CN114044997A - Polyethylene composite material for glass fiber reinforced thermoplastic pipeline - Google Patents
Polyethylene composite material for glass fiber reinforced thermoplastic pipeline Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention relates to a polyethylene composite material for a glass fiber reinforced thermoplastic pipeline, belonging to the technical field of pipeline materials. In order to solve the problem of poor impact resistance in the prior art, the polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight: high density polyethylene: 50-70 parts of; linear low density polyethylene: 10-20; peroxide initiator: 0.01 to 0.03; maleic anhydride: 1-5; dispersing agent: 5.0 to 8.0; activated calcium carbonate: 2.0 to 4.0; carbon black: 1.0 to 3.0; modified glass fiber: 5-15; the modified glass fiber is obtained by firstly adopting an unsaturated silane coupling agent to carry out surface modification treatment on the glass fiber and then grafting polymethyl methacrylate. The invention can effectively improve the compatibility and the interface bonding force between the glass fiber and the matrix material, and realize the high impact strength performance and the ring stiffness strength performance of the material.
Description
Technical Field
The invention relates to a polyethylene composite material for a glass fiber reinforced thermoplastic pipeline, belonging to the technical field of pipeline materials.
Background
The plastic pipelines are divided into thermoplastic pipelines and thermosetting plastic pipelines, the thermoplastic pipelines are various, such as PE (polyethylene) pipes, PVC (polyvinyl chloride) pipes, PP (polypropylene) pipes and the like, and the thermoplastic plastic pipelines have the characteristics of easiness in recycling, strong impact resistance, good fracture toughness, short forming period, high production efficiency and the like, are widely applied to the fields of building materials, electrical equipment, automobiles, aerospace and the like, and are very widely applied to the plastic pipelines in daily life. Thermoplastic materials have low strength properties and are difficult to adapt to the requirements of high stiffness and high pressure, while the thermoplastic composites are often reinforced with fibers to give better properties of impact resistance, high temperature resistance and thermal stability. However, due to the interfacial incompatibility between the fibers and the polyethylene material, the fibers may not be bonded during the melt impregnation process, resulting in poor overall strength, and in order to improve the compatibility and bonding force between the fibers and the matrix material, the fibers are usually modified to enhance the bonding between the fibers and the matrix resin. Therefore, fibers are usually modified first, such as a PE modified material and a preparation method thereof disclosed in the prior document (publication No. CN109694512A), wherein the PE modified material comprises 40-50 parts of high-density polyethylene, 15-25 parts of low-density polyethylene, 5-15 parts of alkali-free fibers, 5-20 parts of diatomite, 10-15 parts of a silane coupling agent, 5-15 parts of polytetrafluoroethylene, 5-10 parts of a compatilizer, 5-10 parts of a flexibilizer, 5-10 parts of a lubricant, and a high-efficiency composite antioxidant. The material is modified mainly by adopting the selected modified alkali-free glass fiber, so that the problems of the material strength performance reduction and the like caused by the water absorption of the material are solved, and the overall impact strength performance of the material is poor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a polyethylene composite material for a glass fiber reinforced thermoplastic pipeline, and solves the problem of how to realize the combination of high impact strength performance and ring stiffness strength performance.
The invention aims to realize the purpose through the following technical scheme, and the polyethylene composite material for the glass fiber reinforced thermoplastic pipeline is characterized by comprising the following components in parts by weight:
high density polyethylene: 50-70 parts of; linear low density polyethylene: 10-20; peroxide initiator: 0.01 to 0.03; maleic anhydride: 1-5; dispersing agent: 5.0 to 8.0; activated calcium carbonate: 2.0 to 4.0; carbon black: 1.0 to 3.0; modified glass fiber: 5-15;
the modified glass fiber is obtained by firstly adopting an unsaturated silane coupling agent to carry out surface modification treatment on the glass fiber and then grafting polymethyl methacrylate.
The surface of the glass fiber is activated by adopting an unsaturated silane coupling agent for surface modification, namely, the silane coupling agent can form a chemical bond function of Si-O-Si bonding with the glass fiber, so that the surface is activated, then a specific polymer polymethyl methacrylate is grafted, grafting can be successfully carried out, and the glass fiber-g-polymethyl methacrylate is formed, so that the grafting efficiency is higher, meanwhile, after the maleic anhydride is added under the action of an initiator to form grafting with polyethylene, the polarity of the polyethylene is increased, the synergistic effect of the two effectively improves the compatibility between the modified glass fiber and a matrix material, improves the interface bonding force between the glass fiber and the matrix material, and realizes the high impact strength performance and the ring stiffness strength performance of the material; meanwhile, the overall strength performance can be improved by adding the carbon black and the activated calcium carbonate, and the compatibility between the activated calcium carbonate and the polyethylene resin is obviously improved.
In the polyethylene composite material for glass fiber reinforced thermoplastic pipe, the unsaturated silane coupling agent is preferably one or a mixture of several selected from vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylethoxysilane, methylvinyldiethoxysilane and methacryloxypropyltrimethylsilane. The surface of the glass fiber can be modified more effectively, and the polymethyl methacrylate can be grafted to the surface of the glass fiber more effectively, so that the interface bonding force between the glass fiber and a base material can be better realized, the glass fiber can be dispersed in the base material more uniformly, and the glass fiber has high impact strength. Preferably, before the silanization surface treatment, hydroxylation treatment is carried out on the surface of the glass fiber to form hydroxylated glass fiber, so that the surface activity of the glass fiber is further improved, and the grafting effectiveness is improved. In another preferred embodiment, the modified glass fiber comprises 3 to 6 parts by weight of glass fiber modified by a triblock copolymer coupling agent, the triblock copolymer coupling agent has a block ratio of a: b: c, and the triblock copolymer coupling agent is polystyrene-b-polybutyl acrylate-b-poly-gamma-methacryloxypropyl trimethoxysilane (PS-b-PBA-b-PMPS), preferably, the block ratio is that a is 50 to 200, b is 50 to 200, and c is 10 to 30. Through the synergistic effect of the two modified glass fibers, the overall impact strength performance of the material can be more effectively improved. The mass ratio of the glass fiber-g-polymethyl methacrylate to the modified glass fiber obtained by modifying the glass fiber with the triblock copolymer coupling agent is preferably 1: 1.0 to 2.0.
In the polyethylene composite material for glass fiber reinforced thermoplastic pipes, the mass percentage of the polymethyl methacrylate in the modified glass fiber is preferably 15 to 20%. The whole grafting rate can be controlled within the range, and the aim is to better improve the compatibility and the whole impact strength performance.
In the polyethylene composite material for glass fiber reinforced thermoplastic pipe, the peroxide initiator is preferably one or more selected from dicumyl peroxide, ditert-butane peroxide, 1, 3-ditert-butyl dicumyl peroxide and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexyne. In the processing process, the initiation reaction can be better carried out, the maleic anhydride grafted polyethylene is promoted, and the integral impact strength performance of the material is improved.
In the above polyethylene composite material for glass fiber reinforced thermoplastic pipes, preferably, the activated calcium carbonate is activated by using a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent. The modified calcium carbonate has the advantages of improving the surface activity of calcium carbonate, having better compatibility with a high-density polyethylene material, having good dispersibility, being more beneficial to uniform dispersion in a matrix material to form a stress concentration point, being more beneficial to fully absorbing the impact force of the material, leading the material not to generate structural damage when being subjected to external pressure, improving the overall impact strength performance, and having obvious effects of enhancing and stiffening under the combined action of the modified calcium carbonate and the added carbon black. More preferably, the particle size of the activated calcium carbonate is 800 to 3000 mesh.
In the polyethylene composite material for the glass fiber reinforced thermoplastic pipeline, preferably, the melt index of the high-density polyethylene is 0.01-2 g/10min, and the melt index of the linear low-density polyethylene is 20-100 g/10 min. The fluidity of the melt can be improved by improving the melt index of the polyethylene, so that the polyethylene can be better bonded with the modified glass fiber in the processing process, and the bonding force of an interface is improved.
In the above polyethylene composite material for glass fiber reinforced thermoplastic pipe, preferably, the dispersant is selected from polyethylene wax and/or polypropylene wax. The integral dispersion performance of the material is improved, so that more effective uniform dispersion performance is formed, and the impact strength performance of the material is improved.
In summary, compared with the prior art, the invention has the following advantages:
1. according to the invention, the glass fiber is modified, the specific material polymethyl methacrylate is adopted, and the added maleic anhydride can form grafting with polyethylene under the action of the initiator, so that the polarity of the polyethylene is increased, the compatibility between the modified glass fiber and the matrix material is effectively improved under the synergistic effect of the two, the interface bonding force between the modified glass fiber and the matrix material is improved, and the high impact strength performance and the ring stiffness strength performance of the material are realized.
2. By adopting the unsaturated silane coupling agent, the interface bonding force between the reality and the matrix material can be better, and the integral impact strength performance is improved.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples, but the present invention is not limited to these examples.
Example 1
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 70; linear low density polyethylene: 20; dicumyl peroxide: 0.03; maleic anhydride: 5; polyethylene wax: 8.0; activated calcium carbonate: 2.0, activating by adopting a titanate coupling agent; furnace carbon black: 3.0; modified glass fiber: 15;
the modified glass fiber is prepared by performing surface modification treatment on the glass fiber by using vinyl trimethoxy silane and grafting polymethyl methacrylate to obtain glass fiber-g-polymethyl methacrylate.
The polyethylene composite material can be obtained by a general method, and can be prepared by the following general methods:
adding high-density polyethylene, linear low-density polyethylene, dicumyl peroxide, maleic anhydride, polyethylene wax and activated calcium carbonate into a mixer according to the weight part ratio of the raw materials, activating by adopting a titanate coupling agent, adding furnace carbon black and modified glass fiber into the mixer for high-speed mixing, controlling the temperature of the mixer to be between 26 and 30 ℃, and obtaining a corresponding mixture for later use after the mixing time is 5 to 15 minutes;
the modified glass fiber is prepared by performing surface modification treatment on the glass fiber by using vinyl trimethoxy silane and grafting polymethyl methacrylate to obtain glass fiber-g-polymethyl methacrylate.
Directly adding the mixture into a double-screw extruder for granulation processing, wherein the set temperature of the extruder is divided into 9 sections from a feed inlet to a neck mold, the temperature of each section is gradually increased by 5-10 ℃ in sequence, the processing temperature of the whole extruder is controlled at 110-220 ℃, the main machine rotating speed of the extruder is controlled to ensure that the retention time of the material in the extruder is 2-5 min, the vacuum degree of vacuum extraction of the extruder is lower than-0.08 MPa, and the length-diameter ratio of the extruder is greater than 36: 1.
Example 2
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 50; linear low density polyethylene: 15; 1, 3-di-tert-butylperoxydiisopropylbenzene: 0.02; maleic anhydride: 2; polyethylene wax: 7.0; activated calcium carbonate: 2.0, activating by using an aluminate coupling agent; furnace carbon black: 2.0; modified glass fiber: 12;
the modified glass fiber is prepared by performing surface modification treatment on glass fiber by adopting dimethyl vinyl ethoxysilane and grafting polymethyl methacrylate to obtain glass fiber-g-polymethyl methacrylate.
The above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 3
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 60, adding a solvent to the mixture; linear low density polyethylene: 14; 1, 3-di-tert-butylperoxydiisopropylbenzene: 0.03; maleic anhydride: 3; polypropylene wax: 5.0; activated calcium carbonate: 3.0, activating by using an aluminate coupling agent; furnace carbon black: 1.0; modified glass fiber: 10;
the modified glass fiber is prepared by performing surface modification treatment on glass fiber by adopting methacryloxypropyltrimethylsilane and grafting polymethyl methacrylate to obtain glass fiber-g-polymethyl methacrylate.
The above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 4
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 65; linear low density polyethylene: 16; 2, 5-dimethyl-2, 5 bis (t-butylperoxy) hexyne: 0.03; maleic anhydride: 4; polyethylene wax: 5.0; activated calcium carbonate: 3.0, activating by adopting a silane coupling agent, wherein the particle size is 1500 meshes; furnace carbon black: 2.0; modified glass fiber: 10;
the melt index of the high-density polyethylene is 0.01-2 g/10min, the melt index of the linear low-density polyethylene is 20-100 g/10min, the modified glass fiber is obtained by performing surface modification treatment on glass fiber by adopting dimethyl vinyl ethoxysilane and grafting polymethyl methacrylate, and the mass percentage of the polymethyl methacrylate in the glass fiber-g-polymethyl methacrylate is 20%;
the above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 5
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 55; linear low density polyethylene: 10; 2, 5-dimethyl-2, 5 bis (t-butylperoxy) hexyne: 0.01; maleic anhydride: 3; polyethylene wax: 6.0; activated calcium carbonate: 2.0, activating by adopting a silane coupling agent, wherein the particle size is 1500 meshes; furnace carbon black: 3.0; modified glass fiber: 5;
the melt index of the high-density polyethylene is 0.01-2 g/10min, the melt index of the linear low-density polyethylene is 20-100 g/10min, the modified glass fiber is glass fiber-g-polymethyl methacrylate obtained by performing surface modification treatment on glass fiber by adopting dimethyl vinyl ethoxysilane and grafting polymethyl methacrylate, and the mass percentage of the polymethyl methacrylate in the glass fiber-g-polymethyl methacrylate is 15%;
the above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 6
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 55; linear low density polyethylene: 10; 2, 5-dimethyl-2, 5 bis (t-butylperoxy) hexyne: 0.01; maleic anhydride: 3; polyethylene wax: 6.0; activated calcium carbonate: 2.0, activating by adopting a silane coupling agent, wherein the particle size is 1500 meshes; furnace carbon black: 3.0; modified glass fiber: 5;
wherein the melt index of the high-density polyethylene is 0.01-2 g/10min, the melt index of the linear low-density polyethylene is 20-100 g/10min, 2 parts of the modified glass fibers are glass fiber-g-polymethyl methacrylate obtained by performing surface modification treatment on glass fibers by adopting dimethylvinylethoxysilane and grafting polymethyl methacrylate, and the mass percent of the polymethyl methacrylate in the glass fiber-g-polymethyl methacrylate is 15%; the other 3 parts by weight are formed by modifying glass fibers by using a triblock copolymer coupling agent, the triblock copolymer coupling agent has a block ratio of a: b: c, the triblock copolymer coupling agent is polystyrene-b-polybutyl acrylate-b-poly gamma-methacryloxypropyltrimethoxysilane (PS-b-PBA-b-PMPS), and in the block ratio, a is 200, b is 200 and c is 30;
the above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 7
The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 65; linear low density polyethylene: 15; 1, 3-di-tert-butylperoxydiisopropylbenzene: 0.03; maleic anhydride: 5; polyethylene wax: 5.0; activated calcium carbonate: 4.0, activating by adopting a silane coupling agent, wherein the particle size is 3000 meshes; furnace carbon black: 2.0; modified glass fiber: 12;
wherein the melt index of the high-density polyethylene is 0.01-2 g/10min, the melt index of the linear low-density polyethylene is 20-100 g/10min, 6 parts of the modified glass fibers are glass fiber-g-polymethyl methacrylate obtained by performing surface modification treatment on glass fibers by adopting dimethylvinylethoxysilane and grafting polymethyl methacrylate, and the mass percentage of the polymethyl methacrylate in the glass fiber-g-polymethyl methacrylate is 20%; in addition, 6 parts by weight of the modified glass fiber is prepared by modifying glass fiber by using a triblock copolymer coupling agent, the triblock copolymer coupling agent has a block ratio of a: b: c, the triblock copolymer coupling agent is polystyrene-b-polybutyl acrylate-b-poly gamma-methacryloxypropyltrimethoxysilane (PS-b-PBA-b-PMPS), and in the block ratio, a is 100, b is 100 and c is 10;
the above polyethylene composite material can be substantially the same as that of example 1, and will not be described herein.
Example 8
The weight ratio of the components of the polyethylene composite of this example was substantially the same as that of example 7, except that the triblock copolymer coupling agent was polystyrene-b-polybutylacrylate-b-poly-gamma-methacryloxypropyltrimethoxysilane (PS-b-PBA-b-PMPS), and the block ratio was 50 for a, 50 for b, and 10 for c.
Comparative example 1
To illustrate the effect of the selection of polymers in the modified glass fibers on the performance of the polyethylene matrix composite of the present invention, example 2 is used as a comparative example, and the present comparative example is illustrated by the ratio of modified glass fibers using other polymers, specifically as follows:
the polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 50; linear low density polyethylene: 15; 1, 3-di-tert-butylperoxydiisopropylbenzene: 0.02; maleic anhydride: 2; polyethylene wax: 7.0; activated calcium carbonate: 2.0, activating by using an aluminate coupling agent; furnace carbon black: 2.0; modified glass fiber: 12;
the modified glass fiber is polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber.
The above polyethylene composite material can be substantially the same as that of example 2, and will not be described herein.
Comparative example 2
To illustrate the effect of the selection of polymers in the modified glass fibers on the performance of the polyethylene matrix composite of the present invention, example 5 is used as a comparative example, and the present comparative example is illustrated by the ratio of modified glass fibers using other polymers, specifically as follows:
the polyethylene composite material for the glass fiber reinforced thermoplastic pipeline comprises the following components in parts by weight:
high density polyethylene: 55; linear low density polyethylene: 10; 2, 5-dimethyl-2, 5 bis (t-butylperoxy) hexyne: 0.01; maleic anhydride: 3; polyethylene wax: 6.0; activated calcium carbonate: 2.0, activating by adopting a silane coupling agent, wherein the particle size is 1500 meshes; furnace carbon black: 3.0; modified glass fiber: 5;
wherein the melt index of the high-density polyethylene is 0.01-2 g/10min, the melt index of the linear low-density polyethylene is 20-100 g/10min, and the modified glass fiber is polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber.
The above polyethylene composite material can be substantially the same as that of example 5, and will not be described herein.
The composite materials obtained in the above examples and comparative examples were randomly selected as samples and processed into corresponding test pipes (160mm x 6.2mm) for corresponding performance tests, and the test results are shown in the following table 1:
table 1:
the specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (8)
1. The polyethylene composite material for the glass fiber reinforced thermoplastic pipeline is characterized by comprising the following components in parts by weight:
high density polyethylene: 50-70 parts of; linear low density polyethylene: 10-20; peroxide initiator: 0.01 to 0.03; maleic anhydride: 1-5; dispersing agent: 5.0 to 8.0; activated calcium carbonate: 2.0 to 4.0; carbon black: 1.0 to 3.0; modified glass fiber: 5-15;
the modified glass fiber is obtained by firstly adopting an unsaturated silane coupling agent to carry out surface modification treatment on the glass fiber and then grafting polymethyl methacrylate.
2. A polyethylene composite material for glass fiber reinforced thermoplastic pipes as claimed in claim 1, wherein the unsaturated silane coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylethoxysilane, methylvinyldiethoxysilane, methacryloxypropyltrimethylsilane.
3. The polyethylene composite material for the glass fiber reinforced thermoplastic pipe as claimed in claim 1, wherein the mass percentage of the polymethyl methacrylate in the modified glass fiber is 15-20%.
4. A polyethylene composite material for glass fibre reinforced thermoplastic pipes according to claim 1 or 2 or 3, characterized in that the peroxide initiator is selected from one or a mixture of dicumyl peroxide, ditert-butane peroxide, 1, 3-ditert-butyl-dicumyl peroxide and 2, 5-dimethyl-2, 5 bis (tert-butylperoxy) hexyne.
5. A polyethylene composite for glass fiber reinforced thermoplastic pipes according to claim 1, 2 or 3, characterized in that the activated calcium carbonate is activated by using a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
6. The polyethylene composite for glass fiber reinforced thermoplastic pipes according to claim 5, wherein the activated calcium carbonate has a particle size of 800 mesh to 3000 mesh.
7. The polyethylene composite material for glass fiber reinforced thermoplastic pipe as claimed in claim 1, 2 or 3, wherein the melt index of the high density polyethylene is 0.01 to 2g/10min, and the melt index of the linear low density polyethylene is 20 to 100g/10 min.
8. A polyethylene composite for glass fiber reinforced thermoplastic pipes according to claim 1, 2 or 3, characterized in that the dispersing agent is selected from polyethylene wax and/or polypropylene wax.
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| CN202111557184.8A CN114044997B (en) | 2021-12-18 | 2021-12-18 | Polyethylene composite material for glass fiber reinforced thermoplastic pipeline |
| PCT/CN2021/141440 WO2023108805A1 (en) | 2021-12-18 | 2021-12-27 | Glass fiber-reinforced polyethylene composite material for thermoplastic pipe |
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| CN202111557184.8A CN114044997B (en) | 2021-12-18 | 2021-12-18 | Polyethylene composite material for glass fiber reinforced thermoplastic pipeline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116653366A (en) * | 2023-04-13 | 2023-08-29 | 日丰企业(天津)有限公司 | Heat-resistant reinforced PPR pipe and preparation method thereof |
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| CN1887947A (en) * | 2006-08-03 | 2007-01-03 | 上海交通大学 | Prepn of composite polyethylene/glass material |
| US20190203024A1 (en) * | 2016-09-19 | 2019-07-04 | Lotte Chemical Corporation | Glass fiber composite material composition having improved impact strength |
| CN108912451A (en) * | 2018-06-29 | 2018-11-30 | 长春智享优创科技咨询有限公司 | Fiber reinforcement composite polyethylene material and preparation method thereof |
| CN112724486A (en) * | 2020-12-22 | 2021-04-30 | 金发科技股份有限公司 | Polyolefin material and preparation method and application thereof |
| CN113773458A (en) * | 2021-09-14 | 2021-12-10 | 安徽华超新材料科技有限公司 | Modification treatment method of chopped glass fibers |
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| CN116653366A (en) * | 2023-04-13 | 2023-08-29 | 日丰企业(天津)有限公司 | Heat-resistant reinforced PPR pipe and preparation method thereof |
| CN116653366B (en) * | 2023-04-13 | 2023-12-29 | 日丰企业(天津)有限公司 | Heat-resistant reinforced PPR pipe and preparation method thereof |
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| CN114044997B (en) | 2022-12-02 |
| WO2023108805A1 (en) | 2023-06-22 |
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