CN113897031A - Thermosetting epoxy resin and preparation method thereof - Google Patents
Thermosetting epoxy resin and preparation method thereof Download PDFInfo
- Publication number
- CN113897031A CN113897031A CN202010641578.0A CN202010641578A CN113897031A CN 113897031 A CN113897031 A CN 113897031A CN 202010641578 A CN202010641578 A CN 202010641578A CN 113897031 A CN113897031 A CN 113897031A
- Authority
- CN
- China
- Prior art keywords
- stirring
- epoxy resin
- liquid
- parts
- bisphenol
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- 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
- C08J2481/00—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
- C08J2481/04—Polysulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a thermosetting epoxy resin and a preparation method thereof, which comprises the following steps: adding liquid polysulfide rubber into half of bisphenol A type epoxy resin, and stirring to obtain first liquid; adding the epoxy-terminated polyurethane resin into the other half of the bisphenol A epoxy resin, and stirring to obtain a second liquid; adding the first liquid into the second liquid, heating, adding the isophorone diamine, and stirring to obtain a mixture; and (3) carrying out vacuum defoaming, high-temperature curing and demoulding on the mixture to obtain the thermosetting epoxy resin. The thermosetting epoxy resin prepared by the preparation method has greatly improved impact resistance under the condition of keeping the tensile strength basically unchanged.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to thermosetting epoxy resin and a preparation method thereof.
Background
Thermoplastic refers to the property that a substance can flow and deform when heated and can keep a certain shape after being cooled, and most linear polymers show thermoplastic property and are easy to be extruded, injected, blown or the like. Thermosetting is different from thermoplastic, and thermosetting plastic refers to plastic which becomes infusible after being heated, no longer has plasticity after being heated again and can not be recycled.
Epoxy resin is a generic name of a polymer containing more than two epoxy groups in a molecule, is a polycondensation product of epoxy chloropropane and bisphenol A or polyol, and can be subjected to ring opening by using various compounds containing active hydrogen due to the chemical activity of the epoxy groups, and a network structure is formed by curing and crosslinking, so that the epoxy resin belongs to one of thermosetting resins.
Because the thermosetting epoxy resin is in a spatial three-dimensional network structure after being heated and cured, molecular chains are not easy to slide and have large internal stress, so that the cured epoxy resin has the defects of insufficient toughness, poor impact resistance, easy cracking and the like.
Disclosure of Invention
In view of the above, the present invention needs to provide a thermosetting epoxy resin and a preparation method thereof, in which liquid polysulfide rubber and epoxy-terminated polyurethane resin are added into bisphenol a type epoxy resin for compounding and toughening, so that the toughness of the prepared thermosetting epoxy resin is significantly improved, thereby solving the above problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a preparation method of thermosetting epoxy resin, which comprises the following steps:
weighing 3-10 parts of liquid polysulfide rubber, 2-5 parts of epoxy-terminated polyurethane resin, 100 parts of bisphenol A epoxy resin and 30-40 parts of isophorone diamine according to parts by weight;
adding the liquid polysulfide rubber into 50 parts of bisphenol A epoxy resin, and stirring to obtain a first liquid;
adding the epoxy-terminated polyurethane resin into another 50 parts of the bisphenol A epoxy resin, and stirring to obtain a second liquid;
adding the first liquid into the second liquid, heating, adding the isophorone diamine, and stirring to obtain a mixture;
and (3) carrying out vacuum defoaming, high-temperature curing and demoulding on the mixture to obtain the thermosetting epoxy resin.
Further, the specific steps of stirring to obtain the first liquid are as follows: stirring at 50-80 ℃ for 10-20min at the stirring speed of 500-800 rpm.
Further, the specific step of stirring to obtain the second liquid is as follows: stirring at 50-80 ℃ for 10-20min at the stirring speed of 500-800 rpm.
Further, the specific steps of adding the isophorone diamine after heating and stirring to obtain a mixture are as follows: the temperature is raised to 120-130 ℃, the isophorone diamine is added, and the mixture is obtained after stirring for 3-5min, wherein the stirring speed is 800-1000 rpm.
Further, the vacuum defoaming time is 5-10 min.
Further, the high-temperature curing specifically comprises the following steps: after vacuum defoaming, the temperature is raised to 170-180 ℃ for curing for 5-6 h.
Preferably, in some exemplary embodiments of the present invention, the bisphenol A type epoxy resin is epoxy resin E-42, which is highly transparent, with volatiles ≦ 0.5%;
the viscosity of the epoxy-terminated polyurethane resin is 50000-80000 mPas;
the isophorone diamine has a viscosity of 18cp · s at 20 ℃ and an active hydrogen equivalent of 42.5.
The invention also provides a thermosetting epoxy resin prepared by adopting the preparation method of any one of the above-mentioned components.
Compared with the prior art, the liquid polysulfide rubber and the epoxy-terminated polyurethane resin are added into the epoxy resin system to carry out compounding toughening, and the toughening effect is excellent. The obtained thermosetting epoxy resin has greatly improved impact resistance under the condition of keeping the tensile strength unchanged basically, and the toughening advantage of the compound toughened epoxy resin is more obvious.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples and comparative examples employ specific raw material components:
the bisphenol A type epoxy resin is epoxy resin E-42 which is highly transparent, volatile matters are less than or equal to 0.5 percent, and a producer is the Qingdao Baichen technology;
the liquid polysulfide rubber is produced by Hubei Xin Rundghe chemical company Limited under the brand JLY-121;
the producer of the epoxy-terminated polyurethane resin is a Hui hong plastic plant of Yuyao city, and the brand number is ETU-140;
isophoronediamine IPDA has a viscosity (20 ℃) of 18 cp.s, an active hydrogen equivalent of 42.5 and was obtained from Pasteur Germany.
It should be noted that, the specific information of manufacturers, brands, etc. is given here to make the technical solution of the embodiments of the present invention clearer, and does not mean that only the raw materials of the manufacturers or brands can be used in the present invention. In addition, the raw materials used in the following examples and comparative examples are all parts by weight unless otherwise specified.
Example 1:
adding 3 parts of liquid polysulfide rubber into 50 parts of bisphenol A type epoxy resin, stirring for 10 minutes at 50 ℃, and stirring at the speed of 500 revolutions per minute to obtain first liquid;
adding 2 parts of epoxy-terminated polyurethane resin into another 50 parts of bisphenol A epoxy resin, and stirring at 50 ℃ for 10 minutes at a stirring speed of 500 revolutions per minute to obtain a second liquid;
adding the first liquid into the second liquid, heating to 120 ℃, adding 30 parts of isophorone diamine, and stirring for 3 minutes at a stirring speed of 800 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 5 minutes; heating to 170 ℃, curing for 5 hours, and demoulding to obtain the thermosetting epoxy resin.
Example 2:
adding 10 parts of liquid polysulfide rubber into 50 parts of bisphenol A type epoxy resin, stirring for 20 minutes at 80 ℃, and stirring at 800 revolutions per minute to obtain a first liquid;
adding 5 parts of epoxy-terminated polyurethane resin into another 50 parts of bisphenol A epoxy resin, and stirring at 80 ℃ for 20 minutes at a stirring speed of 800rpm to obtain a second liquid;
adding the first liquid into the second liquid, heating to 130 ℃, adding 40 parts of isophorone diamine, and stirring for 5 minutes at a stirring speed of 1000 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 10 minutes; heating to 180 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
Example 3:
adding 5 parts of liquid polysulfide rubber into 50 parts of bisphenol A type epoxy resin, stirring for 12 minutes at 60 ℃, and stirring at 600 revolutions per minute to obtain a first liquid;
adding 3 parts of epoxy-terminated polyurethane resin into another 50 parts of bisphenol A epoxy resin, stirring at 60 ℃ for 12 minutes at a stirring speed of 600 revolutions per minute to obtain a second liquid;
adding the first liquid into the second liquid, heating to 125 ℃, adding 35 parts of isophorone diamine, stirring for 4 minutes at a stirring speed of 900 rpm, and obtaining a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 8 minutes; heating to 175 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
Example 4:
adding 8 parts of liquid polysulfide rubber into 50 parts of bisphenol A type epoxy resin, stirring for 15 minutes at 70 ℃, and stirring at 700 revolutions per minute to obtain a first liquid;
adding 4 parts of epoxy-terminated polyurethane resin into another 50 parts of bisphenol A epoxy resin, stirring for 15 minutes at 70 ℃, and stirring at 700 revolutions per minute to obtain a second liquid;
adding the first liquid into the second liquid, heating to 125 ℃, adding 35 parts of isophorone diamine, stirring for 4 minutes at a stirring speed of 900 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 8 minutes; heating to 180 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
Comparative example 1:
adding 12 parts of liquid polysulfide rubber into 100 parts of bisphenol A type epoxy resin, stirring for 15 minutes at 70 ℃, and stirring at 700 revolutions per minute to prepare liquid;
heating the liquid to 125 ℃, adding 35 parts of isophorone diamine, and stirring for 4 minutes at a stirring speed of 900 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 8 minutes; heating to 180 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
Comparative example 2:
adding 12 parts of epoxy-terminated polyurethane resin into 100 parts of bisphenol A epoxy resin, stirring for 15 minutes at 70 ℃, and stirring at 700 revolutions per minute to obtain liquid;
heating the liquid to 125 ℃, adding 35 parts of isophorone diamine, and stirring for 4 minutes at a stirring speed of 900 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 8 minutes; heating to 180 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
Comparative example 3:
adding 8 parts of liquid polysulfide rubber and 4 parts of epoxy-terminated polyurethane resin into 100 parts of bisphenol A epoxy resin, heating to 125 ℃, adding 35 parts of isophorone diamine, stirring for 4 minutes at a stirring speed of 900 revolutions per minute to obtain a mixture;
pouring the mixture into a mold, and carrying out vacuum defoamation for 8 minutes; heating to 180 ℃, curing for 6 hours, and demolding to obtain the thermosetting epoxy resin.
