CN112679843A - Halogen-free flame-retardant polypropylene compound special for new energy automobile and preparation method thereof - Google Patents
Halogen-free flame-retardant polypropylene compound special for new energy automobile and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 54
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 26
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- 238000000034 method Methods 0.000 claims description 4
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- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
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- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001868 water Inorganic materials 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 3
- 230000002093 peripheral effect Effects 0.000 abstract description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 12
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a special halogen-free flame-retardant polypropylene compound for new energy automobiles and a preparation method thereof, and the special halogen-free flame-retardant polypropylene compound comprises the following raw material components: polypropylene, an intumescent flame retardant, a graft, an ionic polymer, chopped glass fiber and a heat stabilizer. The halogen-free flame-retardant polypropylene material has excellent flame-retardant property, overcomes the defects of poor thermal stability and poor water resistance of the traditional halogen-free flame-retardant polypropylene material, and can be applied to peripheral parts of new energy automobile battery packs with flame-retardant requirements.
Description
Technical Field
The invention belongs to the field of high molecular polymer processing, and particularly relates to a special halogen-free flame-retardant polypropylene compound for a new energy automobile and a preparation method thereof.
Background
The polypropylene has gradually replaced engineering plastics such as ABS, PC/ABS and the like and is widely applied to automobile parts due to the advantage of high cost performance. The new energy automobile becomes a development trend of the national automobile industry due to the environmental protection characteristic, and the proportion of the new energy automobile in the automobile market in China is estimated to be more than half by 2030. The new energy automobile adopts the battery pack to replace an engine of a fuel vehicle, so the new energy automobile has excellent flame retardant performance for materials around the battery pack, cannot adopt a brominated flame retardant with extremely high toxicity after combustion, and needs to adopt a halogen-free flame retardant.
At present, the halogen-free flame retardant for polypropylene materials in the industry is mainly an intumescent phosphorus-nitrogen flame retardant, and the components of the halogen-free flame retardant are an acid source, a carbon source and a gas source, wherein the acid source component is ammonium polyphosphate, the carbon source is a main component of pentaerythritol, and the gas source is melamine and derivatives thereof. The halogen-free phosphorus-nitrogen flame retardant has the advantages that the flame retardant performance is excellent, and the products generated after combustion are carbon dioxide, water, nitrogen and other non-toxic gases. The phosphorus-nitrogen intumescent flame retardant has the defects that the surface polarity of the phosphorus-nitrogen intumescent flame retardant is particularly strong, so that the compatibility of the phosphorus-nitrogen intumescent flame retardant with polypropylene is poor, the problems of poor thermal stability and poor hydrolytic stability are caused, after a new energy automobile is used for a long time, the flame retardant is hydrolyzed due to thermal degradation of the flame retardant caused by thermal aging and humid weather, and the flame retardant performance of the final material is seriously reduced. For example, CN102604226A provides a special halogen-free flame-retardant master batch for polypropylene, which is composed of a phosphorus-nitrogen halogen-free flame retardant, a carrier, and a modified ethylene bis-fatty acid amide. In the preparation process, firstly, the carrier and the modified ethylene di-fatty acid amide are banburied for 3-15 min, and then phosphorus-nitrogen halogen-free flame retardant powder is added into a banbury mixer for three times, wherein the interval between each batch feeding is 2-5 min; and the materials are added and then banburied for 5-15 min, so that the problem that the quality of the materials is unstable due to uneven mixing of powder and granules is avoided, and the problems that the halogen-free flame retardant is easy to absorb moisture, degrade and foam are solved. However, the method still does not solve the problems of poor thermal stability and poor water resistance caused by poor compatibility of the phosphorus-nitrogen halogen-free flame retardant and polypropylene.
Disclosure of Invention
The invention aims to solve the technical problem of providing a special halogen-free flame-retardant polypropylene compound for new energy automobiles, which has excellent flame-retardant performance and overcomes the defects of poor thermal stability and poor water resistance of the traditional halogen-free flame-retardant polypropylene material.
The invention provides a halogen-free flame-retardant polypropylene composition special for new energy automobiles, which comprises the following raw materials in parts by weight: polypropylene 23.5-73.9; 10-30 parts of intumescent flame retardant; 2-6 of graft; 4-10 parts of ionic polymer; 10-30 parts of chopped glass fiber; 0.1-0.5 of thermal stabilizer.
