CN115612161A - Method for preparing polymer foam by powder method - Google Patents
Method for preparing polymer foam by powder method Download PDFInfo
- Publication number
- CN115612161A CN115612161A CN202110783380.0A CN202110783380A CN115612161A CN 115612161 A CN115612161 A CN 115612161A CN 202110783380 A CN202110783380 A CN 202110783380A CN 115612161 A CN115612161 A CN 115612161A
- Authority
- CN
- China
- Prior art keywords
- equal
- polymer
- formula
- foaming
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen 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
- C08J2203/06—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
- 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
Landscapes
- 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 provides a novel method for preparing polymer foam by a powder method. The method comprises two steps, firstly, carrying out compression molding on polymer fine powder at room temperature to obtain a non-compact pre-foamed plate, and then foaming the pre-foamed plate by a carbon dioxide foaming technology to obtain the target foam material. Compared with the traditional carbon dioxide mould pressing foaming technology, the invention has the advantages of high efficiency and energy saving, and can greatly reduce the production efficiency and cost of products.
Description
Technical Field
The present invention is in the field of polymer foaming.
Technical Field
The carbon dioxide mould pressing foaming technology is one of the main technologies for preparing the polyaryletherketone (sulfone) foam board, and the foaming technology comprises two steps: the first step is a mould pressing procedure, namely, polymer powder or granules are mould pressed into a plate at high temperature through a hot press, then the plate is taken out after the temperature is reduced to below 100 ℃, wherein the mould pressing temperature is 340 ℃, the mould pressing time is 40-60min, the time of early-stage temperature rise and later-stage temperature reduction is added, and the whole procedure needs 120-180 min; the second step is a foaming process, namely placing the obtained pre-foamed plate in a high-pressure kettle, introducing carbon dioxide, keeping for a period of time under the conditions of high temperature and high pressure (260 ℃ and 10 MPa), and then releasing pressure to complete foaming, wherein the whole process needs 120-240 min. Both processes need to be processed for a long time under high temperature, and the energy consumption is high and the efficiency is low. For example, in patent (CN 201710187545.1), the mold pressing temperature of the first foaming original plate of polyaryletherketone foam preparation is 350 ℃, the whole process is 150min, the temperature in the foaming stage is 230-280 ℃, and the process time is 150min. Due to high processing temperature and long working procedure time, the production energy consumption is high, the efficiency is low, and the cost is high.
Disclosure of Invention
The invention aims to solve the problem of low energy consumption and high efficiency of the traditional carbon dioxide mould pressing foaming technology and can greatly reduce the cost of polyaryletherketone (sulfone) foam.
The invention provides a novel method for preparing polymer foam by a powder method, which comprises the following operation steps:
firstly, molding polyaryletherketone (sulfone) powder into a plate by a vulcanizing machine at room temperature, then placing the plate in a closed foaming kettle, introducing carbon dioxide, keeping at high temperature and high pressure for a certain time, and finally releasing pressure to complete foaming to obtain a foam product.
The room temperature is 10 to 30 ℃, preferably 25 ℃.
The fineness of the polymer powder is 200-1000 meshes, preferably 200-500 meshes. Preferably, the polymer includes, but is not limited to, polyaryletherketones (sulfones). Preferably, the structural formula of the polyaryletherketone (sulfone) is as shown in formula I or formula II:
formula I
Formula II
Wherein X is selected from one or two of the following structures A or B:
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):
the polymer is a main chain random copolymerization structure, and main chain repeating units appear randomly and disorderly;
in the formula I, m and n represent the mole percentage of a repeating unit in a main chain, p is the mole percentage of a repeating unit of a branched chain, m + n + p =1,0.85 is more than or equal to m + p is more than or equal to 1,0 is more than or equal to m and less than or equal to 0.85,0 is more than or equal to p and less than or equal to 0.85,0 is more than or equal to n and less than or equal to 0.15;
80000 < M of the Polymer (w) < 300000,1.8 < PDI < 3.0, preferably 150000 < M (w) < 250000,2.0 < PDI < 2.8, where M (w) The weight average molecular weight (Mw/Mn) and the Polymer Dispersity Index (PDI) are represented by GPC;
in the formula II, m ', n ' represents the mol percent of the repeating unit in the main chain, p ', q ' represents the mol percent of the branched chain repeating unit, m ' + n ' + p ' + q ' =1,0 is more than or equal to m '. Ltoreq.0.85, 0 is more than or equal to p '. Ltoreq.0.85, 0 is more than or equal to q '. Ltoreq.0.85, 0.85 is more than or equal to m ' + p ' + q '. Ltoreq.1, 0 is more than or equal to n '. Ltoreq.0.15;
80000 < M of the polymer (w) < 300000,1.8 < PDI < 3.0, preferably 150000 < M (w) < 250000,2.0 < PDI < 2.8, where M (w) Is weight average molecular weight, PDI is polyThe compound dispersibility index, characterized by GPC.
The molding pressure of the powder is 5 to 200MPa, preferably 10 to 100MPa.
The molding time of the powder is 5-30min, preferably 10-20min.
The thickness of the polymer sheet is 1-15mm, preferably 4-10mm.
The retention time in the foaming kettle is 5-30min, preferably 10-20min.
The temperature in the foaming kettle is 200-350 ℃, and preferably 250-330 ℃.
The pressure in the foaming kettle is 5-20MPa, preferably 10-20MPa.
The density of the foam product is 30-1000kg/m 3 Preferably 50 to 400kg/m 3 。
The invention has the following beneficial effects: the invention adopts the cold press molding technology to replace the traditional hot press molding technology to prepare the pre-foamed plate, and because the long-time heating is not needed to melt and soften the polymer, the time required by the pre-foamed plate molding is greatly shortened, and the energy consumption is obviously reduced. In addition, in the foaming process, because the gaps in the cold-pressed pre-foaming plate are larger than those in the hot-pressing plate, carbon dioxide can be quickly impregnated into the pre-foaming plate, the heat-preservation and pressure-maintaining time is greatly shortened, the production efficiency of polymer foam in the carbon dioxide foaming technology can be obviously improved, and the cost is reduced.
Drawings
FIG. 1 is a scanning electron micrograph of a foam product prepared according to example 1 of the present invention.
Detailed Description
Comparative example 1
Formula III
The preparation method of the polyaryletherketone with the structure of the formula III comprises the following steps: to a three-necked flask, lactone-type phenolphthalein (100 mmol), 4-difluorobenzophenone (117 mmol), and 1, 1-tris (hydroxymethyl) phenol were added(4-hydroxyphenyl) ethane (8 mmol), K 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 constant for 2h, removing the toluene, continuing to heat to 220 ℃ for reaction for 4h, cooling, adding 250ml of DMAc for dilution, precipitating in ethanol/water (volume ratio of 1. (M) (w) =220000,pdi = 2.7). By passing 1 H-NMR, FT-IR, GPC characterized the structure and molecular weight.
And (2) molding the dried polyaryletherketone powder (Tg =220 ℃ and the particle size is 300 meshes) or granules with the structure shown in the formula III in a vulcanizing machine, stopping heating at the temperature of 350 ℃, under the pressure of 10MPa for 30min, and after the temperature is reduced to be below 100 ℃, releasing pressure and taking out a sample plate with the thickness of 5mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and then injecting CO into the foaming kettle through a pressurization system 2 Keeping the temperature in the kettle at 280 ℃ and the pressure at 10MPa, keeping the temperature and the pressure for 150min, opening a pressure release valve of the foaming kettle to quickly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample, and obtaining a foam product with the foam density of 90kg/m 3 。
Example 1
The dried polyaryletherketone micropowder (Tg =220 ℃, fineness 300 mesh) having the structure of formula III prepared in comparative example 1 was molded in a vulcanizer at 25 ℃, pressurized at 20MPa, and decompressed after 10min, and the sample was taken out to have a thickness of 5mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 280 ℃ and the pressure at 10MPa for 10min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample, and obtaining a foam product with the foam density of 80kg/m 3 。
Example 2
The dried polyaryletherketone micropowder having the structure of formula III (Tg =220 ℃, fineness 700 mesh) prepared in comparative example 1 was molded in a vulcanizer at 25 ℃ under 40And (5) releasing the pressure after 10min under the MPa, and taking out the sample plate with the thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature at 260 ℃ and the pressure at 10MPa in the foaming kettle for 10min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample, and obtaining a foam product with the foam density of 100kg/m 3 。
Example 3
Formula IV
