CN115710410A - Preparation method and application of polybutylene adipate-terephthalate material - Google Patents
Preparation method and application of polybutylene adipate-terephthalate material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a polybutylene adipate terephthalate material, which comprises the following steps: dispersing organic modified montmorillonite in water to prepare a suspension, adding a lignosulfonate solution and maleic anhydride, adjusting the pH to be alkaline, heating for reaction, dropwise adding a reaction solution into a hydrochloric acid solution under the stirring action, adjusting the pH to be neutral, adding nano zinc oxide, and performing ultrasonic treatment to obtain a composite filler; mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, 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, the second prepolymer, the composite filler and trimethylolpropane, and reacting to obtain the polybutylene adipate terephthalate material. The prepared material has excellent water resistance, aging resistance and light transmittance, and better strength and toughness, and can be used for preparing films or injection molding products.
Description
Technical Field
The invention relates to the technical field of polyester materials, in particular to a preparation method and application of a polybutylene adipate-terephthalate material.
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 has degradability and is a green environment-friendly material with development prospect. However, the existing PBAT has poor barrier property, water vapor is easy to permeate, and the use requirements in the fields of food preservation, agricultural mulching films and the like are difficult to meet. By adding the layered fillers such as montmorillonite and mica powder, the transmission path of water vapor can be prolonged to a certain extent, so that the purpose of blocking the transmission of water vapor is achieved, but the light transmittance or the mechanical property is easily influenced, so that the existing method is easy to cause the obvious reduction of the performance in other aspects when the performance defect that the PBAT has insufficient blocking property is solved, and the application limitation of the PBAT is difficult to overcome fundamentally. In addition, the cost of the existing PBAT is high, and the cost is also an important factor limiting the industrialization application of the PBAT.
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 a polybutylene adipate terephthalate (PBAT) material, and the prepared PBAT has excellent water resistance, aging resistance and light transmittance, and better strength and toughness.
The invention also provides a polybutylene adipate terephthalate material prepared by the preparation method.
The invention also provides application of the polybutylene adipate terephthalate material.
The preparation method of the polybutylene adipate terephthalate material according to the first aspect of the invention comprises the following steps:
dispersing organic modified montmorillonite in water to prepare suspension;
adding a lignosulfonate solution and maleic anhydride into the suspension, adjusting the pH value to be alkaline, heating for reaction, dropwise adding the reaction solution into a hydrochloric acid solution under the stirring effect, adjusting the pH value to be neutral, adding nano zinc oxide, performing ultrasonic treatment, and performing solid-liquid separation to obtain a composite filler;
mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, 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, the second prepolymer and the composite filler with trimethylolpropane to perform a third esterification reaction to obtain the polybutylene adipate-terephthalate material.
The preparation method of the polybutylene adipate terephthalate material provided by the embodiment of the invention has at least the following beneficial effects:
aromatic rings, phenolic hydroxyl groups and the like in lignin have good absorption capacity on ultraviolet radiation, maleic acid is generated after maleic anhydride is hydrolyzed, lignosulfonate is subjected to graft modification, the compatibility of lignin and polyester is improved, meanwhile, the improved lignin is more easily entangled with organic chain segments on the surface of montmorillonite, and lignin is favorably intercalated between montmorillonite layers or coated on the outer surface of montmorillonite layers. And when the reaction solution is dripped into a hydrochloric acid solution subsequently, the lignin is separated out in a form of particles and then is coated on the surface of the montmorillonite in situ. The method improves the surface area of lignin, improves the interlayer spacing of montmorillonite by in-situ coating of the lignin on the montmorillonite, and is beneficial to doping of nano zinc oxide and intercalation of polyester molecular chains.
The montmorillonite is compositely doped with the modified lignin and the zinc oxide, so that a synergistic ultraviolet ray absorption and shielding effect is generated, meanwhile, the interlayer spacing of the montmorillonite is enlarged, light penetration is facilitated, the adverse effect on light transmittance caused by the doped montmorillonite is reduced, and better mechanical property and water resistance are ensured.