Preferably, the composition comprises the following raw materials in parts by weight: 49.8 parts of polypropylene; an intumescent flame retardant 20; graft 4; an ionic polymer 6; chopped glass fiber 20; 0.2 of thermal stabilizer.
Preferably, in the composition, the polypropylene is homopolymerized polypropylene with a melt index of more than or equal to 10g/10 min. Wherein, the test method of the melt index is GB/T3682-2000, and the test conditions are 230 ℃ and 2.16 Kgf.
Preferably, in the above composition, the graft is polypropylene grafted maleic anhydride. Preferably, the grafting yield is 1.0%, as measured by acid-base titration.
Preferably, in the above composition, the ionic polymer is a saponified product of an ethylene/methacrylic acid copolymer. Preferably, the cation is sodium.
Preferably, in the composition, the chopped glass fiber is surface-modified chopped glass fiber treated by a coupling agent. Preferably, the glass fiber has a diameter of 10-20 microns. More preferably, the glass fiber has a diameter of 13 μm
Preferably, in the composition, the heat stabilizer is one or a mixture of several of a phenolic antioxidant, a phosphite antioxidant and a thioester antioxidant.
The second aspect of the present invention provides a preparation method of a halogen-free flame retardant polypropylene composition, comprising:
(1) fully mixing the ionic polymer and the intumescent halogen-free flame retardant in an internal mixer, and extruding and granulating through a single-screw extruder connected with the internal mixer in series to obtain flame-retardant master batches;
(2) mixing the flame-retardant master batch generated by banburying in the banbury mixer in the step (1) with polypropylene, chopped glass fibers, a heat stabilizer and a processing aid, and then extruding and granulating, wherein the temperature of an extruder is set to be 180-220 ℃.
The above banburying step is carried out according to conventional practice in the art, preferably, sufficient banburying is carried out for 20 minutes or more, or 45 minutes or less, more preferably 30 minutes. The step needs to ensure that the surface of the halogen-free flame retardant is fully coated by the ionic polymer, and the strong polar groups on the surface of the halogen-free flame retardant are passivated, so that the thermal stability and hydrolysis resistance of the halogen-free flame retardant are improved.
Preferably, the extruder used in the above-mentioned extrusion step is a twin-screw extruder. More preferably, to ensure that all raw materials are fully plasticized, a 48:1 aspect ratio is used.
A third aspect of the present invention provides the use of the above polypropylene composition in the automotive field.
Advantageous effects
In order to solve the industrial problems of poor thermal stability and poor water resistance caused by poor compatibility of the phosphorus-nitrogen halogen-free flame retardant and polypropylene, the ionic polymer is added into the traditional expanded halogen-free flame retardant polypropylene formula, an internal mixer is adopted to carry out internal mixing processing on the ionic polymer and the expanded phosphorus-nitrogen halogen-free flame retardant before double-screw extrusion blending, and the polar component on the surface of the halogen-free flame retardant is fully combined with the strong ionic bond of the ionic polymer, so that the halogen-free flame retardant is endowed with excellent heat resistance and hydrolysis resistance.
Compared with the existing polypropylene halogen-free flame retardant modification technology, the inventor unexpectedly discovers that the ionic polymer is adopted to pretreat the surface of the phosphorus-nitrogen halogen-free intumescent flame retardant, the strong ionic bond of the ionic polymer enables polar groups on the surface of the halogen-free flame retardant to be fully coated and passivated, the thermal stability and the hydrolytic stability of the halogen-free flame retardant can be greatly improved, and the finally obtained halogen-free flame retardant polypropylene has excellent flame retardance, thermal stability and hydrolytic stability. Through practical tests, the requirements of peripheral parts of the new energy automobile battery on materials are completely met.
In short, the surface of the halogen-free flame retardant is treated by the ionic polymer, so that polar groups on the surface of the halogen-free flame retardant are passivated, and the halogen-free flame retardant is endowed with excellent thermal stability and hydrolytic stability. The prepared polypropylene composition can obviously improve the thermal stability and the hydrolytic stability of the material, has no loss of flame retardant property after thermal aging and water bath soaking experiments, and ensures the application of the polypropylene material in peripheral parts of new energy automobile batteries.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) Sources of raw materials
Polypropylene: the homopolypropylene PP S700, petrochemical in Lanzhou, has a melt index of 12g/10min under the test conditions of GB/T3682-.