The preparation method of the polyaryletherketone with the structure shown in the formula IV comprises the following steps: into a three-necked flask was charged 3, 3-bis (4-hydroxyphenyl) -3H-isoindolinone (100 mmol), 4-difluorodiphenylsulfone (112.5 mmol), 1,3, 5-tris (4-hydroxyphenyl) benzene (6 mmol), K 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 constant for 2h, removing the toluene, continuously heating to 220 ℃ for reaction for 6h, cooling, adding 250ml DMAc for dilution, precipitating in ethanol/water (volume ratio is 1: 1), filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salt and residual solvent, and drying to obtain the polyarylethersulfone (M) with the structure of formula (IV) (w) =200000,pdi = 2.5). By passing 1 H-NMR, FT-IR, GPC characterized the structure and molecular weight. And (3) molding the dried polyarylethersulfone ultrafine powder (Tg =255 ℃ and fineness of 400 meshes) with the structure of the formula IV in a vulcanizing machine, decompressing after the temperature is 25 ℃, the pressure is 20MPa and 10min, and taking out a sample plate with the thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 300 ℃ and the pressure at 15MPa for 20min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample, and obtaining a foam product with the foam density of 170kg/m 3 。
Example 4
The dried polyarylethersulfone micropowder (Tg =255 ℃ C., fineness 400 mesh) having the structure of formula IV prepared in example 3 was molded in a vulcanizer at a temperature of 25 ℃ under a pressure of 40MPa for 10min, then decompressed and taken out of the mold to a thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and then injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 320 ℃ and the pressure at 15MPa for 20min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample to obtain a foam product with the foam density of 80kg/m 3 。
Example 5
Formula V
The preparation method of the polyaryletherketone with the structure of the formula V is as follows: bisphenol fluorene (100 mmol), 4-difluorobenzophenone (116 mmol), 4', 4' - (ethane-1, 2-tetra-phenyl) tetraphenol (4 mmol), K 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 constant for 2h, removing the toluene, continuing to heat to 220 ℃ for reaction for 6h, cooling, adding 250ml of DMAc for dilution, precipitating in ethanol/water (volume ratio of 1 (w) =180000,pdi = 2.4). By passing 1 H-NMR, FT-IR, GPC characterized the structure and molecular weight.
And (2) carrying out mould pressing on the dried polyaryletherketone superfine powder (Tg =246 ℃, fineness of 400 meshes) with the structure of the formula V in a vulcanizing machine, carrying out pressure relief at the temperature of 25 ℃ and the pressure of 70MPa after 25min, and taking out a sample plate with the thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and then injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 310 ℃ and the pressure at 15MPa for 20min, opening the foaming kettle to release the pressureThe valve rapidly reduces the pressure to normal pressure, and then the foaming kettle is opened to take out the sample, thus obtaining the foam product with the foam density of 55kg/m 3 。
Example 6
Dried polyaryletherketone micropowder (Tg =246 ℃, fineness 400 mesh) having a structure of formula V prepared in example 5 was molded in a vulcanizer at a temperature of 25 ℃, a pressure of 70MPa, and after 25min, a sample plate was removed and the thickness was 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and then injecting CO into the foaming kettle through a pressurization system 2 Keeping the temperature in the kettle at 260 ℃ and the pressure at 20MPa for 20min, opening a pressure release valve of the foaming kettle to quickly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample to obtain a foam product with the foam density of 255kg/m 3 。
Example 7
Formula VI
The preparation method of the polyarylether sulphone with the structure of the formula VI is as follows: bisphenol fluorene (100 mmol), 4-difluorodiphenyl sulfone (115 mmol), phloroglucinol (10 mmol), and K were charged into a three-necked flask 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, continuing to heat to 220 ℃ for reaction for 6h, cooling, adding 250ml of DMAc for dilution, precipitating in ethanol/water (volume ratio of 1 (w) =220000,pdi = 2.3). By passing 1 H-NMR, FT-IR, GPC characterized the structure and molecular weight.
And (2) carrying out mould pressing on the dried polyaryletherketone ultrafine powder (Tg =264 ℃, fineness of 500 meshes) with the structure of the formula VI in a vulcanizing machine, wherein the temperature is 25 ℃, the pressure is 100MPa, and the sample plate is taken out after 25min pressure release and has the thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and thenInjecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 300 ℃ and the pressure at 20MPa for 20min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample, and obtaining a foam product with the foam density of 170kg/m 3 。
Example 8
Dried polyaryletherketone micropowder (Tg =246 ℃, 400 mesh fineness) having the structure of formula VI prepared in example 7 was molded in a vulcanizer at a temperature of 25 ℃, a pressure of 70MPa, and after 25min, the molded product was decompressed and taken out to a thickness of 4mm. Placing the obtained sample plate in a foaming kettle, sealing the kettle body, and then injecting CO into the foaming kettle through a pressurization system 2 Maintaining the temperature in the kettle at 310 ℃ and the pressure at 20MPa for 15min, opening a pressure release valve of the foaming kettle to rapidly reduce the pressure to normal pressure, then opening the foaming kettle to take out a sample to obtain a foam product with the foam density of 105kg/m 3 。
Claims (10)
1. A method of preparing a polymer foam by a powder process, characterized by: firstly, using a vulcanizer to mould polymer powder into a plate at room temperature (10-30 ℃), then placing the plate in a closed foaming kettle, introducing carbon dioxide, keeping at high temperature and high pressure, and finally releasing pressure to complete foaming to obtain a foam product.
2. The method of claim 1, wherein: the particle size fineness of the polymer powder is 200-1000 meshes, and preferably 200-500 meshes.
3. The method of claim 1, wherein: the polymer includes but is not limited to one or more of polyaryletherketone or polyarylethersulfone.
4. The method of claim 3, wherein: the structural formula of the polyaryletherketone (or polyarylethersulfone) is shown as formula I or one or more than two of formula I:
wherein X is selected from one or two of the following structures A or B:
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 and n represent the mole percentage of a repeating unit in a main chain, p is the mole percentage of a repeating unit of a branched chain, m + n + p =1,0.85 is more than or equal to m + p is more than or equal to 1,0 is more than or equal to m and less than or equal to 0.85,0 is more than or equal to p and less than or equal to 0.85,0 is more than or equal to n and less than or equal to 0.15; 80000 < M of the polymer (w) < 300000,1.8 < PDI < 3.0, preferably 150000 < M (w) < 250000,2.0 < PDI < 2.8, where M (w) Is the weight average molecular weight, and PDI is the polymer dispersibility index;
in the formula II, m ', n ' represents the mol percent of the repeating unit in the main chain, p ', q ' represents the mol percent of the branched chain repeating unit, m ' + n ' + p ' + q ' =1,0 is more than or equal to m '. Ltoreq.0.85, 0 is more than or equal to p '. Ltoreq.0.85, 0 is more than or equal to q '. Ltoreq.0.85, 0.85 is more than or equal to m ' + p ' + q '. Ltoreq.1, 0 is more than or equal to n '. Ltoreq.0.15; 80000 < M of the Polymer (w) < 300000,1.8 < PDI < 3.0, preferably 150000 < M (w) < 250000,2.0 < PDI < 2.8, where M (w) The weight average molecular weight, PDI, is the polymer dispersion index.
5. The method of claim 1, wherein: the molding pressure of the powder is 5 to 200MPa, preferably 10 to 100MPa;
the molding time of the powder is 5-30min, preferably 10-20min.
6. The method of claim 1, wherein: the resulting moulded sheet has a thickness of 1 to 15mm, preferably 4 to 10mm.
7. The method of claim 1, wherein: the retention time in the foaming kettle is 5-30min, preferably 10-20min.
8. The method of claim 1, wherein: the temperature in the foaming vessel is from 200 to 350 ℃ and preferably from 250 to 330 ℃.
9. The method of claim 1, wherein: the pressure of introducing carbon dioxide into the foaming kettle is 5-20MPa, preferably 10-20MPa.
10. The method of claim 1, wherein: the obtained foam product has a density of 30-1000kg/m 3 Preferably 50 to 400kg/m 3 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110783380.0A CN115612161B (en) | 2021-07-12 | 2021-07-12 | Method for preparing polymer foam by powder method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110783380.0A CN115612161B (en) | 2021-07-12 | 2021-07-12 | Method for preparing polymer foam by powder method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115612161A true CN115612161A (en) | 2023-01-17 |
| CN115612161B CN115612161B (en) | 2023-08-15 |
Family
ID=84855053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110783380.0A Active CN115612161B (en) | 2021-07-12 | 2021-07-12 | Method for preparing polymer foam by powder method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115612161B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07138401A (en) * | 1993-11-17 | 1995-05-30 | Furukawa Electric Co Ltd:The | Production of polyether sulfone resin foam |
| CN106832384A (en) * | 2016-12-23 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of ketone foamed material of lateral group polyarylether containing phthalein 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 |
| CN107619496A (en) * | 2017-07-05 | 2018-01-23 | 四川大学 | Foamable polymer composite of bimodal hole-closing structure and preparation method thereof |
| CN108081629A (en) * | 2016-11-22 | 2018-05-29 | 常州天晟新材料股份有限公司 | A kind of preparation method of cardo polyetherketone structural foam |
| CN113024993A (en) * | 2021-03-24 | 2021-06-25 | 广州机械科学研究院有限公司 | Polyether-ether-ketone composite material and preparation method and application thereof |
-
2021
- 2021-07-12 CN CN202110783380.0A patent/CN115612161B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07138401A (en) * | 1993-11-17 | 1995-05-30 | Furukawa Electric Co Ltd:The | Production of polyether sulfone resin foam |
| CN108081629A (en) * | 2016-11-22 | 2018-05-29 | 常州天晟新材料股份有限公司 | A kind of preparation method of cardo polyetherketone structural foam |
| CN106832384A (en) * | 2016-12-23 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof |
| CN107619496A (en) * | 2017-07-05 | 2018-01-23 | 四川大学 | Foamable polymer composite of bimodal hole-closing structure 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 |
| CN113024993A (en) * | 2021-03-24 | 2021-06-25 | 广州机械科学研究院有限公司 | Polyether-ether-ketone composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115612161B (en) | 2023-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107474242B (en) | A kind of polymer containing long branched chain structure, preparation method and foamed material | |
| CN101081927A (en) | Glass micro-bead filling modified mould nylon plate and preparation method thereof | |
| CN103232568B (en) | A kind of polymethacrylimide plastic foam and preparation method thereof | |
| CN112708163A (en) | Preparation method of high-resilience biodegradable polyester micro-foaming profiled bar | |
| CN106832384B (en) | One kind ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof | |
| WO2018094763A1 (en) | Method for preparing foaming material of phenolphthalein-based polyaryletherketone structure | |
| CN103087280B (en) | Method for synthesizing phenolic resins by using paraformaldehyde | |
| CN113549305A (en) | Full-biodegradable modified PBAT foamed sheet and preparation method and application thereof | |
| CN113571725A (en) | Preparation process of graphite-based nanocomposite bipolar plate | |
| CN103382260B (en) | Production method of polyether ketone and modified nano silicon dioxide foaming materials and by supercritical carbon dioxide | |
| CN115612161A (en) | Method for preparing polymer foam by powder method | |
| CN107722595B (en) | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material | |
| CN114149684B (en) | Low-temperature-cured low-dielectric high-toughness cyanate resin and preparation method thereof | |
| CN102351170A (en) | Preparation method of high strength resin base foam charcoal material | |
| CN112940417B (en) | High-wave-transmittance tetrafluoroethylene copolymer plastic microporous foam material in wide frequency band and green preparation method thereof | |
| CN113878903A (en) | Wind power blade foam core material, preparation method, wind power blade and wind generating set | |
| CN114249887B (en) | Branched polymer, preparation thereof and foam material | |
| CN103242645B (en) | High wear resistant polymer blend material or goods and preparation method thereof | |
| CN114806134B (en) | Thermoplastic/thermosetting polymer blend foam material and preparation method thereof | |
| CN104497343B (en) | A kind of preparation method of Polymethacrylimide micro-foaming material and products thereof | |
| CN111171345A (en) | Preparation method of polyamide microspheres | |
| CN112694635B (en) | Preparation method of cellulose/PAA anion exchange membrane with double-network structure | |
| CN108589298A (en) | A kind of full bio-based composite material and preparation method thereof based on biology base benzoxazine and plant fiber | |
| CN109852049B (en) | Cast nylon/polymer microsphere composite material and preparation method and application thereof | |
| CN113462006A (en) | Folded polymer foam material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |