CN114249887B - Branched polymer, preparation thereof and foam material - Google Patents
Branched polymer, preparation thereof and foam material Download PDFInfo
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- CN114249887B CN114249887B CN202011015841.1A CN202011015841A CN114249887B CN 114249887 B CN114249887 B CN 114249887B CN 202011015841 A CN202011015841 A CN 202011015841A CN 114249887 B CN114249887 B CN 114249887B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/30—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type branched
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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Abstract
The invention provides a branched polymer and a preparation method thereof, which solve the problem of cross-linking in the existing preparation process of branched polyaryletherketone (sulfone) and realize the unification of the high branching degree and the high molecular weight of the branched polyaryletherketone (sulfone). The structural formula of the polymer is shown as a formula (I) or a formula (II). The invention also provides a foam material prepared by using the polymer as matrix resin, and the foaming mode is supercritical carbon dioxide foaming.
Description
Technical Field
The invention belongs to the field of polymer synthesis and processing, and particularly relates to a branched polymer, a preparation method and a foam material thereof.
Background
Due to the particularity of the fields such as aerospace, rail transit, national defense equipment and the like, a large amount of polymer foam is needed due to the requirement of weight reduction, and the requirements on the polymer foam, such as high temperature resistance, flame retardance, high mechanical strength and the like, are high, so that the development of high-performance foam materials becomes an important research direction. The polyaryletherketone (sulfone) foam is a thermoplastic high-performance foam material, has the characteristics of radiation resistance, chemical corrosion resistance, high heat-resistant grade and good flame retardance, and has wide application prospects in the aspects of weight reduction, heat preservation and the like of high-end equipment. The foaming mode of the polyaryletherketone (sulfone) adopts a supercritical carbon dioxide foaming process, and the preparation of the polyaryletherketone (sulfone) foam with high foaming ratio is always a difficult problem: the crystallization type polyaryletherketone has narrow foaming window, low product repetition rate, high requirement on equipment precision and large difficulty in industrial production. In the patent (CN 201710793564.9), a polyaryletherketone (sulfone) with a long branched chain structure is synthesized by a multifunctional monomer copolymerization mode, so that a high-magnification polyaryletherketone (sulfone) foam material is prepared, the problem of wide foaming window is solved, and the industrial production of the high-magnification polyaryletherketone (sulfone) foam becomes possible. However, the introduction of polyfunctional monomers makes the polymerization process susceptible to crosslinking, which can cause difficulties in post-treatment and processing of the polymer, and the degree of reaction must be reduced to avoid crosslinking, which can reduce the molecular weight and mechanical properties of the polymer, thereby affecting the service properties of the polymer foam.
Disclosure of Invention
The invention firstly provides a novel branched polyaryletherketone (sulfone) with a structural formula shown as one or two of a formula (I) or a formula (II):
wherein X is selected from one or two of the following structures A or B:
ph is selected from one or more than two of the following structures 1-7:
wherein y is the polymerization degree which is an integer and is more than 10 and less than 50;
ar is selected from one or more than two of the following structures alpha-gamma:
ar ' is selected from one or more than two of the following structures a-g, when Ar ' is a-e, the structural formula of the polymer corresponds to the formula (I), and when Ar ' is f-g, the structural formula of the polymer corresponds to the formula (II):
in the formula (I), m, n and p are integers with the polymerization degree of 10 < (m + p) < 100,5 < m < 60,5 < p < 60 and 10 < n < 100;
in the formula (II), m ', n ', p ', q ' are polymerization degrees and are integers, 10 < (m ' + p ' + q ') is less than 100,5 < m ' < 60,5 < p ' < 60,5 < q ' < 60,10 < n ' < 100;
2. the invention also provides a preparation method of the polymer, which comprises the following specific steps: firstly, sequentially adding a bisphenol monomer, 4-dihalobenzophenone and/or 4, 4-dihalodiphenylsulfone monomer, a polyphenol monomer, a solvent, a catalyst and a water-carrying agent into a reaction vessel, reacting at the temperature of 130-180 ℃, refluxing for 1-3h under the protection of nitrogen, then discharging the water-carrying agent and the generated water, heating to 180-230 ℃ for reacting for 2-5h to generate a halogen atom-terminated branched polymer, cooling to 130-160 ℃, adding an AB monomer and the water-carrying agent, refluxing for 1-3h, removing the water-carrying agent, heating to 180-230 ℃ for reacting for 1-4h, ending the reaction, adding N, N-dimethylacetamide (DMAc) for diluting, finally precipitating in an ethanol-water mixed solution, crushing, boiling and washing for 5-6 times by deionized water, each time for 40-90 min, and drying to obtain the target branched polymer powder.
The bisphenol monomer is preferably one or more than two of the following structures α - γ:
the 4, 4-dihalo benzophenone is one or two of 4, 4-difluorobenzophenone or 4, 4-dichlorobenzophenone;
the 4, 4-dihalo diphenyl sulfone is one or two of 4, 4-difluoro diphenyl sulfone or 4, 4-dichloro diphenyl sulfone.
The mass ratio of bisphenol to 4, 4-dihalobenzophenone or 4, 4-dihalodiphenylsulfone is 70:100-99:100;
the mass ratio of the polyhydric phenol to the bisphenol is 1:100-20:100;
the solvent is one or more of sulfolane (TMS), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), and the mass of the solvent is 2-8 times of the theoretical mass yield of the polymer;
the water-carrying agent is one or two of toluene and xylene, and the mass of the water-carrying agent is 5-70% of the mass of the solvent;
the catalyst is one or the combination of more than two of potassium carbonate, sodium carbonate and calcium carbonate, and the amount of the substance of the catalyst is 1.15 to 1.5 times of that of 4, 4-dihalo benzophenone (sulfone);
the mass of DMAc is 0.5-8 times of the theoretical mass yield of the polymer;
the volume ratio of ethanol to water in the ethanol-water mixture is 90:10-40:60;
the AB monomer is a monomer having a phenolic hydroxyl group at one end and a halogenobenzene at the other end, and preferably one or more than two of the following structures 1 to 7, but not limited to structures 1 to 7;
the molar ratio of the AB monomer to the polyhydric phenol monomer is 20:1-100:1;
the polyhydric phenol monomer can be one or more than two of ternary phenol, quaternary phenol, pentabasic phenol and hexabasic phenol, and preferably one or more than two of structures a-g, but not limited to structures a-g:
3. the foamed material of the polymer with the structure of the formula (I) or the formula (II) comprises a foamed plate, foamed beads and a foamed sheet, and is prepared by the following steps:
the preparation method of the foam board comprises the following steps: and (2) die pressing the powdery polymer into a plate on a hot press, wherein the die pressing temperature is 300-380 ℃, the pressure is 5-10 MPa, the die pressing time is 30-60 min, the thickness of the obtained plate is 0.5-10mm, then the obtained plate is placed in an autoclave, the autoclave body is sealed, carbon dioxide is introduced, the pressure is kept at 5-20MPa, the temperature is 200-350 ℃, after 1-5h, the pressure in the autoclave is quickly reduced to normal pressure through a pressure release valve, the autoclave body is opened, a sample is taken out, and the sample is cooled to room temperature, so that the target foamed plate is obtained. Preparation method of foam beads: processing a powdery polymer into granules with uniform size and diameter of 0.5-3mm by a single screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 5-20MPa, the temperature of 200-300 ℃ and the pressure of the pressure release valve to normal pressure under the condition of mechanical stirring, after 0.5-2h, quickly reducing the pressure in the kettle to normal pressure, ejecting foam beads from a pressure release port, collecting and cooling to obtain the target foam beads.
The preparation method of the foam sheet comprises the following steps: and (2) molding the powdery polymer into sheets on a hot press, wherein the molding temperature is 300-380 ℃, the pressure is 5-10 MPa, the molding time is 30-60 min, and the thickness of the sheets is 0.1-0.5mm, then placing the obtained sheets into an autoclave, sealing the autoclave body, introducing carbon dioxide, keeping the pressure at 5-20MPa, the temperature at 35-80 ℃, rapidly reducing the pressure in the autoclave to normal pressure through a pressure relief valve after 1-5h, taking out the polymer sheets, rapidly placing the polymer sheets into a high-temperature oil bath or other high-temperature environments (150-250 ℃) for foaming, taking out the polymer sheets after 10-120s, and cooling to obtain the target foam sheets.
The beneficial effects that this application can produce include: the invention improves the molecular structure and the synthesis process of the long-chain-branch polyaryletherketone (sulfone), firstly synthesizes a branched polymer terminated by halogenobenzene, and then uses an AB monomer to carry out chain extension, thereby improving the molecular weight, solving the problem of cross-linking in the synthesis of the long-chain-branch polyaryletherketone (sulfone) in the prior art, having practical significance for preparing the long-chain-branch polyaryletherketone (sulfone) with both processing performance and mechanical performance, and further having better mechanical strength under the condition of the same density by using a foam material prepared by using the polymer.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the polymer prepared in example 1 of the present invention
FIG. 2 is a SEM photograph of the foam board prepared in example 1 of the present invention
FIG. 3 is a schematic representation of the foam beads prepared in example 1 of the present invention
FIG. 4 SEM photograph of foam sheet prepared in example 1 of the present invention
Detailed Description
Example 1
To a three-necked flask, phenolphthalein (100 mmol), 4-difluorobenzophenone (127 mmol), 1-tris (4-hydroxyphenyl) ethane (8 mmol), and K were added 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature constant for 2h, removing the toluene and the generated water, continuously heating to 220 ℃ for reaction for 2h, cooling to 150 ℃, adding (4-fluorobenzene) - (4-hydroxy-3-phenylbenzene) ketone (150 mmol) and toluene (50 ml) for reaction for 2h, removing the toluene, heating to 220 ℃ for reaction for 2h, ending the reaction, adding 250ml DMAc for dilution, precipitating in an ethanol-water (50) mixed solution, filtering and crushing precipitates, repeatedly boiling and washing with deionized water for 5 times, 60min each time, removing inorganic salt and residual solvent, and drying to obtain the polyaryletherketone containing the long branched chain structure and having the structure of the formula (III). (10<m+p<15,5<m<10,5<p<10,20<n<30,10<y<20)
Molding the crushed and dried powdery sample in a hot press, stopping heating after the temperature is 350 ℃, the pressure is 5MPa and 30min, and after the temperature is reduced to be below 50 ℃, relieving pressure and taking out the sample to obtain a plate with the thickness of 4 mm;
by using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in a high-pressure kettle, sealing the kettle body, and using high-pressure CO 2 The autoclave chamber was purged 2-3 times in order to remove the air from the chamber, and then CO was injected into the autoclave through a pressurization system 2 Controlling the constant pressure of gas to be 10MPa, raising the temperature of the kettle to 280 ℃, preserving heat and pressure for 2.5h, then rapidly reducing the pressure to the normal pressure through a pressure reducing valve, and reducing the pressure at a speed>10MPa, opening the kettle body, taking out a sample, and cooling to room temperature to obtain a foam plate with the foam density of 0.081g/cm 3 The compressive strength was 1.07MPa. Placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, maintaining the pressure at 8MPa and the temperature at 50 ℃, passing through a pressure release valve after 3 hoursAnd (3) rapidly reducing the pressure in the kettle to normal pressure, taking out the polymer sheet, rapidly placing the polymer sheet into a high-temperature oil bath (180 ℃) for foaming, taking out the polymer sheet after 60 seconds, and cooling to obtain the target foam sheet. Processing the crushed sample into granules with uniform size and diameter of 0.7mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 10MPa and the temperature of 230 ℃ under the condition of mechanical stirring, quickly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, spraying foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Comparative example 1
To a three-necked flask, phenolphthalein (100 mmol), 4-difluorobenzophenone (117 mmol), 1-tris (4-hydroxyphenyl) ethane (8 mmol), and K were added 2 CO 3 (115 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature for 2h, removing the toluene and the generated water, continuously heating to 220 ℃ for reaction for 4h, cooling, adding 250ml DMAc for dilution, precipitating in ethanol/water, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times, 60min each time, removing inorganic salt and residual solvent, and drying to obtain the polyaryletherketone containing long branched chain structure with the structure of formula (IV).
The difference from example 1 is that no 4-fluoro-4' -hydroxybenzophenone was added for chain extension, resulting in a lower molecular weight and the same foaming procedure was used to obtain a density of 0.080g/cm 3 The compressive strength of the foam of (1) is only 0.080MPa.
Example 2
Into a three-necked flask, phenolphthalein (100 mmol), 4-difluorodiphenylsulfone (125 mmol), phloroglucinol (8 mmol), and K were added 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature for 2h, removing the toluene, continuing heating to 220 ℃ for reaction for 2h, cooling to 150 ℃, adding 4-fluoro-4' -hydroxyReacting diphenyl sulfone (150 mmol) with toluene (50 ml) for 2h, removing toluene and generated water, heating to 220 ℃ for 2h, ending the reaction, adding 250ml DMAc for dilution, precipitating in ethanol/water (50), filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times, 60min each time, removing inorganic salt and residual solvent, and drying to obtain the polyarylether sulfone containing a long branched chain structure with the structure of formula (V). (10<m+p<15,5<m<10,5<p<10,20<n<30,10<y<20)
And (3) carrying out die pressing on the crushed and dried powdery sample in a hot press, stopping heating after the temperature is 360 ℃, the pressure is 5MPa, and 30min, and after the temperature is reduced to be below 50 ℃, relieving pressure, taking out a sample plate, wherein the thickness is 3.5mm.
By using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in an autoclave, sealing the autoclave body, and using high-pressure CO 2 Purging the kettle cavity for 2-3 times to remove air in the cavity, injecting CO2 gas into the autoclave through a pressurization system, controlling the constant pressure to be 15MPa, raising the temperature of the kettle to 270 ℃, keeping the temperature and the pressure for 2.5h, rapidly reducing the pressure to normal pressure through a pressure reducing valve, and reducing the pressure at a rate of>10MPa, opening the kettle body, taking out a sample, and cooling to room temperature to obtain a foam sample, wherein the foam density is 0.093g/cm 3 The compressive strength was 1.23MPa.
And (3) placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure at 10MPa and the temperature at 50 ℃, quickly reducing the pressure in the kettle to normal pressure through a pressure relief valve after 3 hours, taking out the polymer sheet, quickly placing the polymer sheet in a high-temperature oil bath (170 ℃) for foaming, taking out the polymer sheet after 60 seconds, and cooling to obtain the target foam sheet.
Processing the crushed sample into granules with uniform size and diameter of 0.5mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 10MPa and the temperature of 230 ℃ under the condition of mechanical stirring, rapidly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, ejecting foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Example 3
To a three-necked flask, phenolphthalein (100 mmol), 4-difluorodiphenylsulfone (127 mmol), 1,3, 5-tris (4-hydroxyphenyl) benzene (3 mmol), and K were added 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature for 2h, removing the toluene and the generated water, continuing to heat to 220 ℃ for reaction for 2h, cooling to 150 ℃, adding 4-fluoro-4' -hydroxy diphenyl sulfone (150 mmol) and toluene (50 ml) for reaction for 2h, removing the toluene, heating to 220 ℃ for reaction for 2h, finishing the reaction, adding 250ml of DMAc for dilution, precipitating in ethanol/water (50). (15<m+p<20,5<m<10,5<p<10,20<n<30,10<y<20)
And (3) carrying out die pressing on the crushed and dried powdery sample in a hot press, stopping heating after the temperature is 360 ℃, the pressure is 5MPa, and 30min, and after the temperature is reduced to be below 50 ℃, relieving pressure, taking out a sample plate, wherein the thickness is 4mm.
By using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in a high-pressure kettle, sealing the kettle body, and using high-pressure CO 2 Purging the kettle cavity for 2-3 times to remove air in the cavity, injecting CO2 gas into the autoclave through a pressurization system, controlling the constant pressure to be 15MPa, raising the temperature of the kettle to 270 ℃, keeping the temperature and the pressure for 2.5h, rapidly reducing the pressure to normal pressure through a pressure reducing valve, and reducing the pressure at a rate of>10MPa, opening the kettle body, taking out a sample, and cooling to room temperature to obtain a foam sample, namely foamThe density was 0.120g/cm 3 The compressive strength was 1.9MPa.
And (3) placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure at 8MPa and the temperature at 50 ℃, quickly reducing the pressure in the kettle to normal pressure through a pressure relief valve after 3 hours, taking out the polymer sheet, quickly placing the polymer sheet in a high-temperature oil bath (190 ℃) for foaming, taking out the polymer sheet after 60 seconds, and cooling to obtain the target foam sheet.
Processing the crushed sample into granules with uniform size and diameter of 0.7mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 10MPa and the temperature of 225 ℃ under the condition of mechanical stirring, quickly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, ejecting foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Example 4
To a three-necked flask, phenolphthalein (100 mmol), 4-difluorodiphenylsulfone (117 mmol), 1,3, 5-tris (4-hydroxyphenyl) benzene (3 mmol), K 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature constant for 2h, removing the toluene, continuously heating to 220 ℃ for reaction for 2h, cooling to 150 ℃, adding AB monomer 3 (150 mmol) and toluene (50 ml) for reaction for 2h, removing the toluene and generated water, heating to 220 ℃ for reaction for 2h, ending the reaction, adding 250ml DMAc for dilution, precipitating in ethanol/water (50), filtering and crushing precipitates, repeatedly boiling and washing with deionized water for 5 times, 60min each time, removing inorganic salt and residual solvent, and drying to obtain the polyarylether sulfone containing a long branched chain structure with the structure of formula (VI). (15<m+p<20,5<m<10,5<p<10,20<n<30,10<y<20)
And (3) carrying out die pressing on the crushed and dried powdery sample in a sulfur press, stopping heating after the temperature is 360 ℃, the pressure is 5MPa and 30min, and after the temperature is reduced to be below 50 ℃, relieving pressure and taking out a sample plate with the thickness of 4mm.
By using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in an autoclave, sealing the autoclave body, and using high-pressure CO 2 Purging the kettle cavity for 2-3 times to remove air in the cavity, injecting CO2 gas into the autoclave through a pressurization system, controlling the constant pressure to be 15MPa, raising the temperature of the kettle to 290 ℃, keeping the temperature and the pressure for 2.5h, rapidly reducing the pressure to normal pressure through a pressure reducing valve, and reducing the pressure at a rate of>10MPa, opening the kettle body, taking out the sample, and cooling to room temperature to obtain a foam sample with the foam density of 0.072g/cm 3 The compressive strength was 1.1MPa.
And (3) placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure at 8MPa and the temperature at 50 ℃, quickly reducing the pressure in the kettle to normal pressure through a pressure relief valve after 3 hours, taking out the polymer sheet, quickly placing the polymer sheet in a high-temperature oil bath (180 ℃) for foaming, taking out the polymer sheet after 60 seconds, and cooling to obtain the target foam sheet.
Processing the crushed sample into granules with uniform size and diameter of 0.7mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 10MPa and the temperature of 230 ℃ under the condition of mechanical stirring, quickly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, spraying foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Example 5
Bisphenol fluorene (100 mmol), 4-difluorodiphenyl sulfone (125 mmol), 1,3, 5-tris (4-hydroxyphenyl) benzene (2 mmol), K 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature constant for 2h, removing the toluene, continuously heating to 230 ℃ for reaction for 2h, cooling to 150 ℃, adding 4-fluoro-4' -hydroxy diphenyl sulfone (300 mmol) and toluene (50 ml) for reaction for 2h, removing the toluene and generated water, heating to 220 ℃ for reaction for 2h, finishing the reaction, adding 250ml DMAc for dilution, precipitating in ethanol/water (50), filtering and crushing precipitates, repeatedly boiling with deionized water, boiling with ethanol/water (50Boiling and washing for 5 times, each time for 60min, removing inorganic salt and residual solvent, and oven drying to obtain polyarylether sulfone containing long branched chain structure with formula (VI). (25<m+p<40,10<m<20,10<p<20,20<n<30,30<y<40)
And (3) carrying out die pressing on the pulverized and dried powdery sample in a hot press, stopping heating after the temperature is 370 ℃, the pressure is 5MPa and 30min, and after the temperature is reduced to be below 50 ℃, releasing pressure and taking out a sample plate, wherein the thickness is 4mm.
By using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in an autoclave, sealing the autoclave body, and using high-pressure CO 2 Purging the kettle cavity for 2-3 times to remove air in the cavity, injecting CO2 gas into the autoclave through a pressurization system, controlling the constant pressure to be 15MPa, raising the temperature of the kettle to 270 ℃, keeping the temperature and the pressure for 2.5h, rapidly reducing the pressure to normal pressure through a pressure reducing valve, and reducing the pressure at a rate of>10MPa, opening the kettle body, taking out a sample, and cooling to room temperature to obtain a foam sample, wherein the foam density is 0.220g/cm 3 The compressive strength was 3.7MPa.
And (3) placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure at 8MPa and the temperature at 60 ℃, quickly reducing the pressure in the kettle to normal pressure through a pressure relief valve after 3 hours, taking out the polymer sheet, quickly placing the polymer sheet in a high-temperature oil bath (180 ℃) for foaming, taking out the polymer sheet after 60 seconds, and cooling to obtain the target foam sheet.
Processing the crushed sample into granules with uniform size and diameter of 0.5mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 8MPa and the temperature of 220 ℃ under the condition of mechanical stirring, quickly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, ejecting foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Example 6
Bisphenol fluorene (100 mmol), 4-difluorobenzophenone (120 mmol), tetraphenol fluorene (8 mmol), and K were charged into a three-necked flask 2 CO 3 (125 mmol), TMS (130 ml) and toluene (50 ml), under the protection of nitrogen, heating the mixture to 150 ℃ for azeotropic dehydration, keeping the temperature constant for 2h, removing the toluene, continuously heating to 220 ℃ for reaction for 2h, cooling to 150 ℃, adding 4-fluoro-4' -hydroxybenzophenone (200 mmol) and toluene (50 ml) for reaction for 2h, removing the toluene and generated water, heating to 220 ℃ for reaction for 2h, ending the reaction, adding 250ml DMAc for dilution, precipitating in ethanol/water (50), filtering and crushing precipitates, repeatedly boiling and washing with deionized water for 5 times, 60min each time, removing inorganic salt and residual solvent, and drying to obtain the polyaryletherketone containing the long branched chain structure and having the structure of formula (VII). (10<m’+p’+q’<25,5<m’<10,5<p’<10,5<q’<10,20<n’<30,10<y<20)
And (3) carrying out die pressing on the pulverized and dried powdery sample in a hot press, stopping heating after the temperature is 360 ℃, the pressure is 5MPa and 30min, and releasing pressure and taking out the sample plate after the temperature is reduced to below 50 ℃, wherein the thickness is 4mm.
By using the same molding process as above, a sheet having a thickness of 0.3mm can be obtained by controlling the amount of the added material.
Placing the prepared plate in an autoclave, sealing the autoclave body, and using high-pressure CO 2 The autoclave chamber was purged 2-3 times in order to remove the air from the chamber, and then CO was injected into the autoclave through a pressurization system 2 Controlling the constant pressure of 15MPa, raising the temperature of the kettle to 290 ℃, keeping the temperature and the pressure for 2.5h, then quickly reducing the pressure to the normal pressure through a pressure reducing valve, and reducing the pressure at a speed>10MPa, opening the kettle body, taking out the sample, and cooling to room temperature to obtain a foam sample with the foam density of 0.066g/cm 3 The compressive strength was 0.97MPa.
And (3) placing the obtained sheet in a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure at 8MPa and the temperature at 50 ℃, quickly reducing the pressure in the kettle to normal pressure through a pressure relief valve after 3 hours, taking out the polymer sheet, quickly placing the polymer sheet in a high-temperature oil bath (200 ℃) for foaming, taking out the polymer sheet after 50 seconds, and cooling to obtain the target foam sheet.
Processing the crushed sample into granules with uniform size and diameter of 0.4mm by a single-screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 8MPa and the temperature of 210 ℃ under the condition of mechanical stirring, rapidly reducing the pressure in the kettle to normal pressure by a pressure release valve after 1h, ejecting foam beads from a pressure release port, cooling and collecting to obtain the target foam beads.
Claims (6)
1. A branched polymer, the structural formula is shown as one or two of formula (I) or formula (II):
wherein X is selected from one or two of the following structures A or B:
ph is selected from one or more than two of the following structures 1-7:
wherein y is the polymerization degree and is an integer, and y is more than 10 and less than 50;
ar is selected from one or more than two of the following structures alpha-gamma:
ar ' is selected from one or more than two of the following structures a-g, when Ar ' is a-e, the structural formula of the polymer corresponds to the formula (I), and when Ar ' is f-g, the structural formula of the polymer corresponds to the formula (II):
in the formula (I), m, n and p are integers with the polymerization degree of 10 < (m + p) < 100,5 < m < 60,5 < p < 60 and 10 < n < 100;
in the formula (II), m ', n ', p ', q ' are polymerization degrees and are integers, 10 < (m ' + p ' + q ') is less than 100,5 < m ' < 60,5 < p ' < 60,5 < q ' < 60, and 10 < n ' < 100.
2. A method of producing the polymer of claim 1, characterized by: firstly, sequentially adding a bisphenol monomer, 4-dihalo benzophenone and/or 4, 4-dihalo diphenyl sulfone monomer, a polyphenol monomer, a solvent, a catalyst and a water-carrying agent into a reaction vessel, reacting at the temperature of 130-180 ℃, refluxing for 1-3 hours under the protection of nitrogen, then discharging the water-carrying agent and generated water, heating to 180-230 ℃ for reacting for 2-5 hours to generate a halogen atom-terminated branched polymer, cooling to 130-160 ℃, adding an AB monomer and the water-carrying agent, refluxing for 1-3 hours, removing the water-carrying agent and the generated water, heating to 180-230 ℃ for reacting for 1-4 hours, finishing the reaction, adding N, N-dimethylacetamide (DMAc) for diluting, finally precipitating in an ethanol-water mixed solution, crushing, boiling and washing for 5-6 times with deionized water, wherein each time is 40-90 min, and drying to obtain target branched polymer powder; the bisphenol monomer is selected from one or more than two of the following structures of alpha-gamma:
the 4, 4-dihalo benzophenone is one or two of 4, 4-difluorobenzophenone or 4, 4-dichlorobenzophenone;
the 4, 4-dihalo diphenyl sulfone is one or two of 4, 4-difluoro diphenyl sulfone or 4, 4-dichloro diphenyl sulfone;
the mass ratio of bisphenol to 4, 4-dihalobenzophenone and/or 4, 4-dihalosulfone is 70:100-99:100;
the mass ratio of the polyhydric phenol to the bisphenol is 1:100-20:100, respectively;
the solvent is one or more of sulfolane TMS, dimethyl sulfoxide DMSO and N-methylpyrrolidone NMP, and the mass of the solvent is 2-8 times of the theoretical mass yield of the polymer;
the water-carrying agent is one or two of methylbenzene and dimethylbenzene, and the mass of the water-carrying agent is 5-70% of that of the solvent;
the catalyst is one or the combination of more than two of potassium carbonate, sodium carbonate and calcium carbonate, and the amount of the substance of the catalyst is 1.15 to 1.5 times of that of 4, 4-dihalo-benzophenone and/or 4, 4-dihalo-diphenyl sulfone;
the mass of DMAc is 0.5-8 times of the theoretical mass yield of the polymer;
the volume ratio of ethanol to water in the mixture of ethanol and water is 90:10-40:60;
the AB monomer is a monomer with one end being phenolic hydroxyl and the other end being halobenzene and is selected from one or more than two of the following structures 1-7;
the molar ratio of the AB monomer to the polyhydric phenol monomer is 20:1-100:1;
the polyphenol monomer is one or more than two of ternary phenol, quaternary phenol, pentabasic phenol and hexabasic phenol.
3. The method for producing a polymer according to claim 2, characterized in that:
the mass of the solvent is 3-5 times of the theoretical mass yield of the polymer;
the mass of the water-carrying agent is 10-30% of the mass of the solvent; the mass of DMAc is 0.5-2 times of the theoretical mass yield of the polymer;
the polyphenol monomer is selected from one or more than two of the following structures a-g:
4. a foam material having one or more polymers of formula (I) or formula (II) as defined in claim 1.
5. The foam material of claim 4, wherein the foam material is in the form of a foam slab, foam bead or foam sheet.
6. The foam of claim 5, prepared by the following process:
the preparation method of the foam board comprises the following steps: pressing the powdery polymer on a hot press to form a plate, wherein the pressing temperature is 300-380 ℃, the pressure is 5-10 MPa, the pressing time is 30-60 min, the thickness of the obtained plate is more than 0.5-10mm, then the obtained plate is placed in an autoclave, the autoclave body is sealed, carbon dioxide is introduced, the pressure is kept at 5-20MPa, the temperature is 200-350 ℃, after 1-5h, the pressure in the autoclave is quickly reduced to normal pressure through a pressure release valve, the autoclave body is opened, a sample is taken out, and the sample is cooled to room temperature, so that the target foamed plate is obtained;
preparation method of foam beads: processing a powdery polymer into granules with uniform size and diameter of 0.5-3mm by a single screw extruder, then placing the obtained granules into a high-pressure kettle, sealing the kettle body, introducing carbon dioxide, keeping the pressure of 5-20MPa, the temperature of 200-300 ℃ and 0.5-2h under the condition of mechanical stirring, quickly reducing the pressure in the kettle to normal pressure by a pressure relief valve, ejecting foam beads from a pressure relief port, cooling and collecting to obtain target foam beads;
the preparation method of the foam sheet comprises the following steps: and (2) molding the powdery polymer on a hot press to form a sheet, wherein the molding temperature is 300-380 ℃, the pressure is 5-10 MPa, the molding time is 30-60 min, and the thickness of the sheet is 0.1-0.5mm, then placing the obtained sheet in an autoclave, sealing the autoclave body, introducing carbon dioxide, keeping the pressure at 5-20MPa, the temperature at 35-80 ℃, rapidly reducing the pressure in the autoclave to normal pressure through a pressure relief valve after 1-5h, taking out the polymer sheet, rapidly placing the polymer sheet in a high-temperature oil bath or an environment with the temperature of 150-250 ℃ for foaming, taking out the polymer sheet after 10-120s, and cooling to obtain the target foam sheet.
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| US6743889B1 (en) * | 2002-07-10 | 2004-06-01 | The United States Of America As Represented By The Secretary Of The Air Force | Hyperbranched ether-ketone co-polymers |
| CN101357985A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Hyperbranched poly(aryl ether ketone), preparation method and application thereof in viscosity modifier |
| CN102408558A (en) * | 2011-09-21 | 2012-04-11 | 四川大学 | Long-chain branched poly(p-dioxanone) and preparation method thereof |
| CN107474242A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院长春应用化学研究所 | A kind of polymer containing long branched chain structure, preparation method and foamed material |
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| US6743889B1 (en) * | 2002-07-10 | 2004-06-01 | The United States Of America As Represented By The Secretary Of The Air Force | Hyperbranched ether-ketone co-polymers |
| CN101357985A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Hyperbranched poly(aryl ether ketone), preparation method and application thereof in viscosity modifier |
| CN102408558A (en) * | 2011-09-21 | 2012-04-11 | 四川大学 | Long-chain branched poly(p-dioxanone) and preparation method thereof |
| CN107474242A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院长春应用化学研究所 | A kind of polymer containing long branched chain structure, preparation method and foamed material |
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