CN116284714A - Manufacturing method and application of biodegradable material capable of being heated by microwaves - Google Patents
Manufacturing method and application of biodegradable material capable of being heated by microwaves Download PDFInfo
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Abstract
The invention relates to a method for manufacturing a microwave-heatable biodegradable material and application thereof, wherein the thermal deformation temperature (0.45 MPa) of the microwave-heatable biodegradable material is 100-130 ℃, the melting point is 145-160 ℃, the melt index (190 ℃/2.16 kg) is 4-8 g/10min, the carboxyl end content is 8-22 mmol/kg, the tensile strength is more than 35MPa, the elongation at break is more than 300%, the bending strength is more than 35MPa, the bending modulus is more than 500MPa, and the relative biodegradability of the industrial composting environment in 90 days is more than 90%. The biodegradable material capable of being heated by microwaves has a high melting point, the high softening point can meet the high-temperature-resistant requirement of microwave heating at the temperature of more than 100 ℃ for tableware in the fields of rail transit and aviation, and meanwhile, the material has high strength and good mechanical property, and has important application prospects in the fields of aviation straws, dinner forks, boxes and the like.
Description
Technical Field
The invention belongs to the technical field of degradable materials, and relates to a manufacturing method and application of a biodegradable material capable of being heated by microwaves.
Background
The prior aviation tableware still adopts traditional polypropylene (PP), polyester (PET) and other non-biodegradable high polymer materials, but the traditional polylactic acid (PLA) and the traditional poly terephthalic acid-adipic acid-butanediol ester (PBAT) have low softening temperature and low melting point, so that the prior aviation tableware can not be used because of the low heating temperature resistance requirement of the prior aviation tableware, and the prior tableware which needs to be heated by a microwave oven and has high meal holding temperature can not be used, thereby bringing trouble to the low-carbon environment-friendly development of the aviation industry.
According to the method for improving the heat-resistant stability of the material, the heat-resistant stability of the material is improved by introducing a rigid structure, such as benzene rings and multiple rings, into the molecular structure design, but the damage of the biodegradation characteristic of the material is inevitably caused by the introduction of the rigid structure, particularly the benzene ring structure; the blending processing technology is the most commonly used modification method of the high polymer material, and based on the alloy toughening technology, zhao Mengmeng and the like, the compatibility of polylactic acid and polycarbonate alloy is improved by adopting a comb-shaped molecular solubilizer with reactivity, the impact resistance and high temperature resistance of the polylactic acid are replaced, but the polycarbonate is of a non-biodegradable high polymer structure, so that the biodegradation characteristic of the polycarbonate is influenced; therefore, in order not to change the biodegradation characteristic of the material, the Japanese fine groups are introduced into the polylactic acid matrix by taking degradable polyvinyl alcohol as a resin material and by the crosslinkable characteristic of the polyvinyl alcohol, so that the mechanical property and the heat resistance of the polylactic acid are improved, and meanwhile, the polyvinyl alcohol has the degradability and thus has less influence on the biodegradation characteristic, but toxic substances such as aldehydes are required to be adopted for crosslinking the polyvinyl alcohol, so that the residue in the matrix is difficult to meet the food-grade requirement.
Aiming at the problems that the prior aviation tableware is difficult to biodegrade and the conventional biodegradable material is difficult to meet the high temperature resistant requirement, the ultraviolet light cured crosslinking material is adopted, PLA and PBAT are initiated by ultraviolet light to carry out curing crosslinking, the promotion of the softening point of the material is realized, the development of the high temperature resistant biodegradable material capable of being heated by a microwave oven is realized, and the development of the biodegradable material for the high temperature resistant aviation tableware in the prior country has great significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a manufacturing method and application of a biodegradable material capable of being heated by microwaves. The invention obtains the bioactive chain extender with four reactive functional groups through the reaction of L-serine with biodegradable 1, 4-butanediol, and utilizes the bioactive chain extender to carry out solid-phase polycondensation reaction with polybutylene succinate to prepare the high-temperature-resistant polybutylene succinate with a plurality of branched chains and a star structure, thereby avoiding the difficulty in degradation of the conventional isocyanate chain extender due to biotoxicity, and the difficulty in biodegradation of the conventional anhydride and epoxy chain extender, and the molecular weight increase obtained by the binary functional group structure, but the heat resistance is limited, the mechanical property and the processing property are deteriorated due to transitional crosslinking after the polyfunctional group chain extension, and the problems of difficult meeting the melt processing condition and the like.
In order to achieve the above purpose, the invention adopts the following scheme:
a biodegradable material capable of being heated by microwaves is characterized in that the thermal deformation temperature is 100-130 ℃ under the condition of 0.45MPa, the melting point is 145-160 ℃, the melt index is 4-8 g/10min under the condition of 190 ℃/2.16kg, and the carboxyl end group content is 8-22 mmol/kg.
A biodegradable material capable of being heated by microwaves is characterized in that the tensile strength is more than 35MPa, the breaking elongation is more than 300%, the bending strength is more than 35MPa, the bending modulus is more than 500MPa, and the relative biodegradability of the industrial composting environment in 90 days is more than 90%.
The preparation method of the biodegradable material capable of being heated by microwaves is characterized by comprising the following technical steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The molar ratio of L-serine to 1, 4-butanediol is 1:1.05-1:1.2.
The temperature of the esterification reaction is 165-205 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 0.5-5.0wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid phase tackifying process comprises low-temperature tackifying reaction, medium-temperature tackifying reaction, high-temperature tackifying reaction and negative pressure tackifying reaction;
the low-temperature tackifying reaction temperature is 105-110 ℃, and the low-temperature tackifying reaction time is 30-120 min;
the medium temperature tackifying reaction temperature is 120-125 ℃, and the medium temperature tackifying reaction temperature is 2-5 h;
the high-temperature tackifying reaction temperature is 130-140 ℃, and the high-temperature tackifying reaction time is 4-8 h;
the negative pressure tackifying reaction is carried out at 130-135 ℃ and vacuum degree of 1000-5000 Pa for 30-45 min.
The biodegradable material capable of being heated by microwaves is prepared into straw, fork and box products applied to the fields of rail transit and aviation through injection molding or extrusion, and the processing temperature is 200-220 ℃.
The invention has the beneficial effects that:
(1) The invention relates to a manufacturing method and application of a biodegradable material capable of being heated by microwaves, which aims at solving the problems that the existing aviation tableware material, particularly the biodegradable material taking PBS, PBAT and PLA as matrixes, has a low softening point and is difficult to bear steam at a high temperature of 105-120 ℃ and a microwave heating environment, and the conventional crosslinking structure leads to the processing characteristics of the material, such as poor melt index and mechanical property in fluidity, poor toughness and difficulty in meeting processing and using requirements, and meanwhile, the multifunctional crosslinking structure leads to the problems that the biodegradation is difficult and the biodegradability is influenced. By introducing a biodegradable chain extender structure, particularly an amino acid structure required by organisms, into a matrix, the requirements of the biodegradable characteristics are met on the basis of ensuring the performance required by crosslinking; and the four-functional group structure is utilized to endow a star-shaped structure in the reaction process, so that the problem that the mechanical property becomes brittle due to transitional crosslinking is avoided, and the rheological property in the processing process is ensured.
(2) According to the preparation method and application of the microwave-heated biodegradable material, through a solid-phase tackifying process, the bioactive chain extender with four functional groups and the polybutylene succinate are subjected to solid-phase polycondensation reaction to prepare the high-temperature-resistant polybutylene succinate with a star structure and a plurality of branched chains, so that the problems that the conventional isocyanate chain extender is difficult to degrade due to biotoxicity, the conventional anhydride and epoxy chain extender is difficult to biodegrade, the molecular weight obtained by a binary functional group structure is increased, the heat resistance is improved to a limited extent, the mechanical property and the processing property are deteriorated due to transitional crosslinking after the polyfunctional group chain extension, and the melt processing condition is difficult to be satisfied are solved; meanwhile, by adopting a process of distributing temperature rise and negative pressure in the solid-phase tackifying process, the adhesive deformation of the basic slice of the polybutylene succinate is avoided by utilizing the distribution temperature, and small molecules and oligomers can be better and faster taken away by utilizing the negative pressure, so that the molecular weight is further improved, and the purpose of further tackifying is achieved.
(3) The biodegradable material capable of being heated by microwaves has a high melting point, the high softening point can meet the high temperature resistant requirement of microwave heating of tableware in the fields of rail transit and aviation, and meanwhile, the material has high strength and good mechanical property, and has important application prospects in the fields of aviation straws, dinner forks, boxes and the like.
Drawings
FIG. 1 is a chemical reaction equation for a bioactive chain extender of the present invention;
FIG. 2 is a nuclear magnetic pattern of a bioactive chain extender of the present invention;
FIG. 3 is a schematic diagram of the structure of the microwave-heatable biodegradable material according to the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of a microwave-heatable biodegradable material according to the present invention.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The testing method of each parameter in the invention is as follows:
(1) Heat distortion temperature: testing by adopting an XRW-300 series thermal deformation temperature tester according to a method specified by the national standard GB/T1634.1-2019;
(2) Melting point: measuring by adopting a Q20 differential scanning calorimeter, taking nitrogen as a protective gas, wherein the gas flow is 50mL/min, heating at a rate of 10 ℃/min, and taking the melting maximum peak value in the heating process as the melting point;
(3) Melt index: testing was performed using a Kunspan Hongji HJ-RRZS melt index tester according to the method of standard ASTM D1238;
(4) Carboxyl end group content: a burette is adopted, phenol and chloroform are used as solvents, the volume ratio of the phenol to the chloroform solution is 2:3, and the test is carried out by referring to national standard GB/T14190-2017;
(5) Mechanical properties (tensile strength, elongation at break, flexural strength, flexural modulus): testing by using an Shimadzu AUX-5000 universal testing machine according to a method of national standard GB 1040-2018;
(6) Biodegradable rate: the method adopts a Bipu biodegradation test system and tests according to the method of national standard GB/T19277.1-2011.
Example 1
The microwave-heatable biodegradable material has a heat distortion temperature (0.45 MPa) of 100 ℃, a melting point of 145 ℃, a melt index (190 ℃/2.16 kg) of 8g/10min, a carboxyl end group content of 22mmol/kg, a tensile strength of 35.5MPa, an elongation at break of 350%, a bending strength of 35.9MPa, a bending modulus of 510MPa, and a 90-day industrial composting environment relative biodegradability of 96%.
The preparation method of the microwave-heatable biodegradable material comprises the following steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The mol ratio of the L-serine to the 1, 4-butanediol is 1:1.25, and the temperature of the esterification reaction is 165 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 0.5wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid-phase tackifying technology comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction; the low-temperature tackifying reaction temperature is 105 ℃, and the low-temperature tackifying reaction time is 120min; the medium-temperature tackifying reaction temperature is 120 ℃, and the medium-temperature tackifying reaction temperature is 5 hours; the high-temperature tackifying reaction temperature is 130 ℃, and the high-temperature tackifying reaction time is 8 hours; the negative pressure tackifying reaction is carried out at 130 ℃, the vacuum degree of the negative pressure tackifying reaction is 1000Pa, and the time of the negative pressure tackifying reaction is 45min.
The microwave-heatable biodegradable material is subjected to injection molding to obtain a microwave-heatable fork and a box, the processing temperature of the microwave-heatable fork and box is 210 ℃, and the processing temperature of the microwave-heatable straw obtained by extrusion molding is 200 ℃.
Example 2
The microwave-heatable biodegradable material has a thermal deformation temperature (0.45 MPa) of 130 ℃, a melting point of 160 ℃, a melt index (190 ℃/2.16 kg) of 8g/10min, a carboxyl end group content of 8mmol/kg, a tensile strength of 36MPa, an elongation at break of 350%, a bending strength of 37.8MPa, a bending modulus of 550MPa and a relative biodegradability of 95% in an industrial composting environment of 90 days.
The preparation method of the microwave-heatable biodegradable material comprises the following steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The mol ratio of the L-serine to the 1, 4-butanediol is 1:1.05, and the temperature of the esterification reaction is 205 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 5.0wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid-phase tackifying technology comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction; the low-temperature tackifying reaction temperature is 110 ℃, and the low-temperature tackifying reaction time is 120min; the medium-temperature tackifying reaction temperature is 125 ℃, and the medium-temperature tackifying reaction temperature is 2 hours; the high-temperature tackifying reaction temperature is 140 ℃, and the high-temperature tackifying reaction time is 4 hours; the negative pressure tackifying reaction is that the temperature of the negative pressure tackifying reaction is 135 ℃, the vacuum degree of the negative pressure tackifying reaction is 5000Pa, and the time of the negative pressure tackifying reaction is 30min.
The microwave-heatable biodegradable material is subjected to injection molding to obtain a microwave-heatable fork and a box, the processing temperature of the microwave-heatable fork and box is 220 ℃, and the processing temperature of the microwave-heatable straw obtained by extrusion molding is 210 ℃.
Example 3
The microwave-heatable biodegradable material has a heat distortion temperature (0.45 MPa) of 130 ℃, a melting point of 155 ℃, a melt index (190 ℃/2.16 kg) of 5g/10min, a carboxyl end group content of 10mmol/kg, a tensile strength of 37.4MPa, an elongation at break of 450%, a bending strength of 39.2MPa, a bending modulus of 6500MPa, and a 90-day industrial composting environment relative biodegradability of 95%.
The preparation method of the microwave-heatable biodegradable material comprises the following steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The mol ratio of the L-serine to the 1, 4-butanediol is 1:1.15, and the temperature of the esterification reaction is 195 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 4.0wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid-phase tackifying technology comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction; the low-temperature tackifying reaction temperature is 110 ℃, and the low-temperature tackifying reaction time is 120min; the medium-temperature tackifying reaction temperature is 125 ℃, and the medium-temperature tackifying reaction temperature is 5 hours; the high-temperature tackifying reaction temperature is 140 ℃, and the high-temperature tackifying reaction time is 8 hours; the negative pressure tackifying reaction is that the temperature of the negative pressure tackifying reaction is 135 ℃, the vacuum degree of the negative pressure tackifying reaction is 1000Pa, and the time of the negative pressure tackifying reaction is 45min.
The microwave-heatable biodegradable material is subjected to injection molding to obtain a microwave-heatable fork and a box, the processing temperature of the microwave-heatable fork and box is 210 ℃, and the processing temperature of the microwave-heatable straw obtained by extrusion molding is 210 ℃.
FIG. 1 is a chemical reaction equation for the preparation of an active chain extender, FIG. 2 is a hydrogen spectrum of a nuclear magnetic pattern of the active chain extender, a (4.20-4.28 ppm) and b (3.98-4.08 ppm) are characteristic peaks of ethyl groups in chemical shift structures, c (3.51-3.55 ppm) is a characteristic peak of hydroxyl groups or electron withdrawing groups, d (1.99-2.02 ppm) is a characteristic peak of hydroxyl groups or amino groups, and e (1.48-1.57 ppm) is an ethyl functional group in alkanes. The characteristic peak of carboxylic acid in the map disappears, and a large number of characteristic peaks of hydroxyl structures are contained in the map, which shows that L-serine and 1, 4-butanediol react, meanwhile, the unique ethyl functional group e in the butanediol architecture is observed in the map, and a multiple split peak structure appears in the functional group, so that the reaction of L-serine and 1, 4-butanediol is also confirmed. Meanwhile, the ratio Sab of the sum of the peak areas Sab of a and b to the peak area Se of e is obtained through analysis of the peak area ratio of the characteristic peaks of a, b and e: se is 1:1.01, thus indicating that L-serine and 1, 4-butanediol react in a ratio of 1:1, indicating that the synthesized compound is the desired active chain extender.
FIG. 3 is a schematic molecular structure diagram of a biodegradable material which can be heated by microwaves, FIG. 4 is a nuclear magnetic pattern of the biodegradable material which can be heated by microwaves, 2.64ppm corresponds to a characteristic absorption peak of an ethyl structure on succinic acid in PBS, 5.02ppm in the pattern corresponds to a characteristic peak of a hydrogen nuclear magnetic pattern which is unique to an active chain extender, corresponds to a characteristic peak structure of an alpha-H structure which is connected with carbonyl (C=O) and amino in the active chain extender, and does not find an amino characteristic peak in the structure of the active chain extender in the pattern, thus indicating that the active chain extender and polybutylene succinate (PBS) have undergone a chain extension reaction, and amino (-NH) on the original chain extender 2 ) Chain extension reactions occur and the corresponding active chain extender reacts with PBS to form a star structure. By comparing the characteristic peak area S1 of 2.64ppm with the characteristic peak area S2 of 5.02ppm, S2 is obtained: the ratio of S1 is 1:101, and because the ethyl group is correspondingly 4 hydrogens, the chain extender is 1 hydrogen, and the addition amount of the chain extender is 4.0%, the theoretical ratio of S2 to S1 is 1:100, and the ratio is close to the obtained peak area, and the molecular structure of the designed biodegradable material capable of being heated by microwaves in the figure 3 is formed by the reaction of the chain extender and PBS.
Example 4
The microwave-heatable biodegradable material has a heat distortion temperature (0.45 MPa) of 120 ℃, a melting point of 150 ℃, a melt index (190 ℃/2.16 kg) of 6g/10min, a carboxyl end group content of 18mmol/kg, a tensile strength of 36.2MPa, an elongation at break of 380%, a bending strength of 35.9MPa, a bending modulus of 550MPa and a 90-day industrial composting environment relative biodegradability of 96%.
The preparation method of the microwave-heatable biodegradable material comprises the following steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The mol ratio of the L-serine to the 1, 4-butanediol is 1:1.20, and the temperature of the esterification reaction is 200 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 5.0wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid-phase tackifying technology comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction; the low-temperature tackifying reaction temperature is 110 ℃, and the low-temperature tackifying reaction time is 90min; the medium-temperature tackifying reaction temperature is 120 ℃, and the medium-temperature tackifying reaction temperature is 5 hours; the high-temperature tackifying reaction temperature is 135 ℃, and the high-temperature tackifying reaction time is 6 hours; the negative pressure tackifying reaction is that the temperature of the negative pressure tackifying reaction is 135 ℃, the vacuum degree of the negative pressure tackifying reaction is 1000Pa, and the time of the negative pressure tackifying reaction is 45min.
The microwave-heatable biodegradable material is subjected to injection molding to obtain a microwave-heatable fork and a box, the processing temperature of the microwave-heatable fork and box is 210 ℃, and the processing temperature of the microwave-heatable straw obtained by extrusion molding is 200 ℃.
Example 5
A method for preparing a biodegradable material by microwave heating and application thereof, wherein the thermal deformation temperature (0.45 MPa) of the biodegradable material by microwave heating is 125 ℃, the melting point is 160 ℃, the melt index (190 ℃/2.16 kg) is 5g/10min, the carboxyl end group content is 12mmol/kg, the tensile strength is 35.9MPa, the elongation at break is 360%, the bending strength is 37.0MPa, the bending modulus is 540MPa, and the relative biodegradability of the biodegradable material in an industrial composting environment of 90 days is 95%.
The preparation method of the microwave-heatable biodegradable material comprises the following steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials, put into a reaction kettle, are subjected to esterification reaction in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared.
The mol ratio of the L-serine to the 1, 4-butanediol is 1:1.15, and the temperature of the esterification reaction is 200 ℃.
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of the melt in the polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min, and then extruded to obtain the basic slice of the polybutylene succinate.
The mass fraction of the chain extender in the polybutylene succinate base slice is 4.5wt%.
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
The solid-phase tackifying technology comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction; the low-temperature tackifying reaction temperature is 110 ℃, and the low-temperature tackifying reaction time is 90min; the medium-temperature tackifying reaction temperature is 125 ℃, and the medium-temperature tackifying reaction temperature is 5 hours; the high-temperature tackifying reaction temperature is 140 ℃, and the high-temperature tackifying reaction time is 6 hours; the negative pressure tackifying reaction is that the temperature of the negative pressure tackifying reaction is 135 ℃, the vacuum degree of the negative pressure tackifying reaction is 1000Pa, and the time of the negative pressure tackifying reaction is 45min.
The microwave-heatable biodegradable material is subjected to injection molding to obtain a microwave-heatable fork and a box, the processing temperature of the microwave-heatable fork and box is 220 ℃, and the processing temperature of the microwave-heatable straw obtained by extrusion molding is 210 ℃.
Comparative example 1
Substantially the same as in example 3, except that L-serine was directly used as the chain extender structure in the step (1).
Because the chain extender contains a carboxylic acid structure in a molecular structure, PBS slices are severely decomposed in an acidic high-temperature environment in the melt extrusion and processing processes, so that basic polybutylene succinate slices are difficult to obtain.
Comparative example 2
Substantially the same as in example 3, except that butanediol was changed to butanol in the step (1).
In the polybutylene succinate base slice and the material, the mechanical property of the material is 22.5MPa, the thermal deformation temperature is 105 ℃, the biodegradability is not 56% in the test, and the butanol is easy to be removed in the preparation process, so that the PBS is easy to deactivate in the tackifying process, the tackifying process of the PBS is blocked, meanwhile, the butanol structure which is not completely reacted is not biodegradable, and the material is different from the alcohol structure in the PBS matrix, so that the biodegradability of the material is affected.
Comparative example 3
Substantially the same as in example 3, except that step (3) does not employ a vacuum negative pressure tackifying reaction; the thermal deformation temperature of the obtained material is 80 ℃, the melt index is 10g/10min, the carboxyl end group content is 20mmol/kg, the tensile strength is 25MPa, the elongation at break is 300%, the bending strength is 20MPa, the bending modulus is 400MPa, and the relative biodegradability of the industrial composting environment for 90 days is 95%. Although the material has certain mechanical properties, due to the lack of a vacuum negative pressure tackifying process, more oligomers are arranged in the material, so that the thermal deformation temperature of the material is limited, and due to the influence of the internal oligomers, the mechanical properties of the material are not ideal enough and are seriously reduced.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the concept of the present invention, and are intended to be within the scope of the present invention.
Claims (10)
1. The preparation method of the biodegradable material capable of being heated by microwaves is characterized by comprising the following technical steps:
(1) Preparation of active chain extenders
L-serine and 1, 4-butanediol are taken as raw materials to be put into a reaction kettle, esterification reaction is carried out in nitrogen atmosphere, the water yield of the esterification reaction is controlled to be more than 99%, and then excess 1, 4-butanediol is removed through reduced pressure distillation, so that the active chain extender is prepared;
(2) Preparation of basic slice of polybutylene succinate
Using succinic acid and 1, 4-butanediol as raw materials, using tetrabutyl titanate as a catalyst, adopting a gradual condensation polymerization method, performing gradual condensation polymerization reaction at 200-240 ℃, controlling the vacuum degree in the polycondensation process to be 50-100 Pa, and controlling the reaction time to be 1.5-3.0 h; after the reaction is finished, the temperature of a melt in a polymerization kettle is reduced to 180-200 ℃, then an active chain extender is added into the reaction kettle, and the mixture is melted, stirred and dispersed for 15-45 min and then extruded to obtain basic slices of the polybutylene succinate;
(3) Preparation of biodegradable material capable of being heated by microwaves
Firstly, drying a basic slice of the poly (butylene succinate) for 48 hours at 105 ℃, controlling the moisture of the basic slice of the poly (butylene succinate) to be below 0.1 weight percent, preparing the basic slice of the dried poly (butylene succinate), and then adopting a solid phase polycondensation method to carry out chain extension and viscosity expansion on the basic slice of the dried poly (butylene succinate) in a solid phase viscosity-increasing reaction tower to prepare the required biodegradable material capable of being heated by microwaves.
2. The method of claim 1, wherein in step (1), the molar ratio of L-serine to 1, 4-butanediol is 1:1.05-1:1.2.
3. The method of claim 1, wherein in step (1), the esterification reaction temperature is 165 ℃ to 205 ℃.
4. The method for preparing a biodegradable material according to claim 1, wherein in the step (2), the mass fraction of the chain extender in the polybutylene succinate base slice is 0.5-5.0 wt%.
5. A method of preparing a microwave heatable biodegradable material as defined in claim 1, wherein,
in the step (3), the solid-phase tackifying process comprises a low-temperature tackifying reaction, a medium-temperature tackifying reaction, a high-temperature tackifying reaction and a negative-pressure tackifying reaction.
6. The method for preparing a biodegradable material according to claim 5, wherein the low-temperature tackifying reaction temperature is 105-110 ℃ and the low-temperature tackifying reaction time is 30-120 min.
7. The method for preparing a biodegradable material according to claim 5, wherein the medium-temperature tackifying reaction temperature is 120-125 ℃ and the medium-temperature tackifying reaction temperature is 2-5 h.
8. The method for preparing a biodegradable material according to claim 5, wherein the high-temperature tackifying reaction temperature is 130-140 ℃ and the high-temperature tackifying reaction time is 4-8 h.
9. The method for preparing the biodegradable material capable of being heated by microwaves according to claim 1, wherein the negative pressure tackifying reaction is carried out at a temperature of 130-135 ℃, a vacuum degree of 1000-5000 Pa and a time of 30-45 min.
10. The use of a microwaveable biodegradable material according to claim 1, wherein the microwaveable biodegradable material is used in a straw, fork, box product in rail transit, aviation applications, prepared by injection molding or extrusion, and has a processing temperature of 200 ℃ to 220 ℃.
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