The thermosetting epoxy resins obtained in examples and comparative examples were subjected to respective performance tests, and the test results are shown in table 1.
TABLE 1 test results of thermosetting epoxy resin Properties in examples and comparative examples
| Test items | Tensile Strength (MPa) | Unnotched impact strength (kJ/m) of cantilever beam2) |
| Example 1 | 155 | 52 |
| Example 2 | 142 | 71 |
| Example 3 | 161 | 60 |
| Example 4 | 158 | 68 |
| Comparative example 1 | 119 | 11 |
| Comparative example2 | 157 | 26 |
| Comparative example 3 | 152 | 19 |
In table 1, tensile strength was tested with reference to GB/T1040 using tensile bars of type (200.0 ± 5.0) mm (20.0 ± 0.5) mm (4.0 ± 0.5) mm at a tensile rate of 5 mm/min;
unnotched Izod impact strength was tested with reference to GB/T1843, and the specimens were (120.0. + -. 2.0) mm (15.0. + -. 0.5) mm (10. + -. 0.5) mm.
The test results in table 1 show that the liquid polysulfide rubber and the epoxy-terminated polyurethane resin are added in the preparation process of the thermosetting epoxy resin for compounding and toughening, the toughening effect is excellent, and the impact resistance is greatly improved under the condition of keeping the tensile strength basically unchanged. Compared with the existing polyurethane resin toughened epoxy resin and liquid polysulfide rubber toughened epoxy resin, the composite toughening epoxy resin has more obvious advantages.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of thermosetting epoxy resin is characterized by comprising the following steps:
weighing 3-10 parts of liquid polysulfide rubber, 2-5 parts of epoxy-terminated polyurethane resin, 100 parts of bisphenol A epoxy resin and 30-40 parts of isophorone diamine according to parts by weight;
adding the liquid polysulfide rubber into 50 parts of bisphenol A epoxy resin, and stirring to obtain a first liquid;
adding the epoxy-terminated polyurethane resin into another 50 parts of the bisphenol A epoxy resin, and stirring to obtain a second liquid;
adding the first liquid into the second liquid, heating, adding the isophorone diamine, and stirring to obtain a mixture;
and (3) carrying out vacuum defoaming, high-temperature curing and demoulding on the mixture to obtain the thermosetting epoxy resin.
2. The preparation method according to claim 1, wherein the stirring to obtain the first liquid comprises the following specific steps: stirring at 50-80 ℃ for 10-20min at the stirring speed of 500-800 rpm.
3. The method according to claim 1, wherein the stirring to obtain the second liquid comprises the following specific steps: stirring at 50-80 ℃ for 10-20min at the stirring speed of 500-800 rpm.
4. The preparation method according to claim 1, wherein the specific steps of adding the isophorone diamine after the temperature is raised and stirring to obtain the mixture are as follows: the temperature is raised to 120-130 ℃, the isophorone diamine is added, and the mixture is obtained after stirring for 3-5min, wherein the stirring speed is 800-1000 rpm.
5. The method according to claim 1, wherein the time for vacuum defoaming is 5 to 10 min.
6. The preparation method according to claim 1, wherein the high-temperature curing comprises the following specific steps: after vacuum defoaming, the temperature is raised to 170-180 ℃ for curing for 5-6 h.
7. The method according to claim 1, wherein the bisphenol a type epoxy resin is epoxy resin E-42, which is highly transparent and has a volatile content of 0.5% or less;
the viscosity of the epoxy-terminated polyurethane resin is 50000-80000 mPas;
the isophorone diamine has a viscosity of 18cp · s at 20 ℃ and an active hydrogen equivalent of 42.5.
8. A thermosetting epoxy resin obtained by the production method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010641578.0A CN113897031B (en) | 2020-07-06 | 2020-07-06 | Thermosetting epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010641578.0A CN113897031B (en) | 2020-07-06 | 2020-07-06 | Thermosetting epoxy resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113897031A true CN113897031A (en) | 2022-01-07 |
| CN113897031B CN113897031B (en) | 2023-09-29 |
Family
ID=79186546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010641578.0A Active CN113897031B (en) | 2020-07-06 | 2020-07-06 | Thermosetting epoxy resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113897031B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305170A (en) * | 2012-03-16 | 2013-09-18 | 比亚迪股份有限公司 | Bi-component adhesive composition and preparation method thereof |
| CN103467708A (en) * | 2013-08-30 | 2013-12-25 | 武汉二航路桥特种工程有限责任公司 | Flexible epoxy resin material with low elastic modulus and high elongation |
| US20140357802A1 (en) * | 2011-12-20 | 2014-12-04 | Dow Global Technologies Llc | Toughening agent for epoxy thermoset |
| CN109438926A (en) * | 2018-11-20 | 2019-03-08 | 中国人民解放军海军工程大学 | A kind of polysulfide-rubber-modified epoxy and preparation method thereof |
| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
-
2020
- 2020-07-06 CN CN202010641578.0A patent/CN113897031B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140357802A1 (en) * | 2011-12-20 | 2014-12-04 | Dow Global Technologies Llc | Toughening agent for epoxy thermoset |
| CN103305170A (en) * | 2012-03-16 | 2013-09-18 | 比亚迪股份有限公司 | Bi-component adhesive composition and preparation method thereof |
| CN103467708A (en) * | 2013-08-30 | 2013-12-25 | 武汉二航路桥特种工程有限责任公司 | Flexible epoxy resin material with low elastic modulus and high elongation |
| CN109438926A (en) * | 2018-11-20 | 2019-03-08 | 中国人民解放军海军工程大学 | A kind of polysulfide-rubber-modified epoxy and preparation method thereof |
| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘程等, 北京工业大学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113897031B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101542338B1 (en) | Epoxy resin composition and fiber-reinforced composite material | |
| TW201736426A (en) | Epoxy resin curing agent, epoxy resin composition, carbon fiber-reinforced composite material | |
| CN102898805B (en) | Polycarbonate composite material, its preparation method and application | |
| CN103524948A (en) | Polyvinyl chloride foam and preparation method thereof | |
| CN106589837A (en) | Heat-resisting epoxy resin and carbon fiber composite cured at medium and low temperature and preparation method of composite | |
| CN113897031A (en) | Thermosetting epoxy resin and preparation method thereof | |
| CN103627173A (en) | Glass fiber strengthened polyphenylene sulfide/aromatic polyamide composite material and preparation method thereof | |
| US20210277174A1 (en) | Epoxy resin system for making fiber reinforced composites | |
| CN101445654B (en) | Material of filling and glass fibre reinforced nylon 6 and preparation method thereof | |
| CN114907670A (en) | Single-component fast curing epoxy resin and preparation method thereof | |
| CN107922590B (en) | Stable high glass transition temperature epoxy resin systems for making composites | |
| EP3218421B1 (en) | Fast curing high glass transition temperature epoxy resin system | |
| CN103435979A (en) | Low temperature-resistant and halogen-free flame retardant PBT composite material and preparation method thereof | |
| EP3246346B1 (en) | Tire | |
| CN108250396B (en) | Environment-friendly high-strength impact-resistant molding compound and preparation method thereof | |
| KR101462449B1 (en) | Glycidylamine epoxy curing composition | |
| CN112961497A (en) | Environment-friendly thermoplastic plastic composite pipe and preparation method thereof | |
| CN111849159A (en) | Nylon 6T composite material and preparation method thereof | |
| CN105504703A (en) | Liquid crystal polyester resin composite and preparation method thereof | |
| CN103992477A (en) | Method for preparation of polyimide siloxane/carbon fiber composite material by reactive extrusion | |
| CN107129664B (en) | Preparation method of bio-based network toughened epoxy resin | |
| CN114276649A (en) | Thermosetting resin composition, preparation method and application thereof | |
| CN117844223A (en) | Preparation method of high-temperature-resistant carbon dioxide-based biodegradable foaming material | |
| CN116003957A (en) | Resin composition and resin material for resin transfer molding process | |
| CN112898774A (en) | Polyphenylene sulfide added with calcium sulfate whiskers 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 |