CN114479438B - Aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material and preparation method thereof - Google Patents
Aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material and a preparation method thereof, wherein the PA6 reinforced material comprises the following components in percentage by weight: 45-65% of PA6 resin, 15-40% of glass fiber, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide subjected to surface pretreatment, 0.2-0.4% of antioxidant and 1-2% of black master batch, wherein the flame retardant property can reach the level of 1.6mm V0. Under the condition of the same glass fiber content, compared with the common PA6 fiber-added red phosphorus flame-retardant material, the PA6 fiber-added red phosphorus flame-retardant material with the synergistic flame retardance of the surface-pretreated aluminum hydroxide is added, and the aluminum hydroxide can equally replace the red phosphorus master batch when the same flame-retardant level is achieved, and the tensile property and impact property of the material are basically unchanged, so that the mechanical property of the material is not influenced, the formula cost can be effectively reduced, and the market competitiveness of the product is improved.
Description
Technical Field
The invention relates to flame-retardant modification of nylon 6, belongs to the technical field of flame-retardant modification of high polymer materials, and particularly relates to a low-cost aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material and a preparation method thereof.
Background
At present, the most common method for improving the flame retardant property of the composite polymer material is to add a flame retardant in the preparation process. A large number ofEmerging flame retardants such as halogen-based (e.g., chlorides, bromides, etc.), nitrogen-based (e.g., dicyandiamide, biurea, guanidine salts, melamine, salts thereof, etc.), phosphorus-based (e.g., ammonium polyphosphate, phosphate esters, phosphazenes, phosphonates, phosphorus oxides, etc.), silicon-based (e.g., silicone oils, silicones, silicone rubbers, polysiloxanes with functional groups, polycarbonate-siloxane copolymers, etc.), inorganic flame retardants (e.g., aluminum hydroxide, magnesium hydroxide, boride, calcifications, molybdenum compounds, etc.), etc., have addressed to some extent the need for flame retardant composites in certain fields. However, the use of halogen-containing flame retardants in large quantities severely jeopardizes environmental safety and human health, and more researchers are working on developing new halogen-free flame retardants. Wherein, the red phosphorus is a traditional and efficient halogen-free flame retardant, but the red phosphorus which is not subjected to surface treatment is extremely unstable in air and can react with water vapor to generate PH with high toxicity 3 And has poor compatibility with the matrix material and difficult processing.
The current solution to this problem is mainly to encapsulate red phosphorus micropowder with organic and inorganic substances on its surface to isolate moisture and improve compatibility. The microencapsulated red phosphorus has high moisture resistance, good fluidity, long shelf life, and low pH 3 And (3) generating. In the preparation process of microencapsulated red phosphorus, a suitable shell material is an important factor in determining flame retardant properties.
In addition, some metal hydroxides such as magnesium hydroxide and aluminum trihydrate have also been intensively studied as halogen-free flame retardants. These inorganic metal hydroxides can act in the condensed and gas phases and decompose after endothermic reactions, reducing the heating rate of the polymeric material and releasing water vapor into the gas phase, diluting the oxygen concentration in the combustion zone and thus delaying combustion. In addition, the metal hydroxide generated by combustion is condensed on the surface of the polymer material after being cooled, so that an isolated protective layer is formed, and the polymer flame retardance is also facilitated. However, inorganic flame retardants such as magnesium aluminum have excellent flame retardance and smoke suppression performance, but the required addition amount is large, so that the molding processability and physical and mechanical properties of the material are reduced.
The use of red phosphorus as a flame retardant reinforcing additive for polyamide materials has the following significant advantages: the addition amount is small, the flame retardant efficiency is high, and the flame retardant system can maintain excellent mechanical properties; in addition, the red phosphorus flame-retardant polyamide system has a higher CTI value and is widely applied to the fields of electrical switches, low-voltage circuit breakers, connection contactors, sockets and the like. However, red phosphorus has strong hygroscopicity, and is easily oxidized into various oxygen acids of viscous phosphorus (phosphate is generated by reacting with some inorganic minerals in the material) under the action of water and oxygen, and the acids and the salts not only migrate from the inside to the surface of a polymer material system, but also can cause corrosion to metal components, electrodes, coils and the like in an electric appliance, and disproportionation reaction can occur under the environment containing phosphoric acid and phosphorous acid, so that the oxidation of phosphorus is further accelerated.
In order to solve the above problems, for example, a flame retardant thermoplastic composition and a preparation method thereof are disclosed in chinese patent publication No. CN101619166 a, the composition comprises the following components in parts by weight: 40-80 parts of nylon resin, 3-36 parts of red phosphorus flame retardant, 1-50 parts of filler, 0.01-3 parts of phosphorus precipitation stabilizer and 0-50 parts of other auxiliary agents, wherein the phosphorus precipitation stabilizer is one or a mixture of more than two of copper complex and copper halide. Although the technical scheme can well reduce the phosphorus precipitation amount and stability, the copper complex and the copper halide phosphorus precipitation stabilizer have the defects of high cost and the like.
As another example, a Chinese patent document with publication number of CN 105038211A discloses a low-corrosion and low-odor glass fiber reinforced red phosphorus flame-retardant nylon 66 composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 30-71 parts of nylon 66; 15-40 parts by weight of alkali-free and arsenic-free chopped glass fibers; 5-20 parts of red phosphorus flame retardant; 3-8 parts of metal corrosion resistant low-odor synergist; 1-2 parts of other auxiliary agents. Wherein, the metal corrosion resistant low odor synergist is at least one of magnesium hydroxide, aluminum hydroxide, magnesium oxide, calcium oxide, hydrotalcite, copper inhibitor 1024 and grafted POE, which can inhibit or reduce the pungent odor.
Further, as disclosed in the prior art with publication number CN 107793749B, a low-odor red phosphorus flame-retardant reinforced polyamide material is disclosed, wherein the raw materials comprise polyamide resin, a reinforcing component, a red phosphorus flame retardant and an odor absorption inhibitor; the odor absorption inhibitor is selected from modified diatomite or: a complex of at least one of a metal oxide and an acid absorber with modified diatomaceous earth.
On the other hand, although the red phosphorus treated by the microcapsule has better flame retardant effect, the price of the red phosphorus is high, for example, the price of the red phosphorus master batch is 20000-30000 yuan/T, and the high price limits the application of the red phosphorus. Aiming at the problem, according to the advantage of lower price of aluminum hydroxide, the current market price of the aluminum hydroxide is 4000-5000 yuan/T, through continuous exploration and test, the aluminum hydroxide is subjected to surface treatment by selecting a proper surface coating treatment agent, the flame retardant effect of the aluminum hydroxide can be equivalent to the flame retardant effect of red phosphorus in a certain adding proportion, and compared with other schemes, the adding amount of the aluminum hydroxide is less, so that the mechanical properties of the composite material are not influenced. On the basis, an embodiment of replacing the red phosphorus master batch with the aluminum hydroxide with a certain adding proportion is provided, the formula cost can be effectively reduced, and the synergistic flame retardant effect of the aluminum hydroxide and the red phosphorus master batch can be exerted.
Disclosure of Invention
The invention aims to select a proper surface coating treating agent to carry out surface treatment on aluminum hydroxide, so that the aluminum hydroxide can equally replace the flame retardant effect of red phosphorus in a certain adding proportion, and the adding amount of the aluminum hydroxide is less, so that the mechanical properties of the composite material are not affected. On the basis, the invention further aims to provide an embodiment of replacing red phosphorus master batches with aluminum hydroxide in a certain adding proportion, wherein the scheme can effectively reduce the formula cost, and the PA6 composite material with high flame retardant effect is obtained through the synergistic flame retardant effect of the aluminum hydroxide and the red phosphorus master batches.
In order to achieve the above purpose, the present application adopts the following technical scheme: the aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforcing material comprises the following components in percentage by weight: 45-65% of PA6 resin, 15-40% of glass fiber, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide and 0.2-0.4% of antioxidant, wherein the aluminum hydroxide adopts hydroxyethyl methacrylate phosphate for surface pretreatment. In addition, black matrix 1-2% can be added for color matching.
Wherein, the aluminum hydroxide surface pretreatment process comprises the following steps:
and 1, pouring aluminum hydroxide powder into a high-speed mixer, setting the temperature to 80 ℃, and starting stirring for 10min after the temperature is reached.
And 2, slowly dropwise adding hydroxyethyl methacrylate phosphate from a charging hole of the high-speed mixer in the continuous stirring process of the high-speed mixer, wherein the adding proportion of the hydroxyethyl methacrylate phosphate is one percent of the weight of the aluminum hydroxide powder, and the adding speed is controlled to be not more than 100g/min.
And step 3, continuously mixing at a high speed for 10min after the addition of the hydroxyethyl methacrylate phosphate is completed.
In the technical scheme, the hydroxyethyl methacrylate phosphate is utilized to react with aluminum hydroxide, and besides the coupling effect, the introduced phosphorus element also has the flame-retardant effect.
Preferably, the PA6 resin is a polyamide 6 resin having a viscosity between 2.4 and 2.8.
Preferably, the glass fiber is alkali-free glass fiber, and the diameter of glass fiber monofilaments is 10-17 microns.
Preferably, the red phosphorus master batch is a microencapsulated coated red phosphorus master batch, and the phosphorus content is 40% -50%.
Preferably, the antioxidant is 1098 and the antioxidant 627A are compounded according to a ratio of 1:1.
The application further provides a method for preparing an aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material based on the scheme, which comprises the following steps: 45-65% of PA6 resin, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide pretreated by hydroxyethyl methacrylate phosphate surface, 0.2-0.4% of antioxidant and 1-2% of black master batch are uniformly mixed, melted, mixed and extruded by a double screw extruder, fiber is added in the middle section of the extruder, and the PA6 fiber-added flame-retardant material is obtained through cooling, granulating and homogenizing.
In addition, the lubricant is a conventional lubricant such as PETS, zinc stearate or EBS.
The invention has the following technical effects: according to the invention, the hydroxyethyl methacrylate phosphate is utilized to react with the aluminum hydroxide, and besides the coupling effect, the introduced phosphorus element also plays a role in flame retardance, so that the aluminum hydroxide pretreated by the hydroxyethyl methacrylate phosphate can equally replace the red phosphorus master batch in a certain proportion (3% -5%), thereby obtaining unexpected flame retardance, and the mechanical properties of the material are almost not influenced, and the mechanical properties are equivalent. In addition, the pretreated aluminum hydroxide can effectively reduce the production cost after equivalent replacement of the red phosphorus master batch.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The components and proportions of the components contained in the examples and comparative examples are shown in Table 1.
The technical prejudice in the art generally suggests that although inorganic flame retardants such as aluminum hydroxide have excellent flame retarding and smoke suppressing properties, the required addition amount is large, resulting in degradation of the molding processability of the material and the physical mechanical properties of the product. However, the inventor of the application unexpectedly found in the experimental research process that after the hydroxyethyl methacrylate phosphate is used as a surface treatment agent of aluminum hydroxide for coupling and coating pretreatment, when the mass ratio of the aluminum hydroxide is 18% in a certain proportion range, the aluminum hydroxide can equally replace the red phosphorus in the proportion range of 3% -5% and obtain an unexpected flame-retardant effect, and the synergistic flame-retardant effect of the two is equivalent to the flame-retardant effect of the red phosphorus. The reason is that the hydroxyethyl methacrylate phosphate is utilized to react with aluminum hydroxide, and the introduced phosphorus element has flame retardant effect besides the coupling effect. In view of the above, the inventor performs further screening tests on the proportion selection of the equal amount of aluminum hydroxide to replace red phosphorus, and finally determines that the optimal proportion range of the equal amount of aluminum hydroxide to replace red phosphorus is 3% -5%, and fully plays the synergistic flame retardant effect of the equal amount of aluminum hydroxide to replace red phosphorus.
Therefore, the key point of the application lies in how to select a surface treating agent to carry out coupling and coating treatment on aluminum hydroxide, and the treated aluminum hydroxide can equally replace the implementation scheme of the red phosphorus master batch in a certain proportion range, so that the flame retardant effect of the aluminum hydroxide can completely replace the flame retardant effect of red phosphorus, and the synergistic flame retardant effect of the aluminum hydroxide and the red phosphorus is generated, and the addition amount of the aluminum hydroxide is less, so that the mechanical properties of the composite material are not influenced, and the formula cost is effectively reduced.
In a specific embodiment, the aluminum hydroxide disclosed by the invention is subjected to surface pretreatment by using hydroxyethyl methacrylate phosphate, and the pretreatment process comprises the following steps of:
step 1, pouring aluminum hydroxide powder into a high-speed mixer, setting the temperature to 80 ℃, and starting stirring for 10min after the temperature is reached;
step 2, slowly dropwise adding hydroxyethyl methacrylate phosphate from a charging hole of the high-speed mixer in the continuous stirring process of the high-speed mixer, wherein the adding proportion of the hydroxyethyl methacrylate phosphate is one percent of the weight of the aluminum hydroxide powder, and the adding speed is controlled to be not more than 100g/min;
and step 3, continuously mixing at a high speed for 10min after the addition of the hydroxyethyl methacrylate phosphate is completed.
In a specific embodiment, the following preparation process is adopted:
45-65% of PA6 resin, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide pretreated by hydroxyethyl methacrylate phosphate surface, 0.2-0.4% of antioxidant and 1-2% of black master batch are uniformly mixed, melted, mixed and extruded by a double screw extruder, fiber is added in the middle section of the extruder, and the PA6 fiber-added flame-retardant material is obtained through cooling, granulating and homogenizing.
Table 1 formulation tables of examples and comparative examples
Performance test:
tensile property test: the test was carried out according to ISO 527-2, the stretching speed being 50mm/min.
Bending performance test: the bending speed was 5mm/min as tested according to ISO 178.
Impact resistance test: the bending speed was 2mm/min, tested according to ASTM D792.
The UL94 standard was used to test the burn performance.
TABLE 2 mechanical Properties and flame retardant Properties of PA6 reinforced materials
The test data show that the test of replacing red phosphorus flame retardant master batch with the equal amount of the pretreated and untreated aluminum hydroxide of the hydroxyethyl methacrylate phosphate has the following characteristics:
as can be seen from the comparison of the test data of the first example and the comparative example B (untreated aluminum hydroxide), the aluminum hydroxide which is not pretreated by hydroxyethyl methacrylate phosphate cannot reach the flame retardant V-0 grade when the red phosphorus master batch is replaced equally, so that the red phosphorus master batch cannot be replaced equally, the mechanical properties of the materials are affected, and a large amount of addition is required to reach the expected flame retardant effect, but the tensile strength, the bending strength and the impact strength of the composite material are obviously affected.
Secondly, as can be seen from the data comparison of the examples and the comparative example A (without adding aluminum hydroxide and only adding red phosphorus), the aluminum hydroxide pretreated by the hydroxyethyl methacrylate phosphate can equally replace the red phosphorus master batch, and the mechanical properties of the materials are almost not affected, and the mechanical properties are equivalent. Therefore, the pretreated aluminum hydroxide can effectively reduce the production cost after equivalent replacement of the red phosphorus master batch.
While the foregoing description illustrates and describes the preferred embodiments of the present invention, as noted above, it is to be understood that the invention is not limited to the forms disclosed herein but is not to be construed as excluding other embodiments, and that various other combinations, modifications and environments are possible and may be made within the scope of the inventive concepts described herein, either by way of the foregoing teachings or by those of skill or knowledge of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
1. The aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material is characterized by comprising the following components in percentage by weight: 45-65% of PA6 resin, 15-40% of glass fiber, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide and 0.2-0.4% of antioxidant, wherein the aluminum hydroxide adopts hydroxyethyl methacrylate phosphate for surface pretreatment;
the aluminum hydroxide surface pretreatment process comprises the following steps:
step 1, pouring aluminum hydroxide powder into a high-speed mixer, setting the temperature to 80 ℃, and starting stirring for 10min after the temperature is reached;
step 2, slowly adding hydroxyethyl methacrylate phosphate from a charging port of the high-speed mixer in the continuous stirring process of the high-speed mixer, wherein the adding proportion of the hydroxyethyl methacrylate phosphate is one percent of the weight of the aluminum hydroxide powder, and the adding speed is controlled to be not more than 100g/min;
step 3, continuously mixing at a high speed for 10min after the addition of the hydroxyethyl methacrylate phosphate is completed, so as to obtain the modified acrylic acid modified epoxy resin;
the UL94 flame retardant rating of the PA6 reinforced material is V-0.
2. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to claim 1, characterized in that: the PA6 reinforced material comprises the following components in percentage by weight: 64.3% of PA6 resin, 17% of glass fiber, 13% of red phosphorus master batch, 0.3% of lubricant, 5% of aluminum hydroxide and 0.4% of antioxidant, wherein the UL94 flame retardant rating of the PA6 reinforcing material is V-0.
3. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to claim 1, characterized in that: the PA6 reinforced material comprises the following components in percentage by weight: 54.3% of PA6 resin, 30% of glass fiber, 11% of red phosphorus master batch, 0.3% of lubricant, 4% of aluminum hydroxide and 0.4% of antioxidant, wherein the UL94 flame retardant rating of the PA6 reinforced material is V-0.
4. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to claim 1, characterized in that: the PA6 reinforced material comprises the following components in percentage by weight: 45.8% of PA6 resin, 40% of glass fiber, 10.5% of red phosphorus master batch, 0.3% of lubricant, 3% of aluminum hydroxide and 0.4% of antioxidant, wherein the UL94 flame retardant rating of the PA6 reinforced material is V-0.
5. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to any one of claims 1-4, characterized in that: the PA6 resin is polyamide 6 resin with the viscosity of 2.4-2.8.
6. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to any one of claims 1-4, characterized in that: the glass fiber is alkali-free glass fiber, and the diameter of glass fiber monofilaments is 10-17 microns.
7. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to any one of claims 1-4, characterized in that: the red phosphorus master batch is a microencapsulated coated red phosphorus master batch, and the phosphorus content is 40% -50%.
8. The aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforcing material according to any one of claims 1-4, characterized in that: the antioxidant is 1098 and the antioxidant 627A are compounded according to a ratio of 1:1.
9. A method for preparing the aluminum hydroxide synergistic red phosphorus flame retardant PA6 reinforced material according to claim 1, characterized in that: 45-65% of PA6 resin, 10-15% of red phosphorus master batch, 0.3-0.5% of lubricant, 3-5% of aluminum hydroxide pretreated by hydroxyethyl methacrylate phosphate surface, 0.2-0.4% of antioxidant and 1-2% of black master batch are uniformly mixed, melted, mixed and extruded by a double screw extruder, glass fiber is added in the middle section of the extruder, and the PA6 fiber-added flame-retardant material is obtained through cooling, granulating and homogenizing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1591137A (en) * | 1976-12-13 | 1981-06-17 | Gen Electric | Self-extinguishing polyphenylene ether moulding compositions |
| CN105339465A (en) * | 2013-05-28 | 2016-02-17 | 路博润高级材料公司 | Non-halogen flame retardant polymers |
| CN106279556A (en) * | 2016-08-15 | 2017-01-04 | 三河市洲通光电科技有限公司 | A kind of fiber reinforced plastics pole and production method thereof and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1591137A (en) * | 1976-12-13 | 1981-06-17 | Gen Electric | Self-extinguishing polyphenylene ether moulding compositions |
| CN105339465A (en) * | 2013-05-28 | 2016-02-17 | 路博润高级材料公司 | Non-halogen flame retardant polymers |
| CN106279556A (en) * | 2016-08-15 | 2017-01-04 | 三河市洲通光电科技有限公司 | A kind of fiber reinforced plastics pole and production method thereof and application |
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