CN115873344A - High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof - Google Patents
High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115873344A CN115873344A CN202211565332.5A CN202211565332A CN115873344A CN 115873344 A CN115873344 A CN 115873344A CN 202211565332 A CN202211565332 A CN 202211565332A CN 115873344 A CN115873344 A CN 115873344A
- Authority
- CN
- China
- Prior art keywords
- fibrilia
- antioxidant
- flame retardant
- composite material
- reinforced polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 104
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- -1 polypropylene Polymers 0.000 title claims abstract description 83
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 79
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 59
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 47
- 244000025254 Cannabis sativa Species 0.000 claims description 22
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 22
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 22
- 235000009120 camo Nutrition 0.000 claims description 22
- 235000005607 chanvre indien Nutrition 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000011487 hemp Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 240000000491 Corchorus aestuans Species 0.000 claims description 10
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 10
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 10
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 240000008564 Boehmeria nivea Species 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 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 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001514 detection method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 241000208202 Linaceae Species 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The specification discloses a high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material and a preparation method thereof, wherein the composite material comprises the following raw materials in parts by weight: 29-78 parts of polypropylene resin; 8-36 parts of natural fibrilia; 12-28 parts of a flame retardant; 0.8-4.2 parts of a compatibilizer; 0.3-1.2 parts of antioxidant. The invention also discloses a composite materialThe preparation method of (1); the performance of the fibrilia reinforced polypropylene composite material prepared by the invention is as follows: the flame retardant grade can reach V-0 grade; the tensile strength is more than 43.0MPa; tensile modulus is greater than 1405MPa; the bending strength is more than 34.5MPa; the flexural moduli are all more than 1420MPa; the simple supported beam has no gap and no fracture in impact strength; the impact strength of the gaps of the simply supported beams is more than 21.5kJ/m 2 。
Description
Technical Field
One or more embodiments of the specification relate to the technical field of automobile materials, and particularly relate to a high-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and a preparation method thereof.
Background
In recent years, the Chinese automobile industry keeps a rapid and stable development trend, and the automobile yield and sales are in the top of the world. The application of the plastic to the automobile is long, the usage amount of the modified plastic for the automobile at present becomes an important mark for measuring the design and manufacturing level of the automobile, and the mass application of the plastic ornaments promotes the weight reduction and energy saving of the automobile and improves the aesthetic comfort level of the automobile. In the field of automobiles, polypropylene (PP) is a kind of general plastic, which has the advantages of wide sources, low price, corrosion resistance, excellent mechanical properties, and the like, and thus, is a variety with the largest usage amount, the highest usage frequency, and the fastest development speed of the plastic for automobiles.
Meanwhile, artificial fibers such as carbon fibers, glass fibers and aramid fibers are widely applied to polymer matrix composite materials as reinforcing phases, but the artificial fibers have the defects of poor degradability, high cost and the like. Toxic and harmful gases are generated during the production process, and environmental problems are also caused in the post-treatment (landfill or incineration). In contrast, the plant fiber is derived from natural plants, and has the advantages of low cost, low density, reproducibility, degradability, high specific strength and specific modulus and the like.
At present, the automobile industry is one of the main sources of carbon emission in China, so that the energy conservation and emission reduction of automobiles have important significance for realizing the aim of 'double carbon' in China. The light weight of the automobile is the most direct and effective way for realizing energy conservation and emission reduction at present. Composite materials are important lightweight materials and have become hot spots for automobile lightweight research. Vegetable fibres have a low density, a high specific strength and a high specific modulus, while hemp fibres have a higher specific modulus compared to glass fibres. Thus, vegetable fibers are an ideal substitute for rayon. Compared with carbon fiber and glass fiber reinforced resin matrix composite materials, the fibrilia reinforced resin matrix composite material has the advantages of low price, biodegradability, low production energy consumption, sound insulation, noise reduction and the like, so that the fibrilia reinforced resin matrix composite material has a wide application prospect in the field of automobiles. Namely, the high-performance green environment-friendly composite material can be prepared by introducing the plant fibers with high strength and light weight into the polymer matrix. Although the plant fiber can enable the composite material to have good mechanical properties, the high flammability of the plant fiber composite material limits the application of the composite material in the field of automobiles, so that the improvement of the flame retardant property of the composite material is of great importance. Meanwhile, the polypropylene material has the defect of easy combustion due to excessively low oxygen index, so that the polypropylene material is limited to be used on automobile interior parts with combustion requirements and the like; therefore, a method for modifying plant fibers by adding a flame retardant is needed to overcome the defect of easy combustion. Although halogen flame retardant has high flame retardant efficiency, the halogen flame retardant generates more smoke and toxic and harmful gases during combustion, which has adverse effects on human health and seriously affects the ecological environment.
Moreover, since the plant fiber contains a large amount of hydroxyl groups, the plant fiber has polarity and hydrophilicity, but most thermoplastics are non-polar and hydrophobic, so that the interfacial compatibility of the thermoplastic and the hydrophobic thermoplastic is poor. This results in a more porous structure between the matrix and the fibers of the composite material, which leads to a reduction in the properties of the composite material to less than desired values.
Disclosure of Invention
In view of the above, it is an object of one or more embodiments of the present disclosure to provide a high modulus, halogen free, flame retardant, fibrilia reinforced polypropylene composite. The performance of the fibrilia reinforced polypropylene composite material is as follows: the flame retardant grade can reach V-0 grade; the tensile strength is more than 43.0MPa; tensile modulus is greater than 1405MPa; the bending strength is more than 34.5MPa; the flexural moduli are all more than 1420MPa; the simple supported beam has no gap and no fracture in impact strength; the impact strength of the gaps of the simply supported beams is more than 21.5kJ/m 2 。
The second purpose of the specification is to provide a high-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and a preparation method thereof.
Based on the first item, the present specification provides the following technical solutions:
the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following raw materials in parts by weight:
as an embodiment, the polypropylene resin is selected from polypropylene resin F401 manufactured and sold by beijing yanshan petrochemical company.
As an embodiment, the natural hemp fibers are selected from one or more of ramie, flax, hemp, jute, sisal fibers.
In one embodiment, the flame retardant is a combination of a nitrogen-phosphorus flame retardant and a silicon flame retardant.
As an embodiment, the mass ratio of the nitrogen-phosphorus flame retardant to the silicon flame retardant is 0.5 to 5.5:1.
as a preferred embodiment, the nitrogen-phosphorus flame retardant is selected from one or more of melamine, ammonium polyphosphate and melamine polyphosphate; the silicon flame retardant is selected from one or more of silicon dioxide and organic silicon flame retardant; preferably, the organic silicon flame retardant is one or more of polysiloxane, polyborosiloxane and silicone oil.
As an embodiment, the compatibilizer is one or more of ethylene-butyl acrylate-glycidyl methacrylate (EGMA), triglycidyl isocyanurate (TGIC), triallyl isocyanurate (TAIC), maleic anhydride grafted polypropylene (PP-g-MAH).
As one embodiment, the antioxidant consists of a primary antioxidant and a secondary antioxidant.
As a preferred embodiment, the primary antioxidant is a hindered phenol antioxidant selected from one or more of antioxidants 1035, 1010 and 1076; the auxiliary antioxidant is a sulfur-containing antioxidant, and the sulfur-containing antioxidant is selected from one or two of an antioxidant DLTP and an antioxidant DSTP.
As a preferred embodiment, the mass ratio of the primary antioxidant to the secondary antioxidant is 0.5 to 2.2.
Based on the second item, the present specification provides the following technical solutions:
a high modulus, halogen-free and flame retardant fibrilia reinforced polypropylene composite material and a preparation method thereof comprise the following steps:
1) Cutting natural fibrilia into 2-8mm short-cut fibrilia, soaking the short-cut fibrilia in 1.5-9wt% alkaline solution for 15-90min for modification treatment, filtering, washing with 0.03-0.3wt% acetic acid deionized water solution to neutrality, and drying the modified short-cut fibrilia; or
Cutting natural fibrilia into 2-8mm short-cut fibrilia, soaking the short-cut fibrilia in 10-40wt% of silane coupling agent ethanol solution for 90-240min for modification treatment, filtering, and drying the short-cut fibrilia treated by the coupling agent;
2) Drying the modified chopped fibrilia, the polypropylene resin, the flame retardant, the compatibilizer and the antioxidant at 40-70 ℃ for 4-10h; mechanically mixing the polypropylene resin, the surface-modified chopped fibrilia, the flame retardant, the compatibilizer and the antioxidant in a high-speed mixer for 10-30min according to the formula amount, uniformly mixing, adding into an internal mixer for melt blending for 5-25min, cooling and granulating after mixing is finished, and thus obtaining the high-modulus, halogen-free and flame-retardant fibrilia reinforced polypropylene composite material.
In one embodiment, in step 1), the temperature of the drying treatment is 30 to 70 ℃, and the time of the drying treatment is 6 to 72 hours.
As an embodiment, the high speed mixer has a rotational speed of 500 to 1000rpm; the banburying temperature of the banbury mixer is 170-220 ℃, and the rotor speed is 35-120rpm.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
Compared with the prior art, the invention has the following beneficial effects:
the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material prepared by the invention has excellent mechanical properties, the flame retardant property reaches UL94V-0 level, and the composite material is excellent in flame retardant property, green, environment-friendly and low in cost; the automobile interior and exterior trim part processing method has the advantages that the mass production can be realized, the safety and the reliability are realized, and the method can be widely applied to automobile interior and exterior trim parts of different processing and forming processes;
the performance of the fibrilia reinforced polypropylene composite material is as follows: the flame retardant grade can reach V-0 grade; the tensile strength is more than 43.0MPa; tensile modulus is greater than 1405MPa; the bending strength is more than 34.5MPa; the flexural moduli are all more than 1420MPa; the simple beam has no fracture at the notch impact strength, and the notch impact strength of the simple beam is more than 21.5kJ/m 2 。
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
It is to be noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present specification should have the ordinary meaning as understood by those of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in one or more embodiments of the specification is not intended to indicate any order, quantity, or importance, but rather is used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items.
In the invention, the raw materials are as follows:
polypropylene resin F401, available from beijing yanshan petrochemical company;
natural hemp fibers and jute fibers, purchased from the institute of fibrilia, academy of agricultural sciences of china;
flame retardants (ammonium polyphosphate, polysiloxane, melamine polyphosphate, silica) available from denxinnuo chemical ltd;
compatibilizers (TGIC, TAIC), available from Cheng Cang chemical ltd, santong;
primary antioxidant 1010, secondary antioxidant DLTP, available from lanzhou chemical industry;
the silane coupling agent KH560 is available from New Material science and technology, inc. of Wanshan, henan.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
The performance detection method of the product fibrilia reinforced polypropylene composite material comprises the following steps：
Flame retardant property: testing according to the detection standard of UL-94;
tensile strength, tensile modulus: testing according to ISO 527 standard;
flexural strength, flexural modulus: testing according to ISO 178 standard;
the simple-supported beam has no gap impact strength, and the simple-supported beam has the gap impact strength: testing according to ISO 179 standard;
as one aspect of the invention, the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following raw materials in parts by weight:
as an embodiment, the polypropylene resin is selected from polypropylene resin F401 manufactured and sold by beijing yanshan petrochemical company.
As an embodiment, the natural hemp fibers are selected from one or more of ramie, flax, hemp, jute, and sisal fibers. The natural fibrilia is one of plant fibers, has the advantages of low density, high specific strength and specific modulus, wide source, low price, environmental protection, recyclability and the like.
In one embodiment, the flame retardant is a combination of a nitrogen-phosphorus flame retardant and a silicon flame retardant which are halogen-free. The synergistic flame-retardant effect between the nitrogen-phosphorus flame retardant and the silicon flame retardant is utilized, and the flame retardant performance is improved on the premise that the influence on the mechanical performance is reduced as much as possible by the minimum addition amount.
As an embodiment, the mass ratio of the nitrogen-phosphorus flame retardant to the silicon flame retardant is 0.5 to 5.5:1.
as a preferred embodiment, the nitrogen-phosphorus flame retardant is selected from one or more of melamine, ammonium polyphosphate and melamine polyphosphate; the silicon flame retardant is selected from one or more of silicon dioxide and organic silicon flame retardant; preferably, the organic silicon flame retardant is one or more of polysiloxane, polyborosiloxane and silicone oil.
As an embodiment, the compatibilizer is one or more of ethylene-butyl acrylate-glycidyl methacrylate (EGMA), triglycidyl isocyanurate (TGIC), triallyl isocyanurate (TAIC), maleic anhydride grafted polypropylene (PP-g-MAH). The molecular chain of the polypropylene can be connected to the surface of the fibrilia by adding the compatibilizer, so that the interaction capacity between two phases is enhanced, the adhesion between the two phases is increased, and the mechanical property of the fibrilia reinforced polypropylene composite material is improved.
As an embodiment, the antioxidant consists of a primary antioxidant and a secondary antioxidant. The addition of the antioxidant effectively inhibits or reduces the thermal oxidation and photo-oxidation reaction speeds of the polypropylene material, obviously improves the heat resistance and light resistance of the material, delays the degradation and aging processes of the polypropylene material and prolongs the service life of a product; the invention selects the combined antioxidant, and utilizes the synergistic complementary effect between the main antioxidant and the auxiliary antioxidant to achieve the optimal anti-thermal-oxidative-aging effect with the minimum addition amount and the minimum cost.
As a preferred embodiment, the primary antioxidant is a hindered phenol antioxidant selected from one or more of antioxidants 1035, 1010 and 1076; the auxiliary antioxidant is a sulfur-containing antioxidant, and the sulfur-containing antioxidant is one or two of an antioxidant DLTP and an antioxidant DSTP.
As a preferred embodiment, the mass ratio of the primary antioxidant to the secondary antioxidant is 0.5 to 2.2.
As another aspect of the invention, the invention relates to a high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
1) Surface modification of natural fibrilia: cutting natural fibrilia into 2-8mm short fibrilia, soaking the short fibrilia in 1.5-9wt% alkaline solution for 15-90min for modification, filtering, washing with 0.03-0.3wt% acetic acid solution of deionized water to neutrality, and drying the modified short fibrilia; or
Cutting natural fibrilia into 2-8mm short-cut fibrilia, soaking the short-cut fibrilia in 10-40wt% of silane coupling agent ethanol solution for 90-240min for modification treatment, filtering, and drying the short-cut fibrilia treated by the coupling agent; according to the invention, the polarity of the fiber surface is reduced by surface modification of the natural fibrilia, so that the interface bonding strength between the polypropylene resin and the fiber is improved, the interaction force between the fibrilia and a polypropylene molecular chain can be further improved, and the mechanical property of the fibrilia reinforced polypropylene composite material is improved;
2) Drying the modified chopped fibrilia, the polypropylene resin, the flame retardant, the compatibilizer and the antioxidant at 40-70 ℃ for 4-10h; mechanically mixing the polypropylene resin, the surface-modified chopped fibrilia, the flame retardant, the compatibilizer and the antioxidant in a high-speed mixer for 10-30min according to the formula amount, uniformly mixing, adding into an internal mixer for melt blending for 5-25min, cooling and granulating after mixing is finished, and thus obtaining the high-modulus, halogen-free and flame-retardant fibrilia reinforced polypropylene composite material.
In one embodiment, in step 1), the temperature of the drying treatment is 30-70 ℃, and the time of the drying treatment is 6-72h.
As an embodiment, the speed of the high speed mixer is 500 to 1000rpm; the banburying temperature of the banbury mixer is 170-220 ℃, and the rotor speed is 35-120rpm.
Example 1
The high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following raw materials in parts by weight:
the preparation method of the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following steps:
1) Surface modification of natural fibrilia:
cutting hemp fibers into 5mm chopped hemp fibers, soaking the chopped hemp fibers in a NaOH solution with the mass fraction of 6wt% for 40min for modification treatment, filtering, washing the fibers with a 0.15wt% acetic acid deionized water solution until the fibers are neutral, and finally drying the washed chopped hemp fibers for 24h at 50 ℃;
2) Drying the surface-modified chopped fibrilia, the polypropylene resin, the compatibilizer and the antioxidant at 60 ℃ for 4 hours; according to the formula, the polypropylene resin, the surface modified chopped jute fiber, the flame retardant, the compatibilizer and the antioxidant are mechanically mixed in a high-speed mixer for 10min at the rotating speed of 800rpm, the mixture is uniformly mixed and then put into an internal mixer for melting and blending for 15min, wherein the internal mixing temperature is 190 ℃ and the rotating speed of a rotor is 60rpm, cooling and granulation are carried out after mixing is finished, and the high-modulus halogen-free flame-retardant jute fiber reinforced polypropylene composite material is obtained, and the performance detection result is shown in the following table 1.
Example 2：
The high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following raw materials in parts by weight:
the preparation method of the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following steps:
1) Surface modification of natural fibrilia:
cutting hemp fibers into chopped hemp fibers with the diameter of 8mm, soaking the chopped hemp fibers in a NaOH solution with the mass fraction of 1.5wt% for 90min for modification treatment, filtering, cleaning the fibers with a 0.06wt% acetic acid deionized water solution to be neutral, and finally drying the cleaned chopped hemp fibers for 72h at the temperature of 30 ℃;
2) Drying the surface-modified chopped jute fibers, the polypropylene resin, the compatibilizer and the antioxidant at 40 ℃ for 10 hours; according to the formula, the polypropylene resin, the surface modified chopped fibrilia, the flame retardant, the compatibilizer and the antioxidant are mechanically mixed in a high-speed mixer for 30min, the rotating speed of the mixer is 1000rpm, the mixture is uniformly mixed and then put into an internal mixer for melt blending for 5min, wherein the internal mixing temperature is 220 ℃, the rotating speed of a rotor is 120rpm, the mixture is cooled and granulated after the mixing is finished, and the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material is obtained, and the performance detection result is shown in the following table 1.
Example 3
The high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following components in parts by mass:
the preparation method of the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material comprises the following steps:
1) Surface modification of natural fibrilia:
surface modification of natural fibrilia: cutting natural hemp fiber into 5mm chopped fiber, soaking the chopped hemp fiber in 25wt% ethanol solution of silane coupling agent KH560 for 150min, and filtering. Finally, drying the fibrilia treated by the coupling agent for 12h at 60 ℃;
2) Drying the surface-modified chopped flax fibers, the polypropylene resin, the compatibilizer and the antioxidant for 4 hours at 70 ℃; according to the formula, the polypropylene resin, the surface modified chopped fibrilia, the flame retardant, the compatibilizer and the antioxidant are mechanically mixed in a high-speed mixer for 10min at the rotating speed of 500rpm, the mixture is uniformly mixed and then put into an internal mixer for melt blending for 25min, wherein the internal mixing temperature is 170 ℃, the rotating speed of a rotor is 40rpm, the mixture is cooled and granulated after the mixing is finished, and the high-modulus halogen-free flame-retardant fibrilia reinforced polypropylene composite material is obtained, and the performance detection results are shown in the following table 1.
Example 4
Example 1 was repeated with the only difference that: the natural hemp fiber is made of jute fiber of the research institute of hemp fiber of Chinese academy of agricultural sciences instead of natural hemp fiber, and the performance test results are shown in Table 1 below.
Example 5
Example 1 was repeated with the only difference that: the flame retardant is a mixture of melamine polyphosphate and silicon dioxide, the mass ratio is 4:1, and the performance detection result is shown in table 1 below.
Example 6
Example 1 was repeated with the only difference that: the compatibilizer is a mixture of triglycidyl isocyanurate (TGIC) and triallyl isocyanurate (TAIC) propyl ester, the mass ratio is 1:1, and the performance detection results are shown in the following table 1.
Performance test
The high modulus, halogen-free, flame retardant, fibrilia reinforced polypropylene composites of examples 1-6 were tested for performance and the results are shown in table 1 below:
table 1: performance test results for the high modulus, halogen-free, flame retardant, fibrilia reinforced Polypropylene composites of examples 1-6
As can be seen from the data in Table 1: the invention relates to a high-modulus halogen-free flame-retardant fibrilia fiber additiveThe flame retardant grade of the strong polypropylene composite material can reach V-0 grade; the tensile strength is more than 43.0MPa; tensile modulus is greater than 1405MPa; the bending strength is more than 34.5MPa; the flexural moduli are all more than 1420MPa; the simple beam has no fracture at the notch impact strength, and the notch impact strength of the simple beam is more than 21.5kJ/m 2 。
Comparative example 1
Example 1 was repeated with the only difference that: no natural hemp fiber is added. Other components, amounts and preparation methods are the same as those of example 1, and the product performance detection results are shown in Table 2 below.
Comparative example 2
Example 1 was repeated with the only difference that: no flame retardant is added; other components, amounts and preparation methods are the same as those of example 1, and the product performance detection results are shown in Table 2 below.
Comparative example 3
Example 1 was repeated with the only difference that: only ammonium polyphosphate is used as the flame retardant, a silicon flame retardant is not added, and the total amount of the flame retardant is still 22 parts; other components, amounts and preparation methods are the same as those in example 1, and the product performance detection results are shown in Table 2 below.
Comparative example 4
Example 1 was repeated with the only difference that: only polysiloxane is used as the flame retardant, ammonium polyphosphate is not added, and the total amount of the flame retardant is still 22 parts; other components, amounts and preparation methods are the same as those of example 1, and the product performance detection results are shown in Table 2 below.
Comparative example 5
Example 1 was repeated with the only difference that: no compatibilizer TGIC was added; the other components, amounts and preparation methods were the same as in example 1.
Comparative example 6
Example 1 was repeated with the only difference that: the surface modification of the natural fibrilia is not carried out; other components, amounts and preparation methods are the same as those of example 1, and the product performance detection results are shown in Table 2 below.
Performance test
The different polypropylene composites of comparative examples 1-6 were tested for performance and the results are shown in table 2 below:
table 2: results of Performance testing of the different Polypropylene composites of comparative examples 1-6
As can be seen by comparing the data of example 1 and comparative example 1, the polypropylene material modified without adding natural fibrilia has relatively poor mechanical properties, the tensile strength is only 16.2MPa, and the tensile modulus is 754MPa; the bending strength is only 9.6MPaMPa, and the bending modulus is 608MPa; the unnotched impact strength of the simply supported beam is only 13.2kJ/m 2， The impact strength of the gap of the simply supported beam is 4.3kJ/m 2 (ii) a So that the requirements of parts of high-strength automobile plastic parts are not met.
Comparing the data of example 1 and comparative examples 2-4 again, it can be seen that the polypropylene material without the flame retardant (comparative example 2) has no flame retardant property, and the application thereof to exterior parts requiring flame retardancy, such as automobile interiors, automobile bottom shields, engine compartments, and the like, is limited. The flame retardant effect of only adding one flame retardant (comparative example 3 and comparative example 4) is low, the flame retardant grade is V-1 grade, and the application of the flame retardant to automotive upholsteries with strict flame retardant requirements is limited. Two flame retardants are selected for synergistic flame retardance (example 1), and when the addition amount of the flame retardant is the lowest, a good flame retardant effect can be achieved, energy is saved, efficiency is high, and production cost is reduced.
Further comparing the test results of example 1 and comparative example 5, it can be seen that the addition of the compatibilizer improves the mechanical properties of the polypropylene material, improves the tensile strength, the bending strength and the impact strength, and the addition of the compatibilizer can improve the flame retