CN108410000B - 2, 5-furandicarboxylic acid based polyester foam material and preparation method thereof - Google Patents

2, 5-furandicarboxylic acid based polyester foam material and preparation method thereof Download PDF

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CN108410000B
CN108410000B CN201810357963.5A CN201810357963A CN108410000B CN 108410000 B CN108410000 B CN 108410000B CN 201810357963 A CN201810357963 A CN 201810357963A CN 108410000 B CN108410000 B CN 108410000B
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furandicarboxylic acid
based polyester
foaming
preform
acid based
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CN108410000A (en
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庞永艳
郑文革
刘伟
吴明辉
覃康培
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a 2, 5-furandicarboxylic acid based polyester foaming material and a preparation method thereof. The preparation method comprises the following steps: (a) 2, 5-furandicarboxylic acid based polyester plastic is placed in a mould to be pressed into a sheet-shaped prefabricated product, and then the sheet-shaped prefabricated product is quenched; (b) placing the pre-product after quenching treatment and a first foaming agent in a closed container without contact, wherein the first foaming agent is at least one of chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol; (c) then introducing a second foaming agent into the closed container, wherein the second foaming agent is at least one of carbon dioxide and nitrogen, and keeping the temperature in the closed container at 40-65 ℃ to ensure that the first foaming agent is changed into a gas state from a liquid state, the pressure in the closed container is 1-6 MPa, and the pressure maintaining time is 4-15 h; (d) and (3) removing the gas in the closed container, taking out the prefabricated product, placing the prefabricated product into a foaming medium for foaming, and cooling to obtain the 2, 5-furandicarboxylic acid based polyester foaming material with the cell size of 5-50 microns and the expansion ratio of 2-15 times.

Description

2, 5-furandicarboxylic acid based polyester foam material and preparation method thereof
Technical Field
The invention relates to the technical field of polymer foam materials, in particular to a 2, 5-furandicarboxylic acid based polyester foam material and a preparation method thereof.
Background
The polymer foaming material is a microporous material which takes a polymer as a matrix and has a large number of bubbles inside, and has the advantages of light weight, good impact resistance, high specific strength, heat insulation, sound absorption, slow release of medicines and the like. At present, polymer foam materials are widely applied to the fields of packaging, household appliances, automobile parts, sports, construction, separation membranes, oil absorption materials, medicines and the like. In recent years, 2, 5-furandicarboxylic acid based polyesters have been extensively studied. The reason benefits from the following two points:
the 2, 5-furandicarboxylic acid-based polyester and the bio-based macromolecules (such as polylactic acid (PLA), polybutylene succinate (PBS) and Polyhydroxyalkanoate (PHA)) which are widely used at present all use renewable resources as main raw materials, so that the consumption of high polymer materials on petroleum resources is reduced, the problem of environmental pollution of the petroleum-based raw materials in the production process is solved, and the ecological environment is protected.
Secondly, the mechanical properties (strength, modulus) and heat resistance (heat distortion temperature) and gas barrier properties (gas permeability) of bio-based polymers such as polylactic acid (PLA), polybutylene succinate (PBS), and Polyhydroxyalkanoate (PHA) in practical application are obviously lower than those of petroleum-based aromatic polymers such as polyethylene terephthalate (PET), Polycarbonate (PC), and polybutylene terephthalate (PBT). The reason is the lack of rigid aromatic ring structures in the macromolecular backbone of these bio-based macromolecules, resulting in a lower Tg. The furan rings impart greater rigidity to the 2, 5-furandicarboxylic acid-based polyester and a higher Tg, e.g., the Tg of PEF is 18 ℃ higher than that of PET. Meanwhile, because furan rings cannot freely rotate on the molecular main chain, the polyester has extremely excellent gas barrier property, such as O at 35 DEG C2The permeability coefficient in PEF is only 0.0107 barrer. Therefore, the 2, 5-furandicarboxylic acid-based polyester has wide application prospect.
However, no report on foaming of 2, 5-furandicarboxylic acid based polyesters has been found so far. The 2, 5-furandicarboxylic acid-based polyester has better gas barrier property, so that the gas foaming agent has low dissolution rate and low solubility in the copolyester, the foaming performance is poor, and the kettle pressure foaming is extremely unfavorable.
In order to solve the problem of slow dissolution rate of gas in polymer, the Chinese patent (publication No. CN102504323A) proposes that the dissolution rate of gas in polymer matrix is increased by raising the temperature in a kettle in the gas saturation stage of kettle pressure foaming. This technique is only applicable to some polymers with fast gas dissolution rate but high solubility. For 2, 5-furandicarboxylic acid based polyesters, the dissolution rate of the gas blowing agent in such polyesters is slow at room temperature, while the solubility is low. By raising the temperature in the kettle, although the dissolution rate of the blowing agent in the polyester is increased, the solubility of the blowing agent in the polyester becomes lower, and therefore the method cannot be used for producing a 2, 5-furandicarboxylic acid based polyester foamed material.
Disclosure of Invention
Based on the above, there is a need to provide a 2, 5-furandicarboxylic acid based polyester foam material and a preparation method thereof, wherein the preparation method greatly improves the foaming performance of the 2, 5-furandicarboxylic acid based polyester through the synergistic effect of a gas foaming agent and a liquid foaming agent, and the 2, 5-furandicarboxylic acid based polyester foam material with a certain expansion ratio and a cell size meeting the requirement of a microporous material is prepared.
A preparation method of a 2, 5-furandicarboxylic acid-based polyester foaming material comprises the following steps:
(a) placing 2, 5-furandicarboxylic acid-based polyester plastic in a mold, pressing into a sheet-shaped preform, and quenching the sheet-shaped preform;
(b) placing the pre-product after quenching treatment and a first foaming agent in a closed container; wherein the first foaming agent is not in contact with the preform, and the first foaming agent is at least one of chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol;
(c) introducing a second foaming agent into the closed container, wherein the second foaming agent is at least one of carbon dioxide and nitrogen, and keeping the temperature in the closed container at 40-65 ℃ to change the first foaming agent from a liquid state to a gas state, and simultaneously keeping the pressure in the closed container at 1-6 MPa for 4-15 h;
(d) and (3) removing the gas in the closed container, taking out the prefabricated product, placing the prefabricated product in a foaming medium for foaming, and cooling to obtain the 2, 5-furandicarboxylic acid based polyester foaming material.
In the preparation method, the solubility of the second foaming agents carbon dioxide and nitrogen in the 2, 5-furandicarboxylic acid based polyester plastic is limited, while the boiling point of the first foaming agents chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol is lower, the first foaming agents chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol can be changed into gas from liquid at the saturation temperature, and the first gaseous foaming agents have certain interaction with the 2, 5-furandicarboxylic acid based polyester plastic during the saturation process and are easily dissolved in the 2, 5-furandicarboxylic acid based polyester plastic. When the first foaming agent is dissolved in the 2, 5-furandicarboxylic acid based polyester plastic, the first foaming agent can plasticize the 2, 5-furandicarboxylic acid based polyester plastic, so that the glass transition temperature of the 2, 5-furandicarboxylic acid based polyester plastic is reduced. Meanwhile, the second foaming agent can be promoted to be slowly dissolved in the 2, 5-furan diformyl polyester plastic. The first foaming agent and the second foaming agent play a foaming role at the same time, and the combination of the two foaming agents can improve the solubility of the second foaming agent in the 2, 5-furandicarboxylic acid based polyester plastic matrix, thereby greatly improving the foaming performance of the 2, 5-furandicarboxylic acid based polyester. In addition, the gas saturation stage of the method does not need to be carried out at high temperature, so that the energy consumption can be reduced.
The invention also provides the 2, 5-furandicarboxylic acid based polyester foaming material prepared by the preparation method, wherein the size of the foam pores of the 2, 5-furandicarboxylic acid based polyester foaming material is 5-50 mu m, and the expansion ratio is 2-15 times.
The prepared 2, 5-furandicarboxylic acid based polyester foam material has the cell size reaching the category of polymer microporous foam materials, is uniform in cell size and proper in expansion ratio, can reduce weight of plastics on the premise of not greatly reducing the physical and mechanical properties of the 2, 5-furandicarboxylic acid based polyester, and simultaneously remarkably improves the toughness of the material, so that the 2, 5-furandicarboxylic acid based polyester foam material has a great number of potential applications in the fields of packaging, household appliances, automobile parts, sports, buildings, separation membranes and the like.
Drawings
FIG. 1 is a partial sectional electron microscope image of the polyethylene 2, 5-furandicarboxylate foam of example 1;
FIG. 2 is a sectional electron microscope image of the polyethylene 2, 5-furandicarboxylate foam of example 1;
FIG. 3 is a partial sectional electron microscope image of the polyethylene 2, 5-furandicarboxylate foam of example 2;
FIG. 4 is a sectional electron micrograph of the polyethylene 2, 5-furandicarboxylate material of comparative example 1;
FIG. 5 is a cross-sectional electron micrograph of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol material of comparative example 2.
Detailed Description
The following will further describe the 2, 5-furandicarboxylic acid based polyester foam material and the preparation method thereof provided by the present invention.
The preparation method of the 2, 5-furandicarboxylic acid based polyester foaming material provided by the invention comprises the following steps:
(a) placing 2, 5-furandicarboxylic acid-based polyester plastic in a mold, pressing into a sheet-shaped preform, and quenching the sheet-shaped preform;
(b) placing the pre-product after quenching treatment and a first foaming agent in a closed container; wherein the first foaming agent is not in contact with the preform, and the first foaming agent is at least one of chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol;
(c) introducing a second foaming agent into the closed container, wherein the second foaming agent is at least one of carbon dioxide and nitrogen, and keeping the temperature in the closed container at 40-65 ℃ to change the first foaming agent from a liquid state to a gas state, and simultaneously keeping the pressure in the closed container at 1-6 MPa for 4-15 h;
(d) and (3) removing the gas in the closed container, taking out the prefabricated product, placing the prefabricated product in a foaming medium for foaming, and cooling to obtain the 2, 5-furandicarboxylic acid based polyester foaming material.
Wherein, the 2, 5-furandicarboxylic acid based polyester plastic in the step (a) is at least one of polyethylene glycol 2, 5-furandicarboxylic acid, 1, 3-propylene glycol 2, 5-furandicarboxylic acid, 1, 4-butanediol 2, 5-furandicarboxylic acid, 1, 6-hexanediol 2, 5-furandicarboxylic acid and 1, 8-octanediol 2, 5-furandicarboxylic acid. And the water content of the 2, 5-furandicarboxylic acid-based polyester is less than or equal to 0.05 wt.%. The 2, 5-furandicarboxylic acid based polyester plastic has too high water content, which may cause degradation of the 2, 5-furandicarboxylic acid based polyester plastic in the subsequent step, and thus, the water content of the raw material 2, 5-furandicarboxylic acid based polyester needs to be controlled.
The thickness of the preform in step (a) is less than or equal to 1.5mm, so that the second foaming agent and the gaseous first foaming agent can be better dissolved in the preform. The pressing temperature for pressing the 2, 5-furandicarboxylic acid-based polyester plastic into the prefabricated product is 140-230 ℃, the pressing temperature is higher than the melting temperature of the 2, 5-furandicarboxylic acid-based polyester plastic and lower than the decomposition temperature of the 2, 5-furandicarboxylic acid-based polyester plastic, and the processing conditions of the 2, 5-furandicarboxylic acid-based polyester plastic can be met.
The sheet-like preform in step (a) is in a molten state, and the quenching treatment time is 5 to 10 min. The invention reduces the crystallinity of the 2, 5-furandicarboxylic acid based polyester plastic through quenching treatment, so that the foaming agent is easier to dissolve into the 2, 5-furandicarboxylic acid based polyester plastic. In the process of changing the 2, 5-furandicarboxylic acid-based polyester plastic from a molten state to a glassy state, a temperature range suitable for crystallization exists, and in the vicinity of the temperature range, the 2, 5-furandicarboxylic acid-based polyester plastic can be crystallized. The quenching treatment of the invention can lead the 2, 5-furandicarboxylic acid-based polyester plastic to rapidly pass through the temperature range, so that the 2, 5-furandicarboxylic acid-based polyester plastic can rapidly change into a glass state without time for crystallization. At this time, the molecular chain is fixed, and the polymer can not be crystallized any more, thereby achieving the purpose of reducing the crystallization of the polymer. The quenching medium for quenching treatment can be ice water, liquid nitrogen and the like. The temperature of the liquid nitrogen is very low, the 2, 5-furandicarboxylic acid based polyester plastic is put into the liquid nitrogen from a molten state for quenching treatment, the temperature difference is very large, the temperature of the 2, 5-furandicarboxylic acid based polyester plastic can be rapidly reduced and the plastic can be changed into a glass state, and the effect is good.
The closed container in step (b) above is preferably an autoclave, and the first blowing agent and the preform are placed in the autoclave without contacting, leaving the surface of the preform exposed for the gaseous first blowing agent and second blowing agent to enter the preform. Wherein the ratio of the preform to the first blowing agent in step (b) is: 50 g: (1 mL-5 mL).
And (b) placing the first foaming agent and the prefabricated product in the high-pressure kettle in the step (b), then closing the high-pressure kettle, heating the high-pressure kettle to the saturation temperature of 40-65 ℃ and keeping the saturation temperature constant to change the first foaming agent from liquid state to gas state, then opening a pressure reducing valve, introducing a second foaming agent into the high-pressure kettle and keeping the pressure in the high-pressure kettle from 1MPa to 6MPa constant, and keeping the pressure for 4-15 h until the gaseous first foaming agent and the gaseous second foaming agent are dissolved and saturated in the 2, 5-furandicarboxylic acid based polyester plastic and are in a dissolved equilibrium state. The saturation temperature is higher than the boiling point of the first foaming agent, the first foaming agent can be changed into gas from liquid at the saturation temperature and is dissolved in the 2, 5-furandicarboxylic acid based polyester plastic, and the saturation temperature can ensure that the 2, 5-furandicarboxylic acid based polyester plastic does not foam in the processes of pressure maintaining and pressure relief, so that the saturated 2, 5-furandicarboxylic acid based polyester plastic can be heated and foamed. The original air in the high-pressure kettle does not need to be discharged, the partial pressure of the air in the high-pressure kettle is only 0.1MPa, and the influence on foaming is not great.
And (d) rapidly heating and foaming the saturated 2, 5-furandicarboxylic acid-based polyester plastic to ensure that the gas in the 2, 5-furandicarboxylic acid-based polyester plastic reaches a supersaturated state, inducing the nucleation of foam cells and further forming a foam cell structure.
Wherein in step (d) the gas in the closed container is discharged within 30 s. The gas in the closed container comprises not only the second foaming agent, but also the gaseous first foaming agent, and if the gas in the closed container is not discharged in a short time under the condition that the 2, 5-furandicarboxylic acid-based polyester plastic is completely saturated, the 2, 5-furandicarboxylic acid-based polyester plastic foams in the pressure relief process, and the subsequent temperature rise foaming is adversely affected.
In the step (d), the foaming medium is at least one of simethicone, glycerin and engine oil. The foaming medium is used as a heat transmission medium and can transmit heat to the saturated 2, 5-furandicarboxylic acid-based polyester plastic to foam the plastic. The foaming medium can bear higher temperature, and meets the requirement of foaming temperature.
The foaming temperature in the step (d) is 100-160 ℃, and the foaming time is 8-25 s.
In the preparation method, the solubility of the second foaming agents carbon dioxide and nitrogen in the 2, 5-furandicarboxylic acid-based polyester plastic is limited, the solubility of the first foaming agents chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol in the polymer is high, the boiling point is low, the first foaming agents chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol can be changed into gas from liquid at a lower temperature, and the first foaming agents in the gas state can generate certain interaction with the 2, 5-furandicarboxylic acid-based polyester plastic in the saturation process and are easily dissolved in the 2, 5-furandicarboxylic acid-based polyester plastic. When the first foaming agent is dissolved in the 2, 5-furandicarboxylic acid based polyester plastic, the first foaming agent can plasticize the 2, 5-furandicarboxylic acid based polyester plastic, so that the glass transition temperature of the 2, 5-furandicarboxylic acid based polyester plastic is reduced. This also promotes slow dissolution of the second blowing agent in the 2, 5-furandicarboxylic acid based polyester plastic. The first foaming agent and the second foaming agent play a foaming role at the same time, and the combination of the two foaming agents can improve the solubility of the second foaming agent in the 2, 5-furandicarboxylic acid based polyester plastic matrix, thereby greatly improving the foaming performance of the 2, 5-furandicarboxylic acid based polyester. In addition, the gas saturation stage of the method does not need to be carried out at high temperature, so that the energy consumption can be reduced.
The invention also provides the 2, 5-furandicarboxylic acid based polyester foaming material prepared by the preparation method, wherein the size of the foam pores of the 2, 5-furandicarboxylic acid based polyester foaming material is 5-50 mu m, and the expansion ratio is 2-15 times.
The prepared 2, 5-furandicarboxylic acid based polyester foam material has the cell size reaching the category of microporous foam materials, is uniform in cell size and proper in expansion ratio, can reduce weight of plastics on the premise of not greatly reducing the physical and mechanical properties of the 2, 5-furandicarboxylic acid based polyester, and simultaneously remarkably improves the toughness of the material, so that the 2, 5-furandicarboxylic acid based polyester foam material has a great number of potential applications in the fields of packaging, household appliances, automobile parts, sports, buildings, separation membranes and the like.
Hereinafter, the 2, 5-furandicarboxylic acid based polyester foam and the method for preparing the same will be further described by specific examples.
In the following examples, the 2, 5-furandicarboxylic acid based polyester used was mainly polyethylene 2, 5-furandicarboxylic acid ester (PEF) which was self-prepared by a two-step melting method and the number average molecular weight of the resulting product was 3.8 × 1041, 3-propanediol 2, 5-furandicarboxylate (PTF), prepared by itself using a direct esterification process, the resulting product having a number average molecular weight of 5.9 × 104Self-prepared poly-1, 4-butanediol-2, 5-furandicarboxylate (PBF) by direct esterification, the resulting product having a number average molecular weight of 2.6 × 1041, 6-hexanediol, poly-2, 5-furandicarboxylic acid (PHF), prepared by itself by direct esterification, the number average molecular weight of the product obtained being 2.3 × 1041, 8-octanedionate poly-2, 5-furandicarboxylic acid (POF) prepared by itself by the direct esterification method, the number average molecular weight of the obtained product being 2.1 × 104. And the PEF, the PTF, the PBF, the PHF and the POF are all made into plastic granules after melt extrusion granulation for standby.
Example 1:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 70 ℃ for 10 hours to remove water in the PEF plastic particles so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 c to form a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was quenched in liquid nitrogen for 5min to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact with a beaker containing ether, using 1mL of ether per 50g of preform. Setting the temperature in the autoclave at 45 ℃ to gasify the ether, simultaneously filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 4MPa, and maintaining the pressure for 5 hours.
After the pressure holding, the gas in the autoclave was rapidly removed within 30 seconds, and the preform was taken out and foamed in dimethylsilicone oil at 120 ℃ for 15 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PEF foamed material.
The sectional electron micrographs of the resulting PEF foam are shown in FIGS. 1 and 2, and it can be seen that the preform was foamed completely and uniformly, the cell size was 16.5 μm, and the expansion ratio was 4.93 times.
Example 2:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 70 ℃ for 10 hours to remove water in the PEF plastic particles so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 c to form a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was subjected to a quenching treatment in liquid nitrogen for 6min to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact with a beaker containing ether, using 1mL of ether per 50g of preform. Setting the temperature in the autoclave at 45 ℃ to gasify the ether, filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 5MPa, and maintaining the pressure for 5 hours.
After the pressure holding, the gas in the autoclave was rapidly removed within 30 seconds, and the preform was taken out and foamed in dimethylsilicone oil at 130 ℃ for 10 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PEF foamed material.
The sectional electron micrograph of the resulting PEF foam is shown in fig. 3, and it can be seen that the preform was foamed completely and uniformly, the cell size was 14.8 μm, and the expansion ratio was 4.16 times.
Example 3:
and (3) putting the PEF plastic particles into a vacuum oven, and drying for 15 hours at 70 ℃ to remove water in the PEF plastic particles, so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 c to form a thin plate-like preform having a thickness of 0.5mm, the thin plate-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was put in liquid nitrogen to be quenched for 8min to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact, together with a beaker containing pentane, using 2mL of pentane per 50g of preform. Setting the temperature in the autoclave at 40 ℃ to gasify pentane, filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 6MPa, and maintaining the pressure for 4 hours.
After the pressure holding, the gas in the autoclave was rapidly removed within 30 seconds, and the preform was taken out and foamed in dimethylsilicone oil at 110 ℃ for 25 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PEF foamed material.
The cell size of the resulting PEF foam was 10.1 μm, and the expansion ratio was 3.21 times.
Example 4:
and (3) placing the PTF plastic particles in a vacuum oven, and drying for 15 hours at 70 ℃ to remove moisture in the PTF plastic particles so that the moisture content of the PTF plastic particles is less than or equal to 0.05 wt.%.
The PTF plastic pellets were then placed in a mold, and pressed on a press at 200 ℃ to form a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold was quenched in liquid nitrogen for 10min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact with a beaker containing diethyl ether, using 3mL of diethyl ether per 50g of preform. Setting the temperature in the autoclave at 45 ℃ to gasify the ether, filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 3MPa, and maintaining the pressure for 12 hours.
After the pressure holding, the gas in the autoclave was rapidly removed within 30 seconds, and the preform was taken out and foamed in dimethylsilicone oil at 100 ℃ for 15 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PTF foamed material.
The cell size of the obtained PTF foam was 18.3 μm, and the expansion ratio was 5.13 times.
Example 5:
and (3) placing the PBF plastic particles in a vacuum oven, and drying for 10 hours at 70 ℃ to remove water in the PBF plastic particles, so that the water content of the PBF plastic particles is less than or equal to 0.05 wt.%.
The PBF plastic pellets were then placed in a mold and pressed on a molding press at 180 ℃ into a sheet-like preform having a thickness of 1mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen together with the mold for 7min to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact with a beaker containing diethyl ether, using 4mL of diethyl ether per 50g of preform. Setting the temperature in the autoclave at 48 ℃ to gasify the ether, filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 2MPa, and maintaining the pressure for 12 hours.
After the end of the hold pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 120 ℃ for 15 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PBF foamed material.
The cell size of the resulting PBF foam was 20.6 μm and the expansion ratio was 4.56 times.
Example 6:
and (3) putting the PBF plastic particles into a vacuum oven, and drying at 80 ℃ for 12h to remove water in the PBF plastic particles, so that the water content of the PBF plastic particles is less than or equal to 0.05 wt.%.
The PBF plastic pellets were then placed in a mold and pressed on a molding press at 180 ℃ into a sheet-like preform having a thickness of 1mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 9min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact, together with a beaker containing pentane, using 2mL of pentane per 50g of preform. Setting the temperature in the autoclave at 48 ℃ to gasify pentane, and simultaneously filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 5MPa, and maintaining the pressure for 6 hours.
After the pressure holding, the gas in the autoclave was rapidly discharged within 30 seconds, and the preform was taken out and foamed in an engine oil at a temperature of 130 ℃ for 15 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PBF foamed material.
The cell size of the obtained PBF foam was 25.2 μm, and the expansion ratio was 8.12 times.
Example 7:
and (3) putting the PHF plastic particles into a vacuum oven, and drying for 10 hours at 80 ℃ to remove water in the PHF plastic particles, so that the water content of the PHF plastic particles is less than or equal to 0.05 wt.%. .
The PHF plastic pellets were then placed in a mold, and pressed on a molding press at 160 ℃ into a sheet-like preform having a thickness of 1mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 10min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave with a beaker containing pentane, 5mL of pentane being used per 50g of preform. Setting the temperature in the autoclave at 46 ℃ to gasify pentane, and simultaneously filling nitrogen gas into the autoclave to keep the pressure in the autoclave at 3MPa and maintaining the pressure for 7 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 130 ℃ for 10 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PHF foamed material.
The cell size of the obtained PHF foam was 19.3 μm, and the expansion ratio was 7.05 times.
Example 8:
and (3) putting the PHF plastic particles into a vacuum oven, and drying for 10 hours at 70 ℃ to remove water in the PHF plastic particles, so that the water content of the PHF plastic particles is less than or equal to 0.05 wt.%.
The PHF plastic granules were then placed in a mold, and pressed on a press machine at 160 ℃ into a sheet-like preform having a thickness of 0.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 6min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact, together with a beaker containing pentane, using 3mL of pentane per 50g of preform. Setting the temperature in the autoclave at 48 ℃ to gasify pentane, and simultaneously filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 5MPa, and maintaining the pressure for 5 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 130 ℃ for 15 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PHF foamed material.
The cell size of the obtained PHF foam was 26.8 μm, and the expansion ratio was 8.95 times.
Example 9:
and (3) placing the POF plastic particles in a vacuum oven, and drying at 70 ℃ for 13h to remove water in the POF plastic particles so that the water content of the POF plastic particles is less than or equal to 0.05 wt.%.
Then, the POF plastic pellets were placed in a mold, and pressed on a press machine at 150 ℃ into a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was subjected to a quenching treatment in liquid nitrogen for 8min to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact, together with a beaker containing pentane, using 2mL of pentane per 50g of preform. Setting the temperature in the autoclave at 50 ℃ to gasify pentane, filling carbon dioxide gas into the autoclave, keeping the pressure in the autoclave at 5MPa, and maintaining the pressure for 8 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 140 ℃ for 10 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the POF foaming material.
The cell size of the resulting POF foam was 30.5 μm, and the expansion ratio was 10.25 times.
Example 10:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 80 ℃ for 12h to remove water in the PEF plastic particles, so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 ℃ into a sheet-like preform having a thickness of 1.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 7min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave without contact, along with a beaker containing hexafluoroisopropanol, using 1.5mL of hexafluoroisopropanol per 50g of preform. Setting the temperature in the autoclave at 65 ℃ to gasify hexafluoroisopropanol, and simultaneously charging carbon dioxide gas into the autoclave, maintaining the pressure in the autoclave at 2MPa, and maintaining the pressure for 4 hours.
After the pressure holding, the gas in the autoclave was rapidly removed within 30 seconds, and the preform was taken out and foamed in dimethylsilicone oil at 120 ℃ for 10 seconds. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PEF foamed material.
The cell size of the resulting PEF foam was 7.3 μm, and the expansion ratio was 2.85 times.
Example 11:
and (3) putting the PBF plastic particles into a vacuum oven, drying for 14h at 60 ℃ to remove water in the PBF plastic particles, so that the water content of the PBF plastic particles is less than or equal to 0.05 wt.%.
The PBF plastic pellets were then placed in a mold and pressed on a molding press at 180 ℃ into a sheet-like preform having a thickness of 1.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen together with the mold for 6min to obtain a quenched preform.
The quenched preform was placed in an autoclave with a beaker containing acetone, 4mL of acetone per 50g of preform. Setting the temperature in the autoclave at 58 ℃ to gasify the acetone, filling nitrogen gas into the autoclave, keeping the pressure in the autoclave at 3MPa, and maintaining the pressure for 6 hours.
After the end of the hold pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 120 ℃ for 15 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PBF foamed material.
The cell size of the resulting PBF foam was 19.3 μm and the expansion ratio was 4.35 times.
Example 12:
and (3) putting the PHF plastic particles into a vacuum oven, and drying for 10 hours at 80 ℃ to remove water in the PHF plastic particles, so that the water content of the PHF plastic particles is less than or equal to 0.05 wt.%.
The PHF plastic granules were then placed in a mold, and pressed on a press machine at 160 ℃ into a sheet-like preform having a thickness of 1.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 8min together with the mold to obtain a quenched preform.
The quenched preform was placed in an autoclave with 1mL of chloroform for each 50g preform, along with a beaker containing chloroform. Setting the temperature in the autoclave at 65 ℃ to gasify chloroform, and simultaneously charging carbon dioxide gas into the autoclave, maintaining the pressure in the autoclave at 1MPa, and maintaining the pressure for 15 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 160 ℃ for 8 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping to obtain the PHF foamed material.
The cell size of the obtained PHF foam was 15.8 μm, and the expansion ratio was 4.97 times.
Comparative example 1:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 70 ℃ for 10 hours to remove water in the PEF plastic particles so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 c to form a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was quenched in liquid nitrogen for 5min to obtain a quenched preform.
And (3) placing the quenched prefabricated product into a high-pressure kettle, setting the temperature in the high-pressure kettle to be 45 ℃, filling carbon dioxide gas into the high-pressure kettle, keeping the pressure in the high-pressure kettle to be 4MPa, and maintaining the pressure for 5 hours.
After the pressure holding is finished, the gas in the autoclave is quickly removed within 30s, and the prefabricated product is taken out and placed in a dimethyl silicon source with the temperature of 120 ℃ for foaming for 15 s. Finally, the preform was placed in ice water to be cooled and set, and the sectional electron microscope image of the resulting PEF material is shown in fig. 4, which shows that the PEF material had only a thin foamed layer on the outer surface, a thickness of not more than 200 μm, extremely uneven cells, and no foamed region at all in the inner part of about 800 μm.
Comparative example 2:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 70 ℃ for 10 hours to remove water in the PEF plastic particles so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 180 ℃ into a sheet-like preform having a thickness of 1mm, the sheet-like preform being in a molten state, and the preform in the molten state in the mold together with the mold was subjected to a quenching treatment in liquid nitrogen for 9min to obtain a quenched preform.
And (3) placing the quenched prefabricated product into a high-pressure kettle, setting the temperature in the high-pressure kettle to be 48 ℃, filling carbon dioxide gas into the high-pressure kettle, keeping the pressure in the high-pressure kettle to be 5MPa, and maintaining the pressure for 6 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 130 ℃ for 15 s. Finally, the preform was placed in ice water to be cooled and set, and the sectional electron microscope image of the resulting PEF material is shown in fig. 5, which shows that the PEF material had only a thin foamed layer on the outer surface, a thickness of not more than 200 μm, extremely uneven cells, and no foamed region at all in the inner part of about 800 μm.
Comparative example 3:
and (3) putting the PHF plastic particles into a vacuum oven, and drying for 10 hours at 70 ℃ to remove water in the PHF plastic particles, so that the water content of the PHF plastic particles is less than or equal to 0.05 wt.%.
The PHF plastic granules were then placed in a mold, and pressed on a press machine at 160 ℃ into a sheet-like preform having a thickness of 0.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 6min together with the mold to obtain a quenched preform.
And (3) placing the quenched prefabricated product into a high-pressure kettle, setting the temperature in the high-pressure kettle to be 48 ℃, filling carbon dioxide gas into the high-pressure kettle, keeping the pressure in the high-pressure kettle to be 5MPa, and maintaining the pressure for 5 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 130 ℃ for 15 s. And finally, placing the foamed prefabricated product in ice water for cooling and shaping, so that the PHF foamed material cannot be obtained.
Comparative example 4:
and (3) putting the PEF plastic particles into a vacuum oven, and drying at 80 ℃ for 10 hours to remove water in the PEF plastic particles so that the water content of the PEF plastic particles is less than or equal to 0.05 wt.%.
The PEF plastic pellets were then placed in a mold and pressed on a molding press at 220 ℃ into a sheet-like preform having a thickness of 1.5mm, which was in a molten state, and the preform in the molten state in the mold was then quenched in liquid nitrogen for 7min together with the mold to obtain a quenched preform.
And (3) placing the quenched prefabricated product into a high-pressure kettle, setting the temperature in the high-pressure kettle to be 65 ℃, filling carbon dioxide gas into the high-pressure kettle, keeping the pressure in the high-pressure kettle to be 2MPa, and maintaining the pressure for 4 hours.
After the end of the holding pressure, the autoclave was rapidly degassed within 30s, and the preform was taken out and foamed in glycerol at 120 ℃ for 10 s. And finally, placing the prefabricated product in ice water for cooling and shaping, so that the PEF foaming material cannot be obtained.
In summary, the 2, 5-furandicarboxylic acid based polyester added with the first foaming agent can be completely foamed, and the cell structure is relatively uniform. Whereas 2, 5-furandicarboxylic acid based polyesters, to which no first blowing agent has been added, have a very inhomogeneous cell structure only in the skin layers of the material, whereas the inner layers are not foamed at all. Therefore, the addition of the first foaming agent can obviously promote the swelling and dissolving processes of the foaming agent in the matrix, and obviously improve the foaming performance of the 2, 5-furandicarboxylic acid-based polyester.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The preparation method of the 2, 5-furandicarboxylic acid based polyester foaming material is characterized by comprising the following steps:
(a) placing 2, 5-furandicarboxylic acid-based polyester plastic in a mold, pressing into a sheet-shaped preform, and quenching the sheet-shaped preform;
(b) placing the pre-product after quenching treatment and a first foaming agent in a closed container; wherein the first foaming agent is not in contact with the preform, and the first foaming agent is at least one of chloroform, acetone, diethyl ether, pentane and hexafluoroisopropanol;
(c) introducing a second foaming agent into the closed container, wherein the second foaming agent is at least one of carbon dioxide and nitrogen, keeping the temperature in the closed container at 40-65 ℃, so that the first foaming agent is changed from a liquid state into a gas state, keeping the pressure in the closed container at 1-6 MPa, and keeping the pressure for 4-15 h;
(d) and (3) removing the gas in the closed container, taking out the prefabricated product, placing the prefabricated product in a foaming medium for foaming, wherein the foaming medium is at least one of simethicone, glycerin and engine oil, and cooling to obtain the 2, 5-furandicarboxylic acid based polyester foaming material.
2. The method for preparing 2, 5-furandicarboxylic acid based polyester foamed material according to claim 1, wherein the 2, 5-furandicarboxylic acid based polyester plastic in the step (a) is at least one of polyethylene glycol 2, 5-furandicarboxylate, 1, 3-propylene glycol 2, 5-furandicarboxylate, 1, 4-butylene glycol 2, 5-furandicarboxylate, 1, 6-hexanediol 2, 5-furandicarboxylate, and 1, 8-octanediol 2, 5-furandicarboxylate.
3. The method for preparing 2, 5-furandicarboxylic acid based polyester foam according to claim 1, wherein the water content of the 2, 5-furandicarboxylic acid based polyester in the step (a) is not more than 0.05 wt.%.
4. The method for preparing 2, 5-furandicarboxylic acid-based polyester foam according to claim 1, wherein the thickness of the preform in the step (a) is 1.5mm or less.
5. The method for preparing 2, 5-furandicarboxylic acid-based polyester foam according to claim 1, wherein the sheet-shaped preform in the step (a) is in a molten state, and the quenching process is performed for 5min to 10 min.
6. The method for preparing 2, 5-furandicarboxylic acid-based polyester foam according to claim 1, wherein the ratio of the preform to the first foaming agent in the step (b) is: 50 g: (1 mL-5 mL).
7. The method for preparing 2, 5-furandicarboxylic acid-based polyester foam according to claim 1, wherein the gas in the closed vessel is discharged within 30s in the step (d).
8. The method for preparing 2, 5-furandicarboxylic acid based polyester foaming material according to claim 1, wherein the foaming temperature in step (d) is 100 ℃ to 160 ℃ and the foaming time is 8s to 25 s.
9. The 2, 5-furandicarboxylic acid based polyester foam material obtained by the preparation method of any one of claims 1 to 8, wherein the 2, 5-furandicarboxylic acid based polyester foam material has a cell size of 5 to 50 μm and an expansion ratio of 2 to 15 times.
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CN102952253A (en) * 2012-11-01 2013-03-06 中国科学院宁波材料技术与工程研究所 Epoxy resin based on 2,5-furandicarboxylic acid, preparation method and application thereof
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WO2012162645A2 (en) * 2011-05-25 2012-11-29 E. I. Du Pont De Nemours And Company Closed-cell tannin-based foams without formaldehyde
CN102952253A (en) * 2012-11-01 2013-03-06 中国科学院宁波材料技术与工程研究所 Epoxy resin based on 2,5-furandicarboxylic acid, preparation method and application thereof
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