Halogen-free phosphorus-nitrogen intumescent flame retardant: FP-2200, Idecaco, Japan.
Graft (C): CA100, maleic anhydride grafted polypropylene, grafting rate 1.0%, French Achima.
Ionic polymer: ethylene/methacrylic acid copolymer saponification products Surlyn 8920, Surlyn8900, Surlyn 9910, cation is sodium ion, Dow chemical.
Short-cutting glass fiber: ER13-2000-988A, Zhejiang river boulder.
Main antioxidant: phenolic antioxidant Irganox 1010, basf; phosphite antioxidant Irganox 168, Basff.
Example 1
(1) 4 parts by weight of ionic polymer Surlyn8900 and 30 kilograms of intumescent halogen-free flame retardant FP-2200 are fully mixed in an internal mixer for 30 minutes to ensure that the surface of the halogen-free flame retardant is fully coated by the ionic polymer and passivates strong polar groups on the surface of the halogen-free flame retardant, so that the thermal stability and hydrolysis resistance of the halogen-free flame retardant are improved, and the mixture is extruded and granulated through a single screw extruder connected in series with the internal mixer after being mixed to obtain the flame-retardant master batch.
(2) Fully mixing the flame-retardant master batch generated by the refining of the internal mixer in the first step with 53.5 parts by weight of polypropylene PP S700, chopped glass fiber ER 13-2000-.
Example 2
(1) Fully mixing 6 parts by weight of ionic polymer Surlyn 8920 and 20 kilograms of intumescent halogen-free flame retardant FP-2200 in an internal mixer for 20 minutes to ensure that the surface of the halogen-free flame retardant is fully coated by the ionic polymer and passivates strong polar groups on the surface of the halogen-free flame retardant, so as to improve the thermal stability and hydrolysis resistance of the halogen-free flame retardant, and extruding and granulating the mixture through a single-screw extruder connected in series with the internal mixer after mixing to obtain the flame-retardant master batch.
(2) Fully mixing the flame-retardant master batch generated by the refining of the internal mixer in the first step with 49.8 parts by weight of polypropylene PP S700, chopped glass fiber ER 13-2000-.
Example 3
(1) Fully mixing 10 parts by weight of ionic polymer Surlyn 9910 and 10 kilograms of intumescent halogen-free flame retardant FP-2200 in an internal mixer for 45 minutes to ensure that the surface of the halogen-free flame retardant is fully coated by the ionic polymer and passivates strong polar groups on the surface of the halogen-free flame retardant, so as to improve the thermal stability and hydrolysis resistance of the halogen-free flame retardant, and extruding and granulating the mixture by a single-screw extruder connected in series with the internal mixer after mixing to obtain the flame-retardant master batch.
(2) Fully mixing the flame-retardant master batch generated by the refining of the internal mixer in the first step with 43.8 parts by weight of polypropylene PP S700, short-cut glass fiber ER 13-2000-.
Comparative example 1
According to the weight ratio shown in Table 1, 55.8 parts by weight of polypropylene PP S700, 4 parts by weight of graft CA100, 20 parts by weight of halogen-free flame retardant FP-2200, 0.1 part by weight of hindered phenol type primary antioxidant Irganox 1010 and 0.1 part by weight of phosphite type auxiliary antioxidant Irganox 168 are fully mixed and then added into a double-screw extruder through a main feed, 30 parts by weight of chopped glass fiber is added through a side feed, and the mixture is extruded and granulated after being fully blended, wherein the extrusion temperature is 200 ℃.
Comparative example 2
According to the weight ratio shown in Table 1, 49.8 parts by weight of polypropylene PP S700, 4 parts by weight of graft CA100, 6 parts by weight of ionic polymer Surlyn 8920, 20 parts by weight of halogen-free flame retardant FP-2200, 0.1 part by weight of hindered phenol type main antioxidant Irganox 1010 and 0.1 part by weight of phosphite type auxiliary antioxidant Irganox 168 are fully mixed and then added into a double-screw extruder through main feeding, 20 parts by weight of chopped glass fiber is added through side feeding, and extrusion granulation is carried out after full blending, wherein the extrusion temperature is 200 ℃.
Table 1 examples formulations table (units are parts by weight)
| Prescription table | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| PP S700 | 55.8 | 49.8 | 53.5 | 49.8 | 43.8 |
| CA100 | 4 | 4 | 2 | 4 | 6 |
| FP-2200 | 20 | 20 | 30 | 20 | 10 |
| Surlyn 8920 | / | 6 | / | 6 | / |
| Surlyn 8900 | / | / | 4 | / | / |
| Surlyn 9910 | / | / | / | / | 10 |
| ER13-2000-988A | 20 | 20 | 10 | 20 | 30 |
| Irganox 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Irganox 168 | 0.1 | 0.1 | 0.4 | 0.1 | 0.1 |
The polymers obtained in examples 1-2 and comparative examples 1-3 were subjected to the following performance tests, the results of which are shown in Table 2.
And (5) performance test method specification. And (3) carrying out UL94 flame retardant test on the plastic particles obtained by extrusion by injection molding by an injection molding machine to obtain 1.0mm standard sample strips. The heat aging test is carried out by adopting a standard oven under the condition of 150 ℃/500h, and the UL94 flame retardant test is carried out after the heat aging. The hydrolytic stability is soaked in a water bath at 70 ℃ for 168 hours, and then a UL94 flame retardant test is carried out.
TABLE 2 Polypropylene composition Performance testing
| Test items | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| UL94 flame resistance test | V-0 | V-0 | V-0 | V-0 | V-0 |
| Flame resistance test after Heat aging | V-2 | V-1 | V-0 | V-0 | V-0 |
| Flame retardance test after 70 ℃ water bath immersion | V-2 | V-1 | V-0 | V-0 | V-0 |
Through comparison experiments between comparative examples 1-2 and examples 1-3, the comparative example 1 is not added with the ionic polymer, the conventional flame retardant property reaches the V-0 grade, and the flame retardant property is excellent, but the flame retardant grade is reduced to the V-2 grade after thermal aging and water bath soaking, which shows that the thermal stability and the hydrolytic stability of the conventional halogen-free flame retardant polypropylene material cannot meet the requirements of new energy automobiles on the material; although the ionic polymer is added, the flame retardant is not coated by adopting an internal mixing process, the conventional flame retardant property of the final material can reach V-0, but after thermal aging and water bath soaking, the flame retardant grade is reduced to V-1 grade, and the flame retardant grade is improved to a certain extent compared with the conventional flame retardant system, which shows that the ionic polymer is indeed helpful to the thermal stability and the hydrolytic stability; in the embodiments 1-3, the ionic polymer is adopted to fully coat the halogen-free flame retardant in the internal mixer before the extrusion and blending of the double-screw extruder, so that the conventional flame retardant performance is excellent, and the flame retardant performance is still V-0 grade after the heat aging and the water bath soaking. The invention fully shows that the invention has the unexpected discovery that the halogen-free flame-retardant polypropylene material with excellent flame-retardant property, thermal stability and hydrolytic stability can be finally obtained, and can be used for parts which have flame-retardant requirements around new energy automobile batteries.
Claims (10)
1. The halogen-free flame-retardant polypropylene composition special for the new energy automobile is characterized by comprising the following raw materials in parts by weight: polypropylene 23.5-73.9; 10-30 parts of intumescent flame retardant; 2-6 of graft; 4-10 parts of ionic polymer; 10-30 parts of chopped glass fiber; 0.1-0.5 of thermal stabilizer.
2. The composition as claimed in claim 1, wherein the raw material components comprise, in parts by weight: 49.8 parts of polypropylene; an intumescent flame retardant 20; graft 4; an ionic polymer 6; chopped glass fiber 20; 0.2 of thermal stabilizer.
3. The composition of claim 1, wherein the polypropylene is a homopolypropylene having a melt index of 10g/10min or more.
4. The composition of claim 1 wherein said graft polymer is polypropylene grafted maleic anhydride.
5. The composition of claim 1, wherein the ionic polymer is a saponified product of an ethylene/methacrylic acid copolymer.
6. The composition as claimed in claim 1, wherein the chopped glass fiber is surface-modified chopped glass fiber treated with a coupling agent.
7. The composition of claim 1, wherein the thermal stabilizer is one or more of a phenolic antioxidant, a phosphite antioxidant, and a thioester antioxidant.
8. A preparation method of a halogen-free flame-retardant polypropylene composition comprises the following steps:
(1) fully mixing the ionic polymer and the intumescent halogen-free flame retardant in an internal mixer, and extruding and granulating through a single-screw extruder connected with the internal mixer in series to obtain flame-retardant master batches;
(2) mixing the flame-retardant master batch generated by banburying in the banbury mixer in the step (1) with polypropylene, chopped glass fibers, a heat stabilizer and a processing aid, and then extruding and granulating, wherein the temperature of an extruder is set to be 180-220 ℃.
9. The process according to claim 8, wherein the extruder used is a twin-screw extruder.
10. Use of the polypropylene composition according to claim 1 in the automotive field.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000129042A (en) * | 1998-10-23 | 2000-05-09 | Sumitomo Electric Ind Ltd | Thermally restorable article prepared from ionomer and linear polyolefin |
| US20100159213A1 (en) * | 2008-12-19 | 2010-06-24 | Przybylinski James P | Wood-Plastic Composites Utilizing Ionomer Capstocks and Methods of Manufacture |
| CN102516667A (en) * | 2011-12-19 | 2012-06-27 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant long glass fiber reinforced polypropylene material and preparation method thereof |
| CN103087312A (en) * | 2012-12-19 | 2013-05-08 | 宁波长阳科技有限公司 | P-N fire retardant, flame-retardant master batch, flame-retardant nylon engineering plastic and preparation method thereof |
| CN104672812A (en) * | 2013-12-02 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Core-shell-structure-toughened halogen-free flame-retardancy-modified PET (polyethylene terephthalate) material |
| CN105802021A (en) * | 2016-05-13 | 2016-07-27 | 上海金发科技发展有限公司 | Scratch-resistant flame-retardant polypropylene composition and preparation method thereof |
| CN108117715A (en) * | 2017-12-28 | 2018-06-05 | 广东聚石化学股份有限公司 | A kind of halogen-free flame-retardant master batch and preparation method thereof |
| CN111171380A (en) * | 2020-03-12 | 2020-05-19 | 广东轻工职业技术学院 | Coated flame retardant and preparation method thereof |
-
2020
- 2020-12-15 CN CN202011478341.1A patent/CN112679843A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000129042A (en) * | 1998-10-23 | 2000-05-09 | Sumitomo Electric Ind Ltd | Thermally restorable article prepared from ionomer and linear polyolefin |
| US20100159213A1 (en) * | 2008-12-19 | 2010-06-24 | Przybylinski James P | Wood-Plastic Composites Utilizing Ionomer Capstocks and Methods of Manufacture |
| CN102516667A (en) * | 2011-12-19 | 2012-06-27 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant long glass fiber reinforced polypropylene material and preparation method thereof |
| CN103087312A (en) * | 2012-12-19 | 2013-05-08 | 宁波长阳科技有限公司 | P-N fire retardant, flame-retardant master batch, flame-retardant nylon engineering plastic and preparation method thereof |
| CN104672812A (en) * | 2013-12-02 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Core-shell-structure-toughened halogen-free flame-retardancy-modified PET (polyethylene terephthalate) material |
| CN105802021A (en) * | 2016-05-13 | 2016-07-27 | 上海金发科技发展有限公司 | Scratch-resistant flame-retardant polypropylene composition and preparation method thereof |
| CN108117715A (en) * | 2017-12-28 | 2018-06-05 | 广东聚石化学股份有限公司 | A kind of halogen-free flame-retardant master batch and preparation method thereof |
| CN111171380A (en) * | 2020-03-12 | 2020-05-19 | 广东轻工职业技术学院 | Coated flame retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王鉴等: "聚丙烯用膨胀型阻燃剂与基体相容性改进的研究进展", 《化学工业与工程技术》, vol. 34, no. 04, 28 August 2013 (2013-08-28), pages 16 - 20 * |
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