CN112608584A - PBT modified material with high elongation at break as well as preparation method and application thereof - Google Patents
PBT modified material with high elongation at break as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN112608584A CN112608584A CN202011378570.6A CN202011378570A CN112608584A CN 112608584 A CN112608584 A CN 112608584A CN 202011378570 A CN202011378570 A CN 202011378570A CN 112608584 A CN112608584 A CN 112608584A
- Authority
- CN
- China
- Prior art keywords
- pbt
- modified material
- break
- elongation
- resin
- 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PBT modified material with high elongation at break, a preparation method and application thereof. The PBT modified material comprises the following components: PBT resin, lubricant, hydrolysis stabilizer containing epoxy or imine functional group, and other auxiliary agent; the carboxyl-terminated content of the PBT resin is 10-30 mol/t; the lubricant is one or more of acrylic acid ethylene copolymer wax, oxidized polyethylene wax or polyol ester wax. According to the invention, through the synergistic effect of the PBT resin with the terminal carboxyl group content of 10-30 mol/t, the lubricant, the hydrolysis stabilizer containing epoxy or imine functional group and other additives, the PBT modified material with excellent elongation at break and good rigidity and fluidity is obtained under the condition that no toughening agent is added, and the PBT modified material can still keep good elongation at break after being aged by damp and heat, and the attenuation proportion of the elongation at break is less than or equal to 30%.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PBT modified material with high elongation at break, and a preparation method and application thereof.
Background
Polybutylene terephthalate (PBT), a thermoplastic polyester, is polymerized from butanediol and terephthalic acid or terephthalate. Because of the low elongation at break of PBT material, it is generally necessary to modify the PBT material to increase its elongation at break.
The elongation at break of PBT is usually provided in the prior art by the addition of large amounts of toughening agents. Chinese patent application CN109370199A discloses a high-toughness and high-elongation modified copolymer, wherein the elongation at break of PBT is improved by adding TPU and TPEE; chinese patent application CN105153656A discloses a high elongation at break PBT resin composition, which increases the elongation at break of PBT by adding methyl methacrylate-butadiene-styrene copolymer (MBS), E-MA-GMA, linear low density polyethylene resin (LLDPE). However, the PBT added with a large amount of toughening agent can cause the strength reduction and poor fluidity of the material, and the application of the PBT is influenced. In addition, in certain high-humidity and high-heat environments, the PBT material is easy to age and hydrolyze, and the elongation at break is further deteriorated.
Therefore, the development of a PBT modified material with high elongation at break, which has balanced rigidity and fluidity, and resistance to heat aging is needed.
Disclosure of Invention
The invention provides a PBT modified material, aiming at overcoming the defect that elongation at break, rigidity and fluidity are difficult to combine in the prior art, and the PBT modified material has high elongation at break, good rigidity and fluidity and moisture and heat aging resistance.
The invention also aims to provide a preparation method of the PBT modified material.
The invention also aims to provide application of the PBT modified material.
In order to solve the technical problems, the invention adopts the technical scheme that:
the PBT modified material with high elongation at break comprises the following components in parts by weight:
100 parts of PBT resin,
0.2 to 4 parts of a lubricant,
0.05 to 1.5 parts of hydrolysis stabilizer containing epoxy or imine functional group,
0-1 part of other auxiliary agents;
the carboxyl-terminated content of the PBT resin is 10-30 mol/t;
the lubricant is one or more of acrylic acid ethylene copolymer wax, oxidized polyethylene wax or polyol ester wax.
The inventor researches and discovers that the PBT resin contains a certain amount of terminal carboxyl groups, has a certain degree of compatibility with the molecular structure of the lubricant, and can promote the interaction force of the PBT resin and the lubricant to be effectively improved. However, if the content of terminal carboxyl groups in the PBT resin is too high, the PBT modified material can be severely degraded in a damp and hot environment, so that the elongation at break is seriously reduced after damp and hot aging.
The hydrolysis stabilizer containing epoxy or imine functional groups can further reduce the attenuation ratio of the elongation at break of the PBT modified material after humid heat aging: on one hand, epoxy and imine functional groups can react with terminal carboxyl groups in the PBT, so that the degree of acid catalytic degradation reaction is reduced, and the degradation speed of the PBT material in a damp and hot environment is further reduced; on the other hand, epoxy and imine functional groups can react with terminal carboxyl and terminal hydroxyl on the broken chain segment, so that the molecular chain is repaired to a certain extent, and further degradation of the material is inhibited.
