CN104194161A - Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof - Google Patents

Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof Download PDF

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Publication number
CN104194161A
CN104194161A CN201410512285.7A CN201410512285A CN104194161A CN 104194161 A CN104194161 A CN 104194161A CN 201410512285 A CN201410512285 A CN 201410512285A CN 104194161 A CN104194161 A CN 104194161A
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parts
flame
composite material
preparation
polypropylene
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Inventor
蔡涛涛
蔡书芝
赵航
周晓东
周继波
石广钦
周玉娟
李莹
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JIANGSU LIDA MOLD PLASTIC MANUFACTURING CO LTD
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JIANGSU LIDA MOLD PLASTIC MANUFACTURING CO LTD
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention discloses a precipitation resistant, toughening and flame-retardant polypropylene composite material and a preparation method thereof. The precipitation resistant, toughening and flame-retardant polypropylene composite material comprises the following raw materials ( taking100 parts as a measurement unit ): 50-75 parts of polypropylene, 2-15 parts of a toughening agent, 2-8 parts of a compatilizer, 10-25 parts of flame retardant silicane coated ammonium polyphosphate, 5-10 parts of flame retardant melamine cyanurate, 0.2-2 part (s) of an associative-effect flame retardant, 0.1-0.5 part of an anti-oxidant 168 and 0.1-0.8 part of an anti-oxidant 1010. According to the precipitation resistant, toughening and flame-retardant polypropylene composite material and the preparation method thereof, the manufacturing process has zero hydrolysis, excellent precipitation resistant performance and short production cycle; a produced material has superior performances. The preparation method for the halogen-free flame-retardant composite material, provided by the invention, is simple in the preparation method, easy to operate and relatively low in the cost.

