CN114249887B - Branched polymer, preparation thereof and foam material - Google Patents

Abstract

The invention provides a branched polymer and a preparation method thereof, which solves the problem of cross-linking in the preparation process of the existing branched polyaryletherketone (sulfone), and realizes the branched polyaryletherketone (sulfone) with high branching degree and high Unity of molecular weight. The structural formula of the polymer is shown in formula (I) or formula (II). The invention also provides a foam material prepared by using the polymer as a matrix resin, and the foaming method is supercritical carbon dioxide foaming.

Description

A kind of branched polymer and its preparation and foam material

technical field

The invention belongs to the field of polymer synthesis and processing, and in particular relates to a branched polymer, a preparation method and a foam material thereof.

Background technique

Aerospace, rail transit, national defense equipment and other fields need to use a large amount of polymer foam due to the demand for weight reduction. Due to the particularity of these fields, the requirements for polymer foam are very high, such as high temperature resistance, flame retardancy, high mechanical Therefore, the development of high-performance foam materials has become an important research direction. Polyaryletherketone (sulfone) foam is a kind of thermoplastic high-performance foam material, which has the characteristics of radiation resistance, chemical corrosion resistance, high heat resistance and good flame retardancy. It has broad application in weight loss and heat preservation of high-end equipment. application prospects. The foaming method of polyaryletherketone (sulfone) adopts supercritical carbon dioxide foaming process, and the preparation of polyaryletherketone (sulfone) foam with high expansion ratio has always been a difficult problem: the foaming window of crystalline polyaryletherketone is narrow, and the product The repetition rate is low, the requirements for equipment precision are high, and industrial production is difficult. The patent (CN201710793564.9) synthesized a polyaryletherketone (sulfone) with a long-chain branched structure through the copolymerization of multifunctional monomers, prepared a polyaryletherketone (sulfone) foam material with a high rate, and solved the problem of foaming The problem of wide window makes the industrial production of polyaryletherketone (sulfone) foam with high rate possible. However, due to the introduction of multifunctional monomers, the polymerization process is prone to cross-linking, which will cause difficulties in the post-treatment and processing of the polymer. It is necessary to avoid the occurrence of cross-linking by reducing the degree of reaction, but this will make the polymer The molecular weight and mechanical properties are reduced, which affects the performance of polymer foam.

Contents of the invention

The present invention firstly provides a novel branched polyaryletherketone (sulfone), one or both of which are shown in the formula (I) or formula (II):

Wherein, X is selected from one or both of the following structures A or B:

Ph is selected from one or more of the following structures 1-7:

Among them, y is the polymerization degree, which is an integer, 10<y<50;

Ar is selected from one or more of the following structures α-γ:

Ar' is selected from one or more of the following structures a-g, when Ar' is a-e, the structural formula of the polymer corresponds to formula (I), when Ar' is f-g, the polymer structural formula corresponds to formula (II) Shown:

In the formula (I), m, n, and p are degrees of polymerization, all of which are integers, 10<(m+p)<100, 5<m<60, 5<p<60, 10<n<100;

In formula (II), m', n', p', q' are polymerization degrees, all of which are integers, 10<(m'+p'+q')<100, 5<m'<60, 5<p' <60,5<q'<60,10<n'<100;

2. The present invention also provides the preparation method of above-mentioned polymer, concrete steps are as follows: firstly bisphenol monomer, 4,4-dihalobenzophenone and/or 4,4-dihalodiphenyl sulfone monomer, polyphenol Monomer, solvent, catalyst, and water-carrying agent are added to the reaction vessel in sequence. The reaction temperature is 130°C-180°C. React at 180°C-230°C for 2-5 hours to form a branched polymer terminated by halogen atoms. Cool down to 130°C-160°C, add AB monomer and water-carrying agent, reflux for 1-3 hours, remove the water-carrying agent, and then heat up to React at 180°C-230°C for 1-4h, end the reaction, add N,N-dimethylacetamide (DMAc) to dilute, and finally precipitate in a mixed solution of ethanol-water, grind it, and boil it with deionized water for 5- 6 times, 40min-90min each time, 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-dihalobenzophenone is one or both of 4,4-difluorobenzophenone or 4,4-dichlorobenzophenone;

The 4,4-dihalodiphenylsulfone is one or both of 4,4-difluorodiphenylsulfone or 4,4-dichlorodiphenylsulfone.