The acrylic acid ethylene copolymer wax, the oxidized polyethylene wax or the polyol ester wax have polymers to a certain degree, have good elongation at break, contain polar groups such as ester groups, hydroxyl groups or carboxyl groups and the like, and have good compatibility and dispersibility with the PBT resin. In the processing process, on one hand, the lubricant reduces the friction force of the PBT molecular chain, improves the relative slippage capability of the molecular chain, and improves the elongation at break of the PBT modified material; on the other hand, the lubricant can also cover the melt of the PBT in time, inhibit the degradation process of the PBT, and further improve the elongation at break of the PBT modified material under the humid heat aging.
The inventor researches and discovers that through the synergistic effect of the PBT resin and a specific type of hydrolysis stabilizer, a lubricant and other components, the PBT modified material with excellent elongation at break can be obtained under the condition of maintaining good rigidity and fluidity of the PBT, and the PBT modified material can still maintain good elongation at break after humid heat aging.
Preferably, the PBT resin has an intrinsic viscosity of 0.8dl/g or more under a test condition at 25 ℃.
The intrinsic viscosity of the PBT resin is measured according to ISO 1628-5-2015.
The PBT resin with higher intrinsic viscosity has higher weight average molecular weight, longer molecular chain segment and higher self elongation at break, and can effectively reduce the reduction amplitude of the elongation at break in the material processing process.
More preferably, the PBT resin has an intrinsic viscosity of 0.8 to 1.3dl/g under a test condition of 25 ℃.
Preferably, the PBT resin has a catalyst-remaining amount of 50ppm or less.
The method for detecting the catalyst residue of the PBT resin is carried out according to an ICP-OES method.
In the catalytic synthesis of PBT resins, it is often necessary to use catalysts such as titanates. However, the catalyst remaining in the PBT resin accelerates the degradation of the PBT material during the humid heat aging process, resulting in a decrease in elongation at break. Therefore, the lower the residual amount of the catalyst in the PBT resin, the better.
More preferably, the PBT resin has a catalyst-remaining amount of 10 to 40 ppm.
The catalyst residue is preferably 10-40 ppm after product performance and production cost are comprehensively considered.
Preferably, the hydrolysis stabilizer containing epoxy or imine functional group is one or more of thermoplastic epoxy resin, thermosetting epoxy resin, monomer type carbodiimide, epoxy vegetable oil, glycidyl ester copolymer and glycidyl ester graft.
Preferably, the epoxidized vegetable oil is epoxidized soybean oil.
Preferably, the lubricant is an acrylic acid ethylene copolymer wax.
When the lubricant is acrylic acid ethylene copolymer wax, the PBT modified material has better initial elongation at break, rigidity and fluidity, and has lower attenuation rate of elongation at break after humid heat aging.
The other auxiliary agents comprise an antioxidant, a light stabilizer and an ultraviolet absorber.
Preferably, the antioxidant is one or more of hindered phenol type antioxidant, phosphite ester type antioxidant and sulfo antioxidant.
The light stabilizer is a hindered amine light stabilizer.
The invention also protects a preparation method of the PBT modified material with high elongation at break, which comprises the following steps:
mixing the PBT resin, the lubricant, the hydrolysis stabilizer containing epoxy or imine functional groups and other auxiliary agents, adding the mixture into an extruder, and carrying out melt granulation to obtain the PBT modified material with high elongation at break.
Preferably, the extruder is a twin screw extruder.
Preferably, the temperature of a first zone of the double-screw extruder is 30-200 ℃, the temperature of a second zone is 220-260 ℃, the temperature of a third zone is 220-260 ℃, the temperature of a fourth zone is 200-240 ℃, the temperature of a fifth zone is 200-240 ℃, the temperature of a sixth zone is 200-240 ℃, the temperature of a seventh zone is 200-240 ℃, the temperature of an eighth zone is 200-240 ℃, the temperature of a ninth zone is 200-240 ℃, the temperature of a machine head is 220-260 ℃, the residence time is 1-3 minutes, and the rotating speed of a main machine is 300-500 revolutions per minute.
The invention also protects the application of the PBT modified material with high elongation at break in preparing PBT products with high elongation at break.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through the synergistic effect of the PBT resin with the terminal carboxyl group content of 10-30 mol/t, the lubricant, the hydrolysis stabilizer containing epoxy or imine functional group and other additives, the PBT modified material with excellent elongation at break and good rigidity and fluidity is obtained under the condition that no toughening agent is added, and the PBT modified material can still keep good elongation at break after being aged by damp and heat, and the attenuation proportion of the elongation at break is less than or equal to 30%.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples and comparative examples are commercially available as follows:
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 17
Examples 1 to 17 provide a PBT modified material, and the addition amounts of the components of the PBT modified material are shown in table 1.
TABLE 1 amounts (parts by weight) of each component added in examples 1 to 17
TABLE 1 addition of the components (parts by weight) in examples 1 to 17
The preparation methods of the PBT modified materials of the embodiments 1-17 are all as follows:
and mixing the dried PBT resin, the lubricant, the hydrolysis stabilizer containing epoxy or imine functional groups and other auxiliaries, adding the mixture into a double-screw extruder, and carrying out melt granulation to obtain the PBT modified material.
The temperature of a first zone of the double-screw extruder is 30-200 ℃, the temperature of a second zone is 220-260 ℃, the temperature of a third zone is 220-260 ℃, the temperature of a fourth zone is 200-240 ℃, the temperature of a fifth zone is 200-240 ℃, the temperature of a sixth zone is 200-240 ℃, the temperature of a seventh zone is 200-240 ℃, the temperature of an eighth zone is 200-240 ℃, the temperature of a ninth zone is 200-240 ℃, the temperature of a machine head is 220-260 ℃, the retention time is 1-3 minutes, and the rotating speed of a main machine is 300-500 revolutions per minute.
Comparative examples 1 to 8
Comparative examples 1 to 8 provide PBT modified materials, and the addition amounts of the components of the PBT modified materials are shown in Table 2.
TABLE 2 addition amounts (parts by weight) of respective components in comparative examples 1 to 8
The preparation methods of the PBT modified materials of comparative examples 1-6 are all as follows:
and mixing the dried PBT resin, the lubricant, the hydrolysis stabilizer and other auxiliaries, adding the mixture into a double-screw extruder, and carrying out melt granulation to obtain the PBT modified material.
The temperature of a first zone of the double-screw extruder is 30-200 ℃, the temperature of a second zone is 220-260 ℃, the temperature of a third zone is 220-260 ℃, the temperature of a fourth zone is 200-240 ℃, the temperature of a fifth zone is 200-240 ℃, the temperature of a sixth zone is 200-240 ℃, the temperature of a seventh zone is 200-240 ℃, the temperature of an eighth zone is 200-240 ℃, the temperature of a ninth zone is 200-240 ℃, the temperature of a machine head is 220-260 ℃, the retention time is 1-3 minutes, and the rotating speed of a main machine is 300-500 revolutions per minute.
Performance testing
The PBT modified materials prepared in the above examples and comparative examples were subjected to a performance test.
The detection method specifically comprises the following steps:
elongation at break: according to ISO 527-2-2012;
elongation at break after humid heat aging: after each PBT modified material is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85% r.h for 500h, the elongation at break is detected according to the method of ISO 527-2-2012;
melt flow rate: according to ISO 1133 + 2011 method;
tensile strength: according to ISO 527-2-2012 method.
The test results of examples 1 to 14 are shown in Table 3, and the test results of comparative examples 1 to 8 are shown in Table 4.
Table 3 Performance test results of PBT modified materials of examples 1 to 17
According to the test results in Table 3, it can be seen that the PBT modified material of each example in the invention has excellent elongation at break and good rigidity and fluidity, and the rate of attenuation of elongation at break is less than or equal to 30% after being subjected to 85 ℃ and 85% r.h wet heat aging for 500 h.
From embodiments 1 to 6, the intrinsic viscosity of the PBT resin is preferably not less than 0.8dl/g at 25 ℃, and more preferably, the intrinsic viscosity of the PBT resin is 0.8 to 1.3dl/g at 25 ℃; the PBT resin preferably has a catalyst-remaining amount of 50ppm or less, more preferably 10 to 40 ppm. The PBT resin with higher intrinsic viscosity and lower catalyst residue has better elongation at break attenuation ratio.
