvent to prepare a dispersion liquid;
adding zinc acetate into the dispersion, adjusting the pH value to be neutral, performing hydrothermal treatment, adding a reducing agent for reaction, separating a solid phase, and calcining in an inert atmosphere to obtain zinc oxide @ graphene;
mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer with the zinc oxide @ graphene, and carrying out a first esterification reaction to obtain a first prepolymer;
mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and carrying out a second esterification reaction to obtain a second prepolymer;
and mixing the first prepolymer and the second prepolymer, and carrying out a third esterification reaction to obtain the degradable polybutylene adipate-terephthalate slice.
2. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: the mass ratio of zinc in the zinc acetate to the graphene oxide is 1-10.
3. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: in the first esterification reaction, the amount of the zinc oxide @ graphene is 1-10% of the mass of the terephthalic acid.
4. The method for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: the temperature of the hydrothermal treatment is 60-95 ℃; further, the time of the hydrothermal treatment is 5-20h.
5. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: the first catalyst and the second catalyst are independently selected from tetrabutyl titanate, tetra-n-ethyl titanate and tetra-isopropyl titanate.
6. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: the first stabilizer and the second stabilizer are independently selected from triphenyl phosphate, pentaerythritol phosphate and ethyl phosphate; further, the first stabilizer is triphenyl phosphate, and the second stabilizer is pentaerythritol phosphate.
7. The method for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: the degree of polymerization of the first prepolymer and/or the second prepolymer is independently 3 to 8.
8. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein: in the third esterification reaction, the molar ratio of the terephthalic acid in the first prepolymer to the adipic acid in the second prepolymer is 1.3-1.5.
9. The process for producing a degradable polybutylene adipate terephthalate according to claim 1, wherein:
the temperature of the first esterification reaction is 200-250 ℃, and the pressure is 0.5-1MPa; and/or the presence of a gas in the atmosphere,
the temperature of the second esterification reaction is 200-250 ℃, and the pressure is 0.5-1MPa; and/or the presence of a gas in the gas,
the temperature of the third esterification reaction is 235-250 ℃, and the pressure is 0.4-0.6MPa.
10. Use of the degradable polybutylene adipate terephthalate pellet prepared by the preparation method according to any one of claims 1 to 9 in the preparation of a film product or an injection molded product.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103252227A (en) * 2013-04-27 2013-08-21 北京交通大学 Tetrapod-like zinc oxide/graphene composite material and preparation method thereof
WO2021041493A1 (en) * 2019-08-26 2021-03-04 Xg Sciences, Inc. Graphene-polymer matrix composite materials with controlled intrinsic viscosity and preparation method thereof
CN112876710A (en) * 2021-01-18 2021-06-01 山东阜坤新材料有限公司 Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof
CN113122952A (en) * 2021-03-30 2021-07-16 新疆蓝山屯河化工股份有限公司 PBAT fiber and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103252227A (en) * 2013-04-27 2013-08-21 北京交通大学 Tetrapod-like zinc oxide/graphene composite material and preparation method thereof
WO2021041493A1 (en) * 2019-08-26 2021-03-04 Xg Sciences, Inc. Graphene-polymer matrix composite materials with controlled intrinsic viscosity and preparation method thereof
CN112876710A (en) * 2021-01-18 2021-06-01 山东阜坤新材料有限公司 Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof
CN113122952A (en) * 2021-03-30 2021-07-16 新疆蓝山屯河化工股份有限公司 PBAT fiber and preparation method thereof

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