CN116355190A - Preparation method of chelidonic acid modified PBAT degradation material - Google Patents

Preparation method of chelidonic acid modified PBAT degradation material Download PDF

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Publication number
CN116355190A
CN116355190A CN202310395966.9A CN202310395966A CN116355190A CN 116355190 A CN116355190 A CN 116355190A CN 202310395966 A CN202310395966 A CN 202310395966A CN 116355190 A CN116355190 A CN 116355190A
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reaction
pbat
esterification
bdo
chelidonic acid
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CN202310395966.9A
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于洋
张爽
葛铁军
何晓峰
刘啸凤
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

A preparation method of a chelidonic acid modified PBAT degradation material relates to a preparation method of a degradation material. According to the method, chelidonic acid is introduced into a PBAT chain segment to enable the material to have high strength. And a chelidonic acid rigid group is introduced into a PBAT molecular chain, a material rigid response mechanism is established by utilizing the steric hindrance effect of a ring structure on the rotation in a single bond of the molecular chain, and the rigidity of the PBAT is improved by introducing a rigid molecular structure into the PBAT.

Description

Preparation method of chelidonic acid modified PBAT degradation material
Technical Field
The invention relates to a preparation method of a degradation material, in particular to a preparation method of a chelidonic acid modified PBAT degradation material.
Background
Chelergic acid, formula C 7 H 4 O 6 The molecular weight was 184.1. The appearance is white crystal powder, and the chelidonine is a very important organic synthesis intermediate, and is widely applied to biochemistry, organic chemistry, pharmaceutical chemistry and the like. Furthermore, chelidonic acid is a synthetic raw material for a number of important ligands, which itself is also a very typical multidentate ligandThere is also a great deal of research interest in coordination chemistry.
PBAT, chinese name is polybutylene terephthalate-adipate, belongs to thermoplastic biodegradable plastics, is a copolymer of polybutylene adipate and polybutylene terephthalate, has the characteristics of PBA and PBT, has better ductility and elongation at break, and has better heat resistance and impact property; in addition, the material has excellent biodegradability, and is one of the most popular and most commercially available degradable materials in the research of biodegradable plastics. PBAT is a copolymer of aliphatic polyester and aromatic polyester, and combines the excellent degradation performance of aliphatic polyester and the good mechanical properties of aromatic polyester. The PBAT material can be biodegradable and compostable, so that the PBAT can resist white pollution, and the biodegradable garbage bag produced by the PBAT is a film material used when the biological waste is recovered by a biological composting garbage center, and is mainly applied to: a fully degradable packaging film; the fully degradable packaging bag comprises a shopping bag, a continuous rolling garbage bag, a pet excrement bag, an electronic product packaging bag, a food packaging bag, a mulching film and the like.
Adipic Acid (AA), also known as fatty acid, is an important organic dibasic acid with the structural formula HOOC (CH) 2 ) 4 COOH. Can generate salification reaction, esterification reaction, amidation reaction and the like, and can be polycondensed with diamine or dihydric alcohol to form high molecular polymer and the like. Adipic acid is a dicarboxylic acid with great industrial significance, and has great significance in the aspects of chemical production, organic synthesis industry, medicine, lubricant manufacturing and the like, and the yield is the second place in all dicarboxylic acids.
1, 4-Butanediol (BDO), an organic compound, molecular formula C 4 H 10 O 2 The molecular weight was 90.12. The appearance is colorless or pale yellow oily liquid. Is flammable, with a freezing point of 20.1 ℃ and a refractive index of 1.4461. Can be dissolved in methanol, ethanol, acetone, and slightly dissolved in diethyl ether. Has hygroscopicity and bitter taste, and has slightly sweet taste when being taken in. Used as solvent and moisturizer, and also used for preparing plasticizer, medicine, polyester resin, polyurethane resin, etc.
Disclosure of Invention
The invention aims to provide a preparation method of a chelidonic acid modified PBAT degradation material. According to the invention, before PBAT synthesis, the chelidonic acid is coupled with the raw material micromolecules in the raw material esterification process, and then polycondensation is carried out to obtain the high-strength degradation material PBAT, and the rigidity of the PBAT is improved due to the rigid molecular structure introduced into the PBAT.
The invention aims at realizing the following technical scheme:
a preparation method of a chelidonic acid modified PBAT degradation material, which comprises the following preparation processes:
taking terephthalic acid (PTA), adipic Acid (AA), chelidonic acid and 1, 4-Butanediol (BDO) as raw materials, and adopting a direct esterification method to respectively prepare butylene terephthalate, butylene adipate and butylene chelidonate; alkyd mole ratio 1.4:1, a step of; adding PTA and BDO into a 1L polymerization reaction kettle, and adding a catalyst tetrabutyl titanate; setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is 2 hours; adding AA and BDO into a 1L polymerization reaction kettle, and adding a catalyst tetrabutyl titanate; setting the temperature to 170 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, finishing the esterification reaction, wherein the reaction time is 2 hours; adding chelidonic acid and BDO, setting the temperature to 170 ℃, and taking the collected esterification water yield to 95% of a theoretical value as the end of the esterification reaction, wherein the reaction time is 2 hours; in the polycondensation reaction stage, butylene terephthalate, butylene adipate and chelidonic acid are put into a three-neck flask, stannous octoate is used as a catalyst, the reaction temperature is gradually increased from 200 ℃ to 250 ℃ for pre-polycondensation reaction, when the temperature reaches 250 ℃, the vacuum polycondensation is gradually carried out for 2 hours, the vacuum of the system is stopped, nitrogen is blown in for cooling, and the nitrogen is used for protecting discharge; the catalyst for normal pressure esterification reaction is tetrabutyl titanate, and the catalyst for vacuum polycondensation is stannous octoate; the PBAT is modified by chelidonic acid, so that the strength of the PBAT is improved.
The preparation method of the chelidonic acid modified PBAT degradation material comprises the following raw materials in parts by weight:
AA 131.52g；
BDO 126.16g；
PTA 149.51g；
18.41g of chelidonic acid;
tetrabutyl titanate 1.49g;
stannous octoate 2.24g.
According to the preparation method of the chelidonic acid modified PBAT degradation material, the molar ratio of BDO to (AA+PTA) is 0.45.
The molar ratio of AA to PTA is 0.88.
The invention has the advantages and effects that:
according to the invention, a chelidonic acid rigid group is introduced into a PBAT molecular chain, and a material rigid response mechanism is established by utilizing the steric hindrance effect of a ring structure on the rotation in a single bond of the molecular chain, so that the rigid PBAT is developed. The rigid molecular structure introduced in the PBAT improves the rigidity of the PBAT.
Description of the embodiments
The present invention is further described below by way of specific embodiments, but the present invention is not limited to the following examples. It will be apparent to those skilled in the art that the present invention may be suitably modified and substituted for the same components having the same effects within the scope of the present invention or without departing from the spirit and scope of the present invention, and they are all considered to be included in the scope of the present invention.
Example 1
And (3) carrying out esterification reaction under normal pressure. 149.51g PTA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of the catalyst tetrabutyl titanate was added. Setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 131.52gAA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of tetrabutyl titanate catalyst was added. Setting the temperature to 170 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 126.16g of 1, 4-butanediol and 18.41g of chelidonic acid are firstly added, and the esterification reaction is considered to be finished when the esterification water yield collected at 170 ℃ reaches 95% of the theoretical value, and the reaction time is about 2 hours.
And (3) carrying out vacuum polycondensation reaction. The product was placed in the same reactor, 2.24g of stannous octoate catalyst was added and the temperature was gradually increased to 250℃and the process was pre-polycondensed. When the temperature is raised to 250 ℃, a vacuum pump is started to slowly decompress to less than 50Pa for polycondensation, and the reaction is carried out for about 2 hours. Stopping the system vacuum, blowing nitrogen to cool, and discharging under nitrogen protection to obtain a required material sample for testing.
Example 2
And (3) carrying out esterification reaction under normal pressure. 149.51g PTA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of the catalyst tetrabutyl titanate was added. Setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 131.52gAA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of tetrabutyl titanate catalyst was added. Setting the temperature to 170 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 126.16g of 1, 4-butanediol and 18.51g of chelidonic acid are firstly added, and the esterification reaction is considered to be finished when the esterification water yield collected at 170 ℃ reaches 95% of the theoretical value, and the reaction time is about 2 hours.
And (3) carrying out vacuum polycondensation reaction. The product was placed in the same reactor, 2.24g of stannous octoate catalyst was added and the temperature was gradually increased to 250℃and the process was pre-polycondensed. When the temperature is raised to 250 ℃, a vacuum pump is started to slowly decompress to less than 50Pa for polycondensation, and the reaction is carried out for about 2 hours. Stopping the system vacuum, blowing nitrogen to cool, and discharging under nitrogen protection to obtain a required material sample for testing.
Example 3
And (3) carrying out esterification reaction under normal pressure. 149.51g PTA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of the catalyst tetrabutyl titanate was added. Setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 131.52gAA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of tetrabutyl titanate catalyst was added. Setting the temperature to 170 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 126.16g of 1, 4-butanediol and 18.61g of chelidonic acid are firstly added, and the esterification reaction is considered to be finished when the esterification water yield collected at 170 ℃ reaches 95% of the theoretical value, and the reaction time is about 2 hours.
And (3) carrying out vacuum polycondensation reaction. The product was placed in the same reactor, 2.24g of stannous octoate catalyst was added and the temperature was gradually increased to 250℃and the process was pre-polycondensed. When the temperature is raised to 250 ℃, a vacuum pump is started to slowly decompress to less than 50Pa for polycondensation, and the reaction is carried out for about 2 hours. Stopping the system vacuum, blowing nitrogen to cool, and discharging under nitrogen protection to obtain a required material sample for testing.
Example 4
And (3) carrying out esterification reaction under normal pressure. 149.51g PTA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of the catalyst tetrabutyl titanate was added. Setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 131.52gAA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of tetrabutyl titanate catalyst was added. The temperature is set to 170 ℃, the esterification reaction is considered to be finished when the collected esterification water yield reaches 95% of the theoretical value, the reaction time is about 2 hours, 126.16g of 1, 4-butanediol and 18.71g of chelidonic acid are firstly added, and the esterification reaction is considered to be finished when the collected esterification water yield reaches 95% of the theoretical value, and the reaction time is about 2 hours.
And (3) carrying out vacuum polycondensation reaction. The product was placed in the same reactor, 2.24g of stannous octoate catalyst was added and the temperature was gradually increased to 250℃and the process was pre-polycondensed. When the temperature is raised to 250 ℃, a vacuum pump is started to slowly decompress to less than 50Pa for polycondensation, and the reaction is carried out for about 2 hours. Stopping the system vacuum, blowing nitrogen to cool, and discharging under nitrogen protection to obtain a required material sample for testing.
Example 5
And (3) carrying out esterification reaction under normal pressure. 149.51g PTA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of the catalyst tetrabutyl titanate was added. Setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is about 2 hours; 131.52gAA and 126.16g BDO were added to a 1L polymerization reactor and 1.49g of tetrabutyl titanate catalyst was added. The temperature is set to 170 ℃, the esterification reaction is considered to be finished when the collected esterification water yield reaches 95% of the theoretical value, the reaction time is about 2 hours, 126.16g of 1, 4-butanediol and 18.81g of chelidonic acid are firstly added, and the esterification reaction is considered to be finished when the collected esterification water yield reaches 95% of the theoretical value, and the reaction time is about 2 hours.
And (3) carrying out vacuum polycondensation reaction. The product was placed in the same reactor, 2.24g of stannous octoate catalyst was added and the temperature was gradually increased to 250℃and the process was pre-polycondensed. When the temperature is raised to 250 ℃, a vacuum pump is started to slowly decompress to less than 50Pa for polycondensation, and the reaction is carried out for about 2 hours. Stopping the system vacuum, blowing nitrogen to cool, and discharging under nitrogen protection to obtain a required material sample for testing.
The impact strength of the obtained chelidonic acid modified PBAT degradation material is obviously improved, and compared with the impact strength of a PBAT polymer, the impact strength of the chelidonic acid modified PBAT degradation material is improved. The introduction of chelidonic acid improves the strength of the material and overcomes the defect of insufficient strength of PBAT.
The present invention is described in detail by the specific embodiments, but the embodiments of the present invention are not limited by the above examples, and all technical solutions formed by equivalent substitution or equivalent transformation fall within the scope of the present invention.