In the embodiments 1 and 7 to 8, when the hydrolysis stabilizer containing epoxy or imine functional groups is monomeric carbodiimide, the PBT modified material has a lower percentage of attenuation of elongation at break; from examples 1 and 9 to 11, the hydrolysis stabilizer having an epoxy or imine functional group is preferably 1.0 to 1.5 parts by weight. In the embodiments 1 and 12 to 15, the lubricant is preferably an acrylic acid ethylene copolymer wax, and the lubricant is preferably 0.2 to 2.0 parts by weight. When the lubricant is acrylic acid ethylene copolymer wax, the PBT modified material has better initial elongation at break, rigidity and fluidity, and has lower attenuation rate of elongation at break after humid heat aging.
Table 4 Performance test results of PBT modified materials of comparative examples 1 to 8
According to the test results in Table 4, the PBT in the comparative examples 1-2 has too low or too high carboxyl end group content, and the PBT modified material has elongation at break attenuation ratios of more than 30% after being subjected to damp-heat aging. Comparative examples 3-4 are the PBT modified material prepared by adding no lubricant and adding the toughening agent has very poor flowability, and the attenuation ratio of the elongation at break is more than 40%. Comparative example 5 is that a hydrolysis stabilizer without epoxy or imine functional group is used, comparative example 6 is that no hydrolysis stabilizer is added, and comparative examples 7-8 are that the lubricant in the technical scheme of the invention is not used, and the obtained PBT modified material can not reach the elongation at break attenuation ratio of below 30%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The PBT modified material with high elongation at break is characterized by comprising the following components in parts by weight:
100 parts of PBT resin, 0.2-4 parts of lubricant, 0.05-1.5 parts of hydrolysis stabilizer containing epoxy or imine functional group, and 0-1 part of other auxiliary agent;
the carboxyl-terminated content of the PBT resin is 10-30 mol/t;
the lubricant is one or more of acrylic acid ethylene copolymer wax, oxidized polyethylene wax or polyol ester wax.
2. The PBT-modified material of claim 1, wherein the intrinsic viscosity of the PBT resin is not less than 0.8dl/g at 25 ℃.
3. The PBT-modified material of claim 1, wherein the PBT resin has a catalyst-remaining amount of 50ppm or less.
4. The PBT-modified material according to claim 3, wherein the PBT resin has a catalyst-remaining amount of 10 to 40 ppm.
5. The PBT modified material of claim 1, wherein the hydrolysis stabilizer containing epoxy or imine functional group is one or more of thermoplastic epoxy resin, thermosetting epoxy resin, monomer type carbodiimide, epoxy vegetable oil, glycidyl ester copolymer and glycidyl ester graft.
6. The PBT-modified material of claim 5, wherein the hydrolysis stabilizer comprising an epoxy or imine functional group is a monomeric carbodiimide.
7. The PBT-modified material of claim 1, wherein the lubricant is an acrylic acid ethylene copolymer wax.
8. The PBT modified material of claim 1, wherein the other auxiliary agents are one or more of antioxidants, light stabilizers and ultraviolet absorbers.
9. The preparation method of the PBT modified material of any one of claims 1 to 8, which is characterized by comprising the following steps:
mixing the PBT resin, the lubricant, the hydrolysis stabilizer containing epoxy or imine functional groups and other auxiliary agents, adding the mixture into an extruder, and carrying out melt granulation to obtain the PBT modified material with high elongation at break.
10. Use of the PBT modified material of any one of claims 1 to 8 in the preparation of a PBT product with high elongation at break.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011378570.6A CN112608584B (en) | 2020-11-30 | 2020-11-30 | PBT modified material with high elongation at break as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011378570.6A CN112608584B (en) | 2020-11-30 | 2020-11-30 | PBT modified material with high elongation at break as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112608584A true CN112608584A (en) | 2021-04-06 |
| CN112608584B CN112608584B (en) | 2022-07-12 |
Family
ID=75228319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011378570.6A Active CN112608584B (en) | 2020-11-30 | 2020-11-30 | PBT modified material with high elongation at break as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608584B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114921065A (en) * | 2022-03-18 | 2022-08-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
| CN115895200A (en) * | 2022-03-10 | 2023-04-04 | 上海璟晏新材料有限公司 | Polyester material with good stability and easy processing |
| WO2024139932A1 (en) * | 2022-12-28 | 2024-07-04 | 金发科技股份有限公司 | Pbt resin, and preparation method and use therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694655A (en) * | 2013-12-09 | 2014-04-02 | 方万漂 | Heat-and-humidity-resistant polybutylene terephthalate |
| WO2016179770A1 (en) * | 2015-05-11 | 2016-11-17 | 深圳华力兴新材料股份有限公司 | Pbt engineering plastic composition used for nmt |
| CN107201011A (en) * | 2017-06-26 | 2017-09-26 | 东莞市东翔塑胶有限公司 | It is a kind of can laser marking high shading LED polyester composites and preparation method thereof |
| CN110172235A (en) * | 2019-06-19 | 2019-08-27 | 广州市聚赛龙工程塑料股份有限公司 | A kind of hydrolysis-resistant low-warpage PBT composite and its preparation method and application |
-
2020
- 2020-11-30 CN CN202011378570.6A patent/CN112608584B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694655A (en) * | 2013-12-09 | 2014-04-02 | 方万漂 | Heat-and-humidity-resistant polybutylene terephthalate |
| WO2016179770A1 (en) * | 2015-05-11 | 2016-11-17 | 深圳华力兴新材料股份有限公司 | Pbt engineering plastic composition used for nmt |
| CN107201011A (en) * | 2017-06-26 | 2017-09-26 | 东莞市东翔塑胶有限公司 | It is a kind of can laser marking high shading LED polyester composites and preparation method thereof |
| CN110172235A (en) * | 2019-06-19 | 2019-08-27 | 广州市聚赛龙工程塑料股份有限公司 | A kind of hydrolysis-resistant low-warpage PBT composite and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895200A (en) * | 2022-03-10 | 2023-04-04 | 上海璟晏新材料有限公司 | Polyester material with good stability and easy processing |
| CN114921065A (en) * | 2022-03-18 | 2022-08-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
| CN114921065B (en) * | 2022-03-18 | 2024-03-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
| WO2024139932A1 (en) * | 2022-12-28 | 2024-07-04 | 金发科技股份有限公司 | Pbt resin, and preparation method and use therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112608584B (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112608584B (en) | PBT modified material with high elongation at break as well as preparation method and application thereof | |
| EP3345953A1 (en) | Polyester resin, production method for said polyester resin, and polyester resin composition | |
| CN103102640A (en) | Antistatic polyformaldehyde and preparation method thereof | |
| CN110724377B (en) | Ultra-low temperature high-impact-resistance toughened nylon material and preparation method thereof | |
| CN111073231A (en) | PET material with ultrahigh elongation at break and preparation method thereof | |
| CN111303388B (en) | Preparation method of hydrolysis-resistant PBT polyester resin | |
| CN107987263B (en) | Hydrophilic polyester and preparation method thereof | |
| CA1301403C (en) | Chain extension of polyethylene terephthalate with polyacyllactams | |
| CN103665801A (en) | Resin composition and resin molded article | |
| CN105482388B (en) | A kind of polyester elastomer composition | |
| JP2022536864A (en) | polyester polymer nanocomposite | |
| CN114539735A (en) | PBT/POK composite material and application thereof | |
| JP2011084616A (en) | Modified recycled polyester resin and molded article using the same | |
| CN114213824B (en) | Preparation method of heat-resistant PLA/PBS alloy material | |
| CN112724575B (en) | Low-internal-stress chemical-resistant ACS/PBAT alloy material and preparation method and application thereof | |
| KR102172047B1 (en) | Method for preparing thermoplastic elastomer resin with reduced total volatile organic compounds and improved heat stability | |
| KR20220056346A (en) | Polybutyleneterephthalate resin composition and method for preparing thereof | |
| KR101417413B1 (en) | A method for manufacturing natural fiber poly lactic acid composite materials | |
| CN112898546A (en) | Preparation method of PBAT material with high thermal stability | |
| CN107936232B (en) | Biodegradable polyester and application thereof | |
| CN110305480A (en) | A kind of fire-retardant PPS/PCTG composite material and preparation method of high tenacity and application | |
| CN113845760B (en) | Low-floating-fiber reinforced PBT/PET alloy composition and preparation method and application thereof | |
| WO1999019402A1 (en) | Thermotropic liquid crystalline polymers as stabilizers in thermoplastic polyesters | |
| CN111234470B (en) | Thermal-aging-resistant PET (polyethylene terephthalate) nano composite material and preparation method thereof | |
| CN112175345B (en) | High-impact-resistance wear-resistance glass fiber reinforced POK-HDPE composite 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 |