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, and the compactness is improved. In the last stage of esterification reaction, polyester molecular chain intercalation and the function of a crosslinking point provided by trimethylolpropane are utilized, and functional groups (including carboxyl generated by hydrolysis of maleic anhydride, hydroxyl in lignin and the like) in the composite filler can also participate in the esterification reaction, so that a large-scale network structure wrapping the composite filler is formed, the compactness is further improved, and the remarkable improvement of the mechanical property and the water resistance is realized.
According to some embodiments of the invention, the suspension has a solid to liquid ratio of 10 to 20g/L.
According to some embodiments of the invention, the sonication is performed during the preparation of the suspension. Further, the power of the ultrasonic treatment is 75-150W, the frequency is 25-35kHz, and the time of the ultrasonic treatment is 0.5-2h.
According to some embodiments of the invention, the lignosulfonate solution is sodium lignosulfonate.
According to some embodiments of the invention, the concentration of the lignosulfonate solution is between 20 and 40g/L.
According to some embodiments of the invention, the mass ratio of the organically modified montmorillonite in the suspension to the lignosulfonate in the lignosulfonate solution is 1:0.8-1.2.
According to some embodiments of the invention, the mass ratio of the maleic anhydride to the lignosulfonate in the lignosulfonate solution is 0.4-0.8.
According to some embodiments of the invention, the adjusting the pH to alkaline is adjusting the pH to 10 to 11.
According to some embodiments of the invention, the temperature of the heating reaction is 60 to 70 ℃, and further, the time of the heating reaction is 2.5 to 4.5 hours.
According to some embodiments of the invention, the rotation speed of the stirring is 100-300rpm.
According to some embodiments of the invention, the hydrochloric acid solution has a concentration of 0.01 to 0.1mol/L.
According to some embodiments of the invention, the nano zinc oxide has an average particle size of 50 to 100nm.
According to some embodiments of the invention, the weight ratio of the nano zinc oxide to the lignosulfonate solution is 1.
According to some embodiments of the present invention, the power of the ultrasonic treatment after adding the nano zinc oxide is 50-100W, the frequency is 25-40kHz, and further, the ultrasonic treatment time is 0.5-2h.
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 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. The pentaerythritol phosphate has good stabilizing effect on adipic acid, and the two stabilizers are matched, so that a high-molecular-weight final product can be obtained more easily.
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 first esterification reaction is at a temperature of 200 to 250 ℃ and 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. Of course, gas or liquid chromatography can be used to detect the ester content, or gel permeation chromatography can be used to detect the degree of polymerization, but these operations are more inconvenient and not conducive to monitoring the progress of the reaction.
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.
According to some embodiments of the present invention, the molar ratio of the amount of terephthalic acid in the first prepolymer to the amount of adipic acid in the second prepolymer in the third esterification reaction is in the range of 1.1 to 1.2.
According to some embodiments of the present invention, in the third esterification reaction, the amount of the composite filler is 1.5 to 5% of the total mass of the first prepolymer and the second prepolymer, and further, the amount of the composite filler is 2 to 4% of the total mass of the first prepolymer and the second prepolymer.
According to some embodiments of the present invention, in the third esterification reaction, the mass of the trimethylolpropane is 0.5 to 3% of the total mass of the first prepolymer and the second prepolymer, and further, the mass of the trimethylolpropane is 1 to 2% of the total mass of the first prepolymer and the second prepolymer.
According to some embodiments of the invention, the temperature of the third esterification reaction is between 230 ℃ and 240 ℃ and the pressure is between 0.1 MPa and 0.5MPa. Further, the time of the third esterification reaction is 2-4h. 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 an embodiment of another aspect of the present invention, there is provided a polybutylene adipate terephthalate material prepared by the above-described preparation method.
According to some embodiments of the invention, the polybutylene adipate terephthalate material has a molar ratio of phthalic acid to adipic acid monomer of 1.1 to 1.2.
The invention also provides application of the polybutylene adipate terephthalate material prepared by the preparation method in preparing film products or injection-molded products. 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 montmorillonite layer and the microcrystal area are oriented, so that the tensile strength and the barrier property are improved.
According to some embodiments of the invention, the stretching comprises longitudinal stretching at a stretch ratio of 2 to 3.
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 the practice of the invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for illustration only and is not to be construed as limiting the invention.
In the following examples, the organically modified montmorillonite is fenghong DK32B. The average grain diameter of the nano zinc oxide is 50nm. 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 are all conventional products on the market if not specifically indicated.
Example 1
The embodiment provides a preparation method of a polybutylene adipate terephthalate material, which comprises the following specific steps:
dispersing organic modified montmorillonite in water at solid-to-liquid ratio of 15g/L, and performing ultrasonic treatment at 100W and 30kHz for 1.5h to obtain suspension.
Dissolving sodium lignosulfonate in distilled water to prepare a 30g/L sodium lignosulfonate solution, adding the sodium lignosulfonate solution into the suspension, controlling the weight ratio of the organic modified montmorillonite to the sodium lignosulfonate to be 1.
Preparing 0.03mol/L hydrochloric acid solution, starting stirring until the rotating speed is 150rpm, dropwise adding the obtained reaction solution into the hydrochloric acid solution, adjusting the pH value to be neutral, adding nano zinc oxide to ensure that the weight ratio of sodium lignosulfonate to nano zinc oxide is 7, carrying out ultrasonic treatment for 1 hour at 50W and 25kHz, filtering, washing and drying to obtain the composite filler.
Mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, and carrying out a first esterification reaction at 235 ℃ and 0.7MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.3, the dosage of the first catalyst is 30ppm, and the dosage of the first stabilizer is 150ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butanediol phthalate), 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.
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.
Mixing the first prepolymer, the second prepolymer, the composite filler and trimethylolpropane, reacting for more than 3 hours at 235 ℃ and 0.3MPa, wherein the actually measured water yield reaches more than 97.5 percent of the theoretical water yield, so as to obtain the polybutylene adipate terephthalate material; wherein the molar ratio of the terephthalic acid in the first prepolymer to the adipic acid in the second prepolymer is 1.2, the dosage of the composite filler is 3% of the total mass of the first prepolymer and the second prepolymer, and the dosage of the trimethylolpropane is 1% of the total mass of the first prepolymer and the second prepolymer.
Example 2
The embodiment provides a preparation method of a polybutylene adipate terephthalate material, which comprises the following specific steps:
dispersing organic modified montmorillonite in water according to a solid-to-liquid ratio of 15g/L, and performing ultrasonic treatment at 100W and 30kHz for 1.5h to prepare suspension.
Dissolving sodium lignosulfonate in distilled water to prepare a 30g/L sodium lignosulfonate solution, adding the sodium lignosulfonate solution into the suspension, controlling the weight ratio of the organically modified montmorillonite to the sodium lignosulfonate to be 1.
Preparing 0.03mol/L hydrochloric acid solution, starting stirring until the rotating speed is 150rpm, dropwise adding the obtained reaction solution into the hydrochloric acid solution, adjusting the pH value to be neutral, adding nano zinc oxide to ensure that the weight ratio of sodium lignosulfonate to nano zinc oxide is 8, carrying out ultrasonic treatment for 1h at 50W and 25kHz, filtering, washing and drying to obtain the composite filler.
Mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, 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 1.3, the dosage of the first catalyst is 30ppm, and the dosage of the first stabilizer is 150ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butanediol phthalate), 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.
Mixing adipic acid, butanediol, a second catalyst and a second stabilizer, and performing 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.
Mixing the first prepolymer, the second prepolymer, the composite filler and trimethylolpropane, reacting for more than 3 hours at 240 ℃ under 0.5MPa, wherein the actually measured water yield reaches more than 97.5 percent of the theoretical water yield, so as to obtain the polybutylene adipate terephthalate material; wherein the molar ratio of the consumption of the terephthalic acid in the first prepolymer to the consumption of the adipic acid in the second prepolymer is 1.2.
Comparative example 1 (without nano-zinc oxide)
The comparative example provides a preparation method of a polybutylene adipate terephthalate material, which comprises the following specific steps:
dispersing organic modified montmorillonite in water at solid-to-liquid ratio of 15g/L, and performing ultrasonic treatment at 100W and 30kHz for 1.5h to obtain suspension.
Dissolving sodium lignosulfonate in distilled water to prepare a 30g/L sodium lignosulfonate solution, adding the sodium lignosulfonate solution into the suspension, controlling the weight ratio of the organic modified montmorillonite to the sodium lignosulfonate to be 1.
Preparing 0.03mol/L hydrochloric acid solution, starting stirring until the rotating speed is 150rpm, dropwise adding the obtained reaction solution into the hydrochloric acid solution, adjusting the pH value to be neutral, filtering, washing and drying to obtain the composite filler.
Mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, and carrying out a first esterification reaction at 235 ℃ and 0.7MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.3, the dosage of the first catalyst is 30ppm, and the dosage of the first stabilizer is 150ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butanediol phthalate), 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.
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.
Mixing the first prepolymer, the second prepolymer and the composite filler with trimethylolpropane, reacting for more than 3 hours at 235 ℃ and 0.3MPa, and actually measuring the water yield to be more than 97.5 percent of the theoretical water yield to obtain a polybutylene adipate-terephthalate material; wherein the molar ratio of the consumption of the terephthalic acid in the first prepolymer to the consumption of the adipic acid in the second prepolymer is 1.2.
Comparative example 2 (without maleic anhydride)
The comparative example provides a preparation method of a polybutylene adipate terephthalate material, which comprises the following specific steps:
dispersing organic modified montmorillonite in water at solid-to-liquid ratio of 15g/L, and performing ultrasonic treatment at 100W and 30kHz for 1.5h to obtain suspension.
Dissolving sodium lignosulfonate in distilled water to prepare a 30g/L sodium lignosulfonate solution, adding the sodium lignosulfonate solution into the suspension, and controlling the weight ratio of the organic modified montmorillonite to the sodium lignosulfonate to be 1.
Preparing 0.03mol/L hydrochloric acid solution, starting stirring until the rotating speed is 150rpm, dropwise adding the mixed solution obtained in the previous step into the hydrochloric acid solution, adjusting the pH value to be neutral, adding nano zinc oxide to ensure that the weight ratio of sodium lignosulfonate to nano zinc oxide is 7, performing ultrasonic treatment for 1h at 50W and 25kHz, filtering, washing and drying to obtain the composite filler.
Mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, and performing a first esterification reaction at 235 ℃ and 0.7MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.3, the dosage of the first catalyst is 30ppm, and the dosage of the first stabilizer is 150ppm; when the reaction reaches the target polymerization degree of 3 (the number of chain links of the butanediol phthalate), 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.
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.
Mixing the first prepolymer, the second prepolymer, the composite filler and trimethylolpropane, reacting for more than 3 hours at 235 ℃ and 0.3MPa, wherein the actually measured water yield reaches more than 97.5 percent of the theoretical water yield, so as to obtain the polybutylene adipate terephthalate material; wherein the molar ratio of the terephthalic acid in the first prepolymer to the adipic acid in the second prepolymer is 1.2, the dosage of the composite filler is 3% of the total mass of the first prepolymer and the second prepolymer, and the dosage of the trimethylolpropane is 1% of the total mass of the first prepolymer and the second prepolymer.
Comparative example 3 (No trimethylolpropane)
The embodiment provides a preparation method of a polybutylene adipate terephthalate material, which comprises the following specific steps:
dispersing organic modified montmorillonite in water at solid-to-liquid ratio of 15g/L, and performing ultrasonic treatment at 100W and 30kHz for 1.5h to obtain suspension.
Dissolving sodium lignosulfonate in distilled water to prepare a 30g/L sodium lignosulfonate solution, adding the sodium lignosulfonate solution into the suspension, controlling the weight ratio of the organic modified montmorillonite to the sodium lignosulfonate to be 1.
Preparing 0.03mol/L hydrochloric acid solution, starting stirring until the rotating speed is 150rpm, dropwise adding the obtained reaction solution into the hydrochloric acid solution, adjusting the pH value to be neutral, adding nano zinc oxide to ensure that the weight ratio of sodium lignosulfonate to nano zinc oxide is 7, carrying out ultrasonic treatment for 1h at 50W and 25kHz, filtering, washing and drying to obtain the composite filler.
Mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, and carrying out a first esterification reaction at 235 ℃ and 0.7MPa to obtain a first prepolymer; wherein the molar ratio of terephthalic acid to butanediol is 1.3, the dosage of the first catalyst is 30ppm, and the dosage of the first stabilizer is 150ppm; when the reaction is carried out until the target polymerization degree is 3 (the number of chain links of the butanediol phthalate), 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.
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.
Mixing the first prepolymer, the second prepolymer and the composite filler, reacting for more than 3 hours at 235 ℃ and 0.3MPa, wherein the actually measured water yield reaches more than 97.5 percent of the theoretical water yield, so as to obtain the polybutylene adipate-terephthalate material; wherein the molar ratio of the consumption of the terephthalic acid in the first prepolymer to the consumption of the adipic acid in the second prepolymer is 1.2.
Test example
Tensile properties, water vapor transmission rate, light transmittance and degradation properties were tested for each of the examples and comparative examples.
1. Tensile Properties
The final products of the respective examples and comparative examples were dried at 90 ℃ to a constant weight, subjected to single-screw extrusion film blowing, and stretched at a draw ratio of 2. The sample was taken in the longitudinal direction (stretching direction, MD) and a specimen of type II specified in GB/T1040 was prepared at a stretching speed of 50mm/min. The test was repeated for 5 splines and the average was taken.
2. Light transmittance
The film with the thickness of 0.015mm is prepared by adopting a tape casting method and is tested by an ultraviolet-visible spectrophotometer.
3. Water vapor transmission rate
The sample is tested for the same tensile property, the water vapor transmission capacity is tested according to GB/T1037-2021, the test method is a weighting method, and the test conditions are as follows: 23 +/-0.5 ℃ and relative humidity of 50% +/-2%.
4. Degradation Properties
And (3) testing the same tensile property of the sample, and carrying out accelerated aging in an aging box: UVA-340 irradiation, 0.8W/m2, stopping for 2 hours every 2 hours of irradiation, and circulating the way, and accumulating the irradiation for 40 hours. Weighing an initial mass M 0 And mass M after accelerated aging 1 . Calculating the mass M of the sample after accelerated ageing is completed relative to the initial mass 0 Mass loss (M) of 0 -M 1 ) Calculating the mass loss in M 0 The mass percentage of (b) is the degradation rate. And burying the film after accelerated aging in loose and moist soil, and naturally degrading for four months to realize complete biodegradation of each group of samples.
TABLE 1
TABLE 2
The test results are shown in tables 1 and 2. It can be seen that the embodiments can obtain obviously better water vapor transmission rate and light transmittance on the basis of ensuring excellent mechanical properties, and solve the problem that the existing materials are difficult to take into account the above properties in all aspects. Moreover, the PBAT material is prepared by adopting an in-situ synthesis method, the process is simple, the tensile strength of the obtained material is obviously higher than that of the conventional PBAT (generally below 20 MPa) sold in the market, the elongation at break is equivalent, and compared with a method for directly purchasing PBAT raw materials for modification, the PBAT material has the advantages of lower cost, excellent comprehensive performance and contribution to expanding the industrial application range of the PBAT.
As can be seen from comparison of comparative example 1 with example 1, the degradation rate in the accelerated aging stage is too fast without adding zinc oxide, which affects the service life of the material.
As can be seen from comparison of the comparative example 2 and the example 1, the mechanical property, the light transmittance, the water vapor transmission rate and the degradation rate are obviously affected without adding maleic anhydride, and the maleic anhydride modification is probably more beneficial to lignin intercalation, the dispersion uniformity of the lignin is improved, the specific surface area of the lignin is increased, meanwhile, the interlayer spacing of montmorillonite is enlarged, and the compounding of the lignin and zinc oxide is facilitated, so that a better anti-photoaging effect is achieved. On the other hand, the interlayer spacing of the montmorillonite is increased, which is beneficial to the intercalation of polyester molecules, thereby constructing a more efficient barrier and reinforcing network.
As can be seen from comparison of comparative example 3 and example 1, trihydroxypropane can significantly improve mechanical properties and reduce water vapor transmission rate. Probably because the trihydroxy propane provides cross-linking points, a large-scale network structure is formed, the dispersion form of the montmorillonite can be fixed, and the compactness is improved.
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 without departing from the gist of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A preparation method of polybutylene adipate terephthalate material is characterized by comprising the following steps: the method comprises the following steps:
dispersing organic modified montmorillonite in water to prepare suspension;
adding a lignosulfonate solution and maleic anhydride into the suspension, adjusting the pH value to be alkaline, heating for reaction, dropwise adding a reaction solution into a hydrochloric acid solution under the stirring action, adjusting the pH value to be neutral, adding nano zinc oxide, performing ultrasonic treatment, and performing solid-liquid separation to obtain a composite filler;
mixing terephthalic acid, butanediol, a first catalyst and a first stabilizer, and performing 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, the second prepolymer and the composite filler with trimethylolpropane to perform a third esterification reaction to obtain the polybutylene adipate terephthalate material.
2. The method of preparing polybutylene adipate terephthalate material according to claim 1, wherein the method comprises the following steps: the mass ratio of the organic modified montmorillonite in the suspension to the lignosulfonate in the lignosulfonate solution is 1:0.8-1.2; further, the mass ratio of the maleic anhydride to the lignosulfonate in the lignosulfonate solution is 0.4-0.8; further, the weight ratio of the nano zinc oxide to the lignosulfonate solution is 1.
3. The method of preparing polybutylene adipate-terephthalate material according to claim 1, wherein the method comprises the following steps: the temperature of the heating reaction is 60-70 ℃; further, the pH is adjusted to be alkaline, namely the pH is adjusted to be 10-11.
4. The method of preparing polybutylene adipate terephthalate material according to claim 1, wherein the method comprises the following steps: the first catalyst and the second catalyst are independently selected from tetrabutyl titanate, tetra-n-ethyl titanate and tetra-isopropyl titanate.
5. The method of preparing polybutylene adipate terephthalate material according to claim 1, wherein the method comprises the following steps: 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.
6. The method of preparing polybutylene adipate-terephthalate material according to claim 1, wherein the method comprises the following steps: the degree of polymerization of the first prepolymer and/or the second prepolymer is independently 3 to 8.
7. The method of preparing polybutylene adipate-terephthalate material according to claim 1, wherein the method comprises the following steps: 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 1.1-1.2.
8. The method of preparing polybutylene adipate terephthalate material according to claim 1, wherein the method comprises the following steps: in the third esterification reaction, the mass of the trimethylolpropane is 0.5 to 3% of the total mass of the first prepolymer and the second prepolymer.
9. The method of preparing polybutylene adipate-terephthalate material according to claim 1, wherein the method comprises the following steps:
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 gas,
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 230-250 ℃, and the pressure is 0.4-0.6MPa.
10. Use of polybutylene adipate terephthalate material produced by the production method according to any one of claims 1 to 9 for producing a film article or an injection-molded article.
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| US20170362373A1 (en) * | 2014-12-05 | 2017-12-21 | Basf Se | Biodegradable copolyesters |
| CN105623209A (en) * | 2016-03-25 | 2016-06-01 | 江苏裕兴薄膜科技股份有限公司 | Method for preparing high-water vapor barrier polyester thin film by melt polymerization method |
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