The ratio of bisphenol to 4,4-dihalobenzophenone or 4,4-dihalodiphenylsulfone is 70:100-99:100;

The ratio of polyphenols to bisphenols is 1:100-20:100;

The solvent is one or more of sulfolane (TMS), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP), and the quality of the solvent is 2-8 times the theoretical mass output of the polymer;

The water-carrying agent is one or both of toluene and xylene, and the mass of the water-carrying agent is 5%-70% of the solvent mass;

The catalyst is one or more combinations of potassium carbonate, sodium carbonate, and calcium carbonate, and the amount of the catalyst is 1.15-1.5 times that of 4,4-dihalobenzophenone (sulfone);

The quality of DMAc is 0.5-8 times of the theoretical mass output of the polymer;

The volume ratio of ethanol and water in the ethanol-water mixture is 90:10–40:60;

AB monomer refers to a monomer with a phenolic hydroxyl group at one end and a halobenzene at the other end, preferably one or more of the following structures 1-7, but not limited to structures 1-7;

The molar ratio of AB monomer to polyphenol monomer is 20:1-100:1;

Polyhydric phenol monomers can be one or more of trihydric phenols, tetrahydric phenols, pentahydric phenols, and hexahydric phenols, preferably one or more than two of structures a-g, but not limited to structures a-g:

3. have the foam material of the polymer of formula (I) or formula (II) structure, the form of described foam material comprises foam plate, foam bead and foam sheet, and its preparation method is as follows:

The preparation method of the foam board: mold the powdered polymer into a board on a hot press, the molding temperature is 300°C-380°C, the pressure is 5MPa-10MPa, the molding time is 30min-60min, the thickness of the obtained board is 0.5-10mm, and then the obtained board is Put it in an autoclave, seal the kettle body, feed carbon dioxide, keep the pressure at 5-20MPa, and the temperature at 200°C-350°C, after 1-5h, quickly reduce the pressure in the kettle to normal pressure through the pressure relief valve, open the kettle body and take it out The sample was cooled to room temperature, and the target foam board was obtained. The preparation method of foam beads: Process the powdery polymer into pellets of uniform size with a diameter of 0.5-3mm through a single-screw extruder, then place the obtained pellets in an autoclave, seal the kettle body, and pass in carbon dioxide , under the condition of mechanical stirring, keep the pressure at 5-20MPa, the temperature at 200°C-300°C, after 0.5-2h, quickly reduce the pressure in the kettle to normal pressure through the pressure relief valve, and the foam beads will be sprayed out from the pressure relief port. Collect and cool to obtain the target foam beads.

The preparation method of the foam sheet: mold the powdered polymer into a sheet on a hot press, the molding temperature is 300°C-380°C, the pressure is 5MPa-10MPa, the molding time is 30min-60min, and the thickness of the sheet is 0.1-0.5mm, and then Place the obtained sheet in an autoclave, seal the body of the autoclave, feed in carbon dioxide, keep the pressure at 5-20MPa, and the temperature at 35°C-80°C. After 1-5h, quickly reduce the pressure in the autoclave to normal pressure through the pressure relief valve, and take out The polymer sheet is quickly placed in a high-temperature oil bath or other high-temperature environment (150°C-250°C) for foaming, and after 10-120s, it is taken out and cooled to obtain the target foam sheet.

The beneficial effects that can be produced by this application include: the present invention improves the molecular structure and synthesis process of long-chain branched polyaryletherketone (sulfone). Chain, increase molecular weight, solve the problem of crosslinking in the synthesis of long-chain branched polyaryletherketone (sulfone) in the prior art, and have practical application for the preparation of long-chain branched polyaryletherketone (sulfone) with both processability and mechanical properties Meaning, further, the foam material prepared with this polymer has better mechanical strength under the same density condition.

Description of drawings

Fig. 1 is the nuclear magnetic spectrum of the polymer that the embodiment of the present invention 1 prepares

Fig. 2 is the foam board and its SEM photo prepared by Example 1 of the present invention

Fig. 3 is the foam bead that the embodiment of the present invention 1 prepares

The SEM photo of the foam sheet prepared by Fig. 4 embodiment 1 of the present invention

Detailed ways

Example 1

Add phenolphthalein (100mmol), 4,4-difluorobenzophenone (127mmol), 1,1,1-tris(4-hydroxyphenyl)ethane (8mmol), K ₂ CO ₃ (125mmol) into the three-necked flask , TMS (130ml), toluene (50ml), under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene and the water produced, continue to heat to 220°C for 2h, cool down to 150°C , add (4-fluorobenzene)-(4-hydroxy-3-phenylbenzene)methanone (150mmol) and toluene (50ml) to react for 2h, remove the toluene, then raise the temperature to 220°C for 2h, end the reaction, add 250ml of DMAc to dilute , precipitated in a mixed solution of ethanol-water (50:50), filtered, pulverized, and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dry to obtain A polyaryletherketone with a structure of formula (III) containing a long-chain branched structure. (10<m+p<15,5<m<10,5<p<10,20<n<30,10<y<20)

Mold the pulverized and dried powdery sample in a hot press at a temperature of 350°C and a pressure of 5MPa. Stop heating after 30 minutes. After the temperature drops below 50°C, release the pressure and take out the sample to obtain a plate with a thickness of 4mm;

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure CO ₂ for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO ₂ gas into the autoclave through the pressurization system to control The constant pressure is 10MPa, raise the temperature of the kettle to 280°C, keep the temperature and keep the pressure for 2.5h, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, open the kettle body, take out the sample and cool it to room temperature, so as to obtain Foam board, foam density is 0.081g/cm ³ , compressive strength is 1.07MPa. Place the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, maintain a pressure of 8 MPa, and a temperature of 50°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through a pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (180°C) for foaming, take it out after 60 seconds and cool it to obtain the target foam sheet. The pulverized above-mentioned samples are processed into pellets of uniform size by a single-screw extruder, with a diameter of 0.7 mm, and then the obtained pellets are placed in an autoclave, the kettle body is sealed, and carbon dioxide is introduced. Under mechanical stirring conditions, Keep the pressure at 10 MPa and the temperature at 230°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected to obtain the target foam beads.

Comparative example 1

Add phenolphthalein (100mmol), 4,4-difluorobenzophenone (117mmol), 1,1,1-tris(4-hydroxyphenyl)ethane (8mmol), K ₂ CO ₃ (115mmol) into the three-necked flask , TMS (130ml), toluene (50ml), under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene and the water produced, continue to heat to 220°C for 4h, cool down, add 250ml DMAc is diluted, precipitated in ethanol/water, and the precipitate is filtered, pulverized, and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dry to obtain the compound with the structure of formula (IV). Polyaryletherketone with long-chain branched structure.

The difference from Example 1 is that 4-fluoro-4'-hydroxybenzophenone is not added for chain extension, resulting in a low molecular weight. The same foaming process is used to obtain a foam with a density of 0.080g/cm ³ , compressed The strength is only 0.080MPa.

Example 2

Add phenolphthalein (100mmol), 4,4-difluorodiphenyl sulfone (125mmol), phloroglucinol (8mmol), K ₂ CO ₃ (125mmol), TMS (130ml), toluene (50ml) to the three-necked flask, nitrogen Under protective conditions, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene, continue heating to 220°C for 2h, cool down to 150°C, add 4-fluoro-4'-hydroxydiphenylsulfone (150mmol) React with toluene (50ml) for 2h, remove the toluene and the water produced, then raise the temperature to 220°C for 2h, end the reaction, add 250ml of DMAc to dilute, precipitate in ethanol/water (50:50), filter and pulverize the precipitate , and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dry to obtain polyaryl ether sulfone with long-chain branched structure having a structure of formula (V). (10<m+p<15,5<m<10,5<p<10,20<n<30,10<y<20)

Mold the pulverized and dried powder sample in a hot press at a temperature of 360°C and a pressure of 5 MPa. After 30 minutes, stop heating. After the temperature drops below 50°C, release the pressure and take out the sample, with a thickness of 3.5mm.

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure _CO2 for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO2 gas into the autoclave through the pressurization system to control the constant pressure. The pressure is 15MPa, raise the temperature of the kettle to 270°C, keep the temperature for 2.5 hours, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, open the kettle body, take out the sample and cool it to room temperature, so as to obtain the foam The sample has a foam density of 0.093g/cm ³ and a compressive strength of 1.23MPa.

Put the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, keep the pressure at 10 MPa, and the temperature at 50°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through the pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (170° C.) for foaming, take it out after 60 seconds and cool it to obtain the target foam sheet.

The crushed above-mentioned samples were processed into pellets with a uniform size and a diameter of 0.5mm by a single-screw extruder, and then the obtained pellets were placed in an autoclave, the kettle body was sealed, and carbon dioxide was fed into it under mechanical stirring conditions. Keep the pressure at 10 MPa and the temperature at 230°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected to obtain the target foam beads.

Example 3

Phenolphthalein (100mmol), 4,4-difluorodiphenylsulfone (127mmol), 1,3,5-tris(4-hydroxyphenyl)benzene (3mmol), K ₂ CO ₃ (125mmol), TMS (130ml), toluene (50ml), under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene and produced water, continue to heat to 220°C for 2h, cool down to 150°C, Add 4-fluoro-4'-hydroxydiphenyl sulfone (150mmol) and toluene (50ml) to react for 2h, remove the toluene, then raise the temperature to 220°C for 2h to complete the reaction, add 250ml of DMAc for dilution, and dilute in ethanol/water (50: 50) Precipitation, the precipitate is filtered, pulverized, and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dry to obtain the long-chain branched structure having the structure of formula (VI) Polyarylethersulfone. (15<m+p<20,5<m<10,5<p<10,20<n<30,10<y<20)

Mold the pulverized and dried powder sample in a hot press at a temperature of 360°C and a pressure of 5 MPa. After 30 minutes, stop heating. After the temperature drops below 50°C, release the pressure and take out the sample, with a thickness of 4mm.

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure _CO2 for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO2 gas into the autoclave through the pressurization system to control the constant pressure. The pressure is 15MPa, raise the temperature of the kettle to 270°C, keep the temperature for 2.5 hours, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, open the kettle body, take out the sample and cool it to room temperature, so as to obtain the foam The sample has a foam density of 0.120 g/cm ³ and a compressive strength of 1.9 MPa.

Place the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, maintain a pressure of 8 MPa, and a temperature of 50°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through a pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (190°C) for foaming, take it out after 60 seconds and cool it to obtain the target foam sheet.

The pulverized above-mentioned samples are processed into pellets of uniform size by a single-screw extruder, with a diameter of 0.7 mm, and then the obtained pellets are placed in an autoclave, the kettle body is sealed, and carbon dioxide is introduced. Under mechanical stirring conditions, Keep the pressure at 10 MPa and the temperature at 225°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected to obtain the target foam beads.

Example 4

Phenolphthalein (100mmol), 4,4-difluorodiphenyl sulfone (117mmol), 1,3,5-tris(4-hydroxyphenyl)benzene (3mmol), K ₂ CO ₃ (125mmol), TMS (130ml), toluene (50ml), under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene, continue heating to 220°C for 2h, cool down to 150°C, add AB monomer 3 (150mmol) reacted with toluene (50ml) for 2h, removed the toluene and the produced water, and then raised the temperature to 220°C for 2h to complete the reaction, added 250ml of DMAc to dilute, and precipitated in ethanol/water (50:50), the precipitate After filtration, crushing, and repeated boiling and washing with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and drying, the polyarylethersulfone with long-chain branched structure having the structure of formula (VI) was obtained. (15<m+p<20,5<m<10,5<p<10,20<n<30,10<y<20)

Mold the pulverized and dried powdery sample in a sulfur press at a temperature of 360°C and a pressure of 5MPa. After 30 minutes, stop heating. After the temperature drops below 50°C, release the pressure and take out the sample, with a thickness of 4mm.

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure _CO2 for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO2 gas into the autoclave through the pressurization system to control the constant pressure. The pressure is 15MPa, raise the temperature of the kettle to 290°C, keep the pressure for 2.5 hours, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, open the kettle body, take out the sample and cool it to room temperature, so as to obtain the foam The sample has a foam density of 0.072g/cm ³ and a compressive strength of 1.1MPa.

Place the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, maintain a pressure of 8 MPa, and a temperature of 50°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through a pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (180°C) for foaming, take it out after 60 seconds and cool it to obtain the target foam sheet.

The pulverized above-mentioned samples are processed into pellets of uniform size by a single-screw extruder, with a diameter of 0.7 mm, and then the obtained pellets are placed in an autoclave, the kettle body is sealed, and carbon dioxide is introduced. Under mechanical stirring conditions, Keep the pressure at 10 MPa and the temperature at 230°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected to obtain the target foam beads.

Example 5

Add bisphenol fluorene (100mmol), 4,4-difluorodiphenyl sulfone (125mmol), 1,3,5-tris(4-hydroxyphenyl)benzene (2mmol), K ₂ CO ₃ (125mmol) into a three-necked flask ), TMS (130ml), toluene (50ml), under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene, continue to heat to 230°C for 2h, cool to 150°C, add 4 -Fluoro-4'-hydroxydiphenyl sulfone (300mmol) and toluene (50ml) were reacted for 2h, toluene and the water produced were removed, the temperature was raised to 220°C for 2h, and the reaction was terminated. After adding 250ml of DMAc for dilution, the mixture was diluted in ethanol/water ( 50:50), the precipitate was filtered, crushed, and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dried to obtain the long-containing compound with the structure of formula (VI). Branched structure polyarylethersulfone. (25<m+p<40,10<m<20,10<p<20,20<n<30,30<y<40)

Mold the pulverized and dried powder sample in a hot press at a temperature of 370°C and a pressure of 5 MPa. After 30 minutes, stop heating. After the temperature drops below 50°C, release the pressure and take out the sample, with a thickness of 4mm.

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure _CO2 for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO2 gas into the autoclave through the pressurization system to control the constant pressure. The pressure is 15MPa, raise the temperature of the kettle to 270°C, keep the temperature for 2.5 hours, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, open the kettle body, take out the sample and cool it to room temperature, so as to obtain the foam The sample has a foam density of 0.220g/cm ³ and a compressive strength of 3.7MPa.

Place the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, maintain a pressure of 8 MPa, and a temperature of 60°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through a pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (180°C) for foaming, take it out after 60 seconds and cool it to obtain the target foam sheet.

The crushed above-mentioned samples were processed into pellets with a uniform size and a diameter of 0.5mm by a single-screw extruder, and then the obtained pellets were placed in an autoclave, the kettle body was sealed, and carbon dioxide was fed into it under mechanical stirring conditions. Keep the pressure at 8 MPa and the temperature at 220°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected to obtain the target foam beads.

Example 6

Add bisphenol fluorene (100mmol), 4,4-difluorobenzophenone (120mmol), tetraphenol fluorene (8mmol), K ₂ CO ₃ (125mmol), TMS (130ml), toluene (50ml) into the three-necked flask, Under the condition of nitrogen protection, heat the above mixture to 150°C to azeotropically remove water, keep the temperature for 2h, remove toluene, continue heating to 220°C for 2h, cool down to 150°C, add 4-fluoro-4'-hydroxybenzophenone (200mmol ) reacted with toluene (50ml) for 2h, removed the toluene and the water produced, then raised the temperature to 220°C for 2h, ended the reaction, added 250ml of DMAc to dilute, precipitated in ethanol/water (50:50), filtered and pulverized , and repeatedly boiled and washed with deionized water for 5 times, each time for 60 minutes, to remove inorganic salts and residual solvents, and dry to obtain polyaryletherketone with long-chain branched structure having a structure of formula (VII). (10<m'+p'+q'<25,5<m'<10,5<p'<10,5<q'<10,20<n'<30,10<y<20)

Mold the pulverized and dried powder sample in a hot press at a temperature of 360°C and a pressure of 5 MPa. After 30 minutes, stop heating. After the temperature drops below 50°C, release the pressure and take out the sample, with a thickness of 4mm.

Using the same molding process as above, a sheet with a thickness of 0.3 mm can be obtained by controlling the feeding amount.

Place the prepared plate in the autoclave, seal the body of the autoclave, and purge the autoclave cavity with high-pressure CO ₂ for 2-3 times, the purpose is to remove the air in the cavity, and then inject CO ₂ gas into the autoclave through the pressurization system to control The constant pressure is 15MPa, raise the temperature of the kettle to 290°C, keep the pressure for 2.5h, then quickly reduce the pressure to normal pressure through the pressure reducing valve, the pressure reduction rate is >10MPa, and open the kettle body to take out the sample and cool it to room temperature, so as to obtain The foam sample has a foam density of 0.066g/cm ³ and a compressive strength of 0.97MPa.

Place the obtained sheet in an autoclave, seal the body of the autoclave, feed carbon dioxide, maintain a pressure of 8 MPa, and a temperature of 50°C. After 3 hours, quickly reduce the pressure in the autoclave to normal pressure through a pressure relief valve, take out the polymer sheet and quickly Put it into a high-temperature oil bath (200°C) for foaming, take it out after 50 seconds and cool it to obtain the target foam sheet.

The pulverized above-mentioned samples are processed into pellets of uniform size by a single-screw extruder, with a diameter of 0.4 mm, and then the obtained pellets are placed in an autoclave, the kettle body is sealed, and carbon dioxide is introduced. Under mechanical stirring conditions, Keep the pressure at 8 MPa and the temperature at 210°C. After 1 hour, the pressure in the kettle is quickly reduced to normal pressure through the pressure relief valve, and the foam beads are sprayed out from the pressure relief port, cooled and collected 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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