Description

A kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out
Technical field
The present invention relates to a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out, belong to flame-proof composite material technical field.
Background technology
Polypropylene is a kind of thermoplastics of high comprehensive performance, at aspects such as industrial construction, automotive industry, household electrical appliances, electronics, packing, building materials households, have a wide range of applications, but polyacrylic oxygen index is lower, natural afterwards from fire, belong to inflammable material, polypropylene Application Areas is many, and the fire hazard bringing is thus also increasing.
In the phosphorus flame retardant of low cigarette, halogen, applied research with ammonium polyphosphate is the most extensive, because of its phosphorus, nitrogen content high, and phosphorus, nitrogen have cooperative flame retardant effect, flame retardant effect is superior, but also exists water absorbability large, facile hydrolysis, after interpolation, due to poor with matrix resin consistency, cause composite material toughness significantly to reduce.
Patent of invention: CN200310103218.1, a kind of < < toughening flame-proof polypropene composition and preparation method thereof > > (Granted publication number: CN1611537A) is disclosed, this patent be take ammonium polyphosphate as fire retardant, by introducing grafting elastomerics, improve the consistency of polypropylene and fire retardant, improve the shock strength of matrix material, but moisture absorption in the ammonium polyphosphate course of processing, facile hydrolysis problem still exist simultaneously.Patent of invention: CN201210285636.6, a kind of < < expansion type flame-retardant > > (application notification number: CN102796319 A) is disclosed, this patent is with ammonium polyphosphate, polyvalent alcohol and trimeric cyanamide are fire retardant, by be coated PE wax on fire retardant surface in the course of processing, solve the moisture absorption in the ammonium polyphosphate course of processing, hydrolysis problem, but fire retardant is carried out to PE wax coated processing in advance, PE wax can hinder compatilizer and contact with the effective of fire retardant in melt blending, the compatible effect of compatilizer can not effectively be brought into play, and can not solve polypropylene fire retardant matrix material fire retardant in use separates out, moisture absorption problem.
Summary of the invention
The object of the invention is in order to solve existing ammonium polyphosphate expandable flame retardant efficiency ratio lower, addition is large, the easy moisture absorption of ammonium polyphosphate, hydrolysis, goods fire retardant in life-time service process is easily separated out, the moisture absorption, cause goods flame retardant properties to decline, simultaneously, owing to adding fire retardant, cause the especially problem of toughness degradation of Mechanical Properties of Products, a kind of resistance to toughened halogen-free expanded flame-retardant polypropylene matrix material of separating out is provided, it is fire retardant that siloxanes coated ammonium polyphosphate and melamine cyanurate are take in the present invention, take metal nano oxide compound as synergistic flame retardant, ethylene-vinyl acetate copolymer (EVA) etc. is toughner, prepared and there is good consistency with PP melt blending, the polypropylene miser of flame retardant properties and mechanical property, can be widely used in automotive industry, electronics, packing, the fields such as building materials.
Object of the present invention is achieved through the following technical solutions:
A kind of toughening flame-proof polypropylene composite material, it is characterized in that, comprise following raw material (take 100 parts as): 50~75 parts of polypropylene, 2~15 parts of toughner, 2~8 parts of compatilizers, 10~25 parts of fire retardant silane coated ammonium polyphosphates, 5~10 parts of fire retardant melamine cyanurates, 0.2~2.0 part of synergistic flame retardant, 0.1~0.5 part of irgasfos 168,0.1~0.8 part of antioxidant 1010.
Described a kind of toughening flame-proof polypropylene composite material, it is characterized in that, comprise following raw material (take 100 parts as): 55~75 parts of polypropylene, 3~10 parts of toughner, 2~5 parts of compatilizers, 10~25 parts of fire retardant silane coated ammonium polyphosphates, 5~10 parts of fire retardant melamine cyanurates, 0.5~1.5 part of synergistic flame retardant, 0.1~0.5 part of irgasfos 168,0.2~0.8 part of antioxidant 1010.
Described acrylic plastering be brand-new polypropylene material or polypropylene reclaimed material any or mix.
Described toughner be ethylene-octene copolymer, ethylene-vinyl acetate copolymer any.
Described compatilizer is one or more mixing in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafted ethene-octene copolymer, glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethylene-octene copolymer.
In described fire retardant silane coated ammonium polyphosphate, the massfraction of ammonium polyphosphate is not less than 50%.
Described ammonium polyphosphate is crystallization II-type ammonium polyphosphate with high degree of polymerization.
Described synergistic flame retardant is a kind of or mixing in nano zine oxide, nano lanthanum oxide.
The resistance to toughening flame-proof polypropylene composite material preparation method that separates out, is characterized in that, comprises the steps:
(1) by fire retardant siloxanes coated ammonium polyphosphate, fire retardant melamine cyanurate, synergistic flame retardant, irgasfos 168, antioxidant 1010 adds in high mixer, stirs and mixes for 2~5 minutes;
(2) in mixture, add polypropylene, toughner, compatilizer, high-speed stirring 2~10 minutes, obtains mixture;
(3) add single screw extrusion machine or twin screw extruder to carry out mixing plasticizing step 2 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, can obtain the toughness reinforcing resistance to halogen-free flame retardant polypropylene composite material of separating out.
Compared with prior art, tool has the following advantages in the present invention:
(1) to take the coated crystallization II-type ammonium polyphosphate with high degree of polymerization of siloxanes and melamine cyanurate be fire retardant in the present invention, employing is through the coated ammonium polyphosphate of siloxanes, in the course of processing, be not hydrolyzed, and there is the excellent resistance to performance of separating out, meanwhile, ammonium polyphosphate is after siloxanes is coated, and a large amount of active groups are contained on surface, without re-using coupling agent to its modification, be conducive to shorten the production cycle;
(2) on the basis of halogen-free expanded flame-retardant agent, by adding synergistic flame retardant nano zine oxide or nano lanthanum oxide, greatly improved the flame retarding efficiency of system, lower addition just can make material reach UL94 V-0 rank;
(3) by adding expanding material maleic anhydride inoculated polypropylene (PP-g-MAH) etc., increase the consistency of fire retardant and PP matrix, be conducive to the raising of system over-all properties;
(4) the resulting flame-retardant polypropylene composite material of the present invention, by adding toughner ethylene-octene copolymer or ethylene-vinyl acetate copolymer, can significantly improve the toughness of matrix material;
(5) halogen-free flame-retardant composite material preparation method provided by the present invention is simple, easy handling, and cost is lower.
Embodiment
For a better understanding of the present invention, with example, describe technology contents of the present invention in detail below, but content of the present invention is not limited to this.
Embodiment 1:
Prepare starting material: 73 parts of polypropylene T30S, 3 parts of POE, 2 parts of POE-g-MAH, 14 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 1 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.
Preparation method is:
1) by 14 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 1 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 antioxidant 1010 part.Add in high mixer, stir and mix for 4 minutes, then add 73 parts of polypropylene, 3 parts of POE, 2 parts of POE-g-MAH, continue to stir after 5 minutes, obtain mixture.
2) add twin screw extruder to carry out mixing plasticizing step 1 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, obtains the resistance to toughening flame-proof polypropylene granules of separating out.
Embodiment 2:
Prepare raw material: 65.5 parts of polypropylene T30S, 6 parts of EVA, 3 parts of PP-g-MAH, 18 parts of siloxanes coated ammonium polyphosphates, 6 parts of melamine cyanurates, 0.5 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.
Preparation method is:
1) by 18 parts of siloxanes coated ammonium polyphosphates, 6 parts of melamine cyanurates, 1 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.Add in high mixer, stir and mix for 4 minutes, then add 65.5 parts of polypropylene, 6 parts of EVA, 3 parts of PP-g-MAH, continue to stir after 5 minutes, obtain mixture.
2) add twin screw extruder to carry out mixing plasticizing step 1 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, obtains the resistance to toughening flame-proof polypropylene granules of separating out.
Embodiment 3:
Prepare raw material: 59 parts of polypropylene T30S, 8 parts of EVA, 3 parts of PE-g-GMA, 22 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 0.5 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.
Preparation method is:
1) by 22 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 0.5 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.Add in high mixer, stir and mix for 4 minutes, then add 59 parts of polypropylene, 8 parts of EVA, 3 parts of PE-g-GMA, continue to stir after 5 minutes, obtain mixture.
2) add twin screw extruder to carry out mixing plasticizing step 1 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, obtains the resistance to toughening flame-proof polypropylene granules of separating out.
Embodiment 4:
Prepare raw material: 65.5 parts of polypropylene EPS30R, 5 parts of POE, 3 parts of PP-g-MAH, 19 parts of siloxanes coated ammonium polyphosphates, 6 parts of melamine cyanurates, 1 part of nano lanthanum oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.
Preparation method is:
1) by 19 parts of siloxanes coated ammonium polyphosphates, 6 parts of melamine cyanurates, 1 part of nano lanthanum oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.Add in high mixer, stir and mix for 4 minutes, then add 65.5 parts of EPS30R of polypropylene, 5 parts of POE, 3 parts of PP-g-MAH, continue to stir after 5 minutes, obtain mixture.
2) add twin screw extruder to carry out mixing plasticizing step 1 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, obtains the resistance to toughening flame-proof polypropylene granules of separating out.
Embodiment 5:
Prepare raw material: 63 parts of polypropylene EPS30S, 3 parts of POE, 3 parts of POE-g-MAH, 23 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 0.5 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.
Preparation method is:
1) by 23 parts of siloxanes coated ammonium polyphosphates, 7 parts of melamine cyanurates, 0.5 part of nano zine oxide, 0.3 part of irgasfos 168,0.2 part of antioxidant 1010.Add in high mixer, stir and mix for 4 minutes, then add 63 parts of polypropylene EPS30S, 3 parts of POE, 3 parts of POE-g-MAH, continue to stir after 5 minutes, obtain mixture.
2) add twin screw extruder to carry out mixing plasticizing step 1 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, obtains the resistance to toughening flame-proof polypropylene granules of separating out.
The resulting polypropylene composite material of above-described embodiment 1~5 is injected into test bars, measures flame retardant properties and every mechanical property of fire retardant material, test data is in Table 1.
The resulting Properties of Polypropylene Composite of embodiment 1~5 is according to following standard testing:
Limiting oxygen index(LOI) (LOI) test, tests according to GB/T2046.2-2009 standard, and sample is of a size of: 150*10*4mm.
Vertical combustion test, tests according to GB/T2408-2008 standard, and sample is of a size of: 150*13*3.2mm
Tensile strength test, tests rate of extension 50mm/min according to GB/T1040-2006 standard;
Flexural strength test, tests trial speed 3mm/min according to GB/T9341-2008 standard;
The test of socle girder notch shock, tests according to GB/T1843-2008 standard.
The mechanical property of table 1 halogen-free flame retardant polypropylene composite material and flame retardant properties
For further studying the water tolerance of this flame-proof composite material, polypropylene fire retardant matrix material is processed to 168h in 80 ℃ of hot water, then test its fire-retardant parameter, object is whether LOI and the UL94 rank of the material that checking is crossed through water bath processing can change, and test result is in Table 2.
LOI after the water-bath of table 2 flame-retardant polypropylene composite material and UL94 test result
By table 1 and table 2 data, matrix material is after water bath processing, and limiting oxygen index(LOI) declines to some extent, owing to having adopted the resistance to flame-retardant composition of separating out, embodiment 1 down ratio is minimum, is that 6.4%, embodiment, 4 down ratios are maximum, only reduced by 7.8%, main flame retardant ammonium polyphosphate is after siloxanes is coated, and the resistance to excellent performance of separating out of matrix material, can see from UL94 test, after treatment, the fire-retardant performance of matrix material has obtained maintenance.
Compared with prior art, material prepared by the present invention has the excellent fire-retardant and resistance to performance of separating out, and has kept the comprehensive mechanical property of material simultaneously.

Claims (9)

1. resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out, it is characterized in that, comprise following raw material (take 100 parts as): 50~75 parts of polypropylene, 2~15 parts of toughner, 2~8 parts of compatilizers, 10~25 parts of fire retardant silane coated ammonium polyphosphates, 5~10 parts of fire retardant melamine cyanurates, 0.2~2.0 part of synergistic flame retardant, 0.1~0.5 part of irgasfos 168,0.1~0.8 part of antioxidant 1010.
2. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, it is characterized in that, comprise following raw material (take 100 parts as): 55~75 parts of polypropylene, 3~10 parts of toughner, 2~5 parts of compatilizers, 10~25 parts of fire retardant silane coated ammonium polyphosphates, 5~10 parts of fire retardant melamine cyanurates, 0.5~1.5 part of synergistic flame retardant, 0.1~0.5 part of irgasfos 168,0.2~0.8 part of antioxidant 1010.
3. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: described acrylic plastering be brand-new polypropylene material or polypropylene reclaimed material any or mix.
4. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: described toughner be ethylene-octene copolymer, ethylene-vinyl acetate copolymer any.
5. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: described compatilizer is one or more mixing in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafted ethene-octene copolymer, glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethylene-octene copolymer.
6. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: in described fire retardant silane coated ammonium polyphosphate, the massfraction of ammonium polyphosphate is not less than 50%.
7. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: described ammonium polyphosphate is crystallization II-type ammonium polyphosphate with high degree of polymerization.
8. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as claimed in claim 1, is characterized in that: described synergistic flame retardant is a kind of in nano zine oxide, nano lanthanum oxide or mixes.
9. a kind of resistance to toughening flame-proof polypropylene composite material and preparation method thereof of separating out as described in claim 1-8, is characterized in that, comprises the steps:
(1) by fire retardant siloxanes coated ammonium polyphosphate, fire retardant melamine cyanurate, synergistic flame retardant, irgasfos 168, antioxidant 1010 adds in high mixer, stirs and mixes for 2~5 minutes;
(2) in mixture, add polypropylene, toughner, compatilizer, high-speed stirring 2~10 minutes, obtains mixture;
(3) add single screw extrusion machine or twin screw extruder to carry out mixing plasticizing step 2 gained mixture, plasticization temperature is 190 ℃~240 ℃, and extruded stock, through water-cooled, air-dry, pelletizing, can obtain the toughness reinforcing resistance to halogen-free flame retardant polypropylene composite material of separating out.
CN201410512285.7A 2014-09-29 2014-09-29 Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof Pending CN104194161A (en)

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CN108148260A (en) * 2016-12-05 2018-06-12 合肥杰事杰新材料股份有限公司 A kind of water-fast halogen-free polypropylene flame redardant compound and preparation method thereof
CN108727691A (en) * 2018-05-07 2018-11-02 苏州睿烁环境科技有限公司 A kind of enhancing PP plastics and its preparation method and application
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CN110066460A (en) * 2019-05-09 2019-07-30 王金琪 A kind of the environment-friendly type flame-retardant plastic masterbatch and preparation method of anti-bloom precipitation
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CN110592692A (en) * 2019-09-27 2019-12-20 什邡市长丰化工有限公司 Flame-retardant material for textiles and preparation method thereof
CN110885498A (en) * 2019-12-20 2020-03-17 广东道生科技股份有限公司 Flame-retardant toughened polypropylene material and preparation method thereof
CN111057316A (en) * 2019-12-23 2020-04-24 清远市普塞呋磷化学有限公司 Non-sticking ammonium polyphosphate flame-retardant modified polypropylene material and preparation method thereof
CN111171446A (en) * 2020-01-15 2020-05-19 常州塑料研究所有限公司 Composite high-oxygen-index flame-retardant polypropylene master batch and preparation method thereof
CN111484664A (en) * 2019-12-20 2020-08-04 四川鑫达企业集团有限公司 Environment-friendly flame-retardant anti-aging polypropylene composite material and preparation method thereof
CN112266541A (en) * 2020-10-16 2021-01-26 张雪飞 Nitrogen-phosphorus flame-retardant polypropylene material and preparation method thereof
CN112469786A (en) * 2018-06-15 2021-03-09 博里利斯股份公司 Flame retardant composition
CN114921026A (en) * 2022-07-13 2022-08-19 陕西延长泾渭新材料科技产业园有限公司 Antistatic flame-retardant organic silicon modified polyolefin elastomer material and preparation method thereof
CN116410542A (en) * 2023-03-16 2023-07-11 广东亨嘉橡塑科技有限公司 Modified polypropylene material for new energy automobile battery shell and preparation method thereof
CN117327347A (en) * 2023-09-19 2024-01-02 江苏海聚新材料科技有限公司 Flame-retardant polypropylene and preparation method and application thereof

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