Claims (4)

1. The preparation method of the chelidonic acid modified PBAT degradation material is characterized by comprising the following preparation processes:
taking terephthalic acid (PTA), adipic Acid (AA), chelidonic acid and 1, 4-Butanediol (BDO) as raw materials, and adopting a direct esterification method to respectively prepare butylene terephthalate, butylene adipate and butylene chelidonate; alkyd mole ratio 1.4:1, a step of; adding PTA and BDO into a 1L polymerization reaction kettle, and adding a catalyst tetrabutyl titanate; setting the temperature to 200 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, treating the esterification reaction as ending, wherein the reaction time is 2 hours; adding AA and BDO into a 1L polymerization reaction kettle, and adding a catalyst tetrabutyl titanate; setting the temperature to 170 ℃, and when the collected esterification water yield reaches 95% of a theoretical value, finishing the esterification reaction, wherein the reaction time is 2 hours; adding chelidonic acid and BDO, setting the temperature to 170 ℃, and taking the collected esterification water yield to 95% of a theoretical value as the end of the esterification reaction, wherein the reaction time is 2 hours; in the polycondensation reaction stage, butylene terephthalate, butylene adipate and chelidonic acid are put into a three-neck flask, stannous octoate is used as a catalyst, the reaction temperature is gradually increased from 200 ℃ to 250 ℃ for pre-polycondensation reaction, when the temperature reaches 250 ℃, the vacuum polycondensation is gradually carried out for 2 hours, the vacuum of the system is stopped, nitrogen is blown in for cooling, and the nitrogen is used for protecting discharge; the catalyst for normal pressure esterification reaction is tetrabutyl titanate, and the catalyst for vacuum polycondensation is stannous octoate; the PBAT is modified by chelidonic acid, so that the strength of the PBAT is improved.
2. The preparation method of the chelidonic acid modified PBAT degradation material as claimed in claim 1, wherein the degradation material is prepared from the following raw materials in parts by weight:
AA 131.52g；
BDO 126.16g；
PTA 149.51g；
18.41g of chelidonic acid;
tetrabutyl titanate 1.49g;
stannous octoate 2.24g.
3. The method for preparing a chelidonic acid modified PBAT degradation material according to claim 2, wherein the molar ratio of BDO to (aa+pta) is 0.45.
4. The method for preparing a chelidonic acid modified PBAT degradation material as defined in claim 2, wherein the molar ratio of AA to PTA is 0.88.
CN202310395966.9A 2023-04-14 2023-04-14 Preparation method of chelidonic acid modified PBAT degradation material Pending CN116355190A (en)

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CN116355190A true CN116355190A (en) 2023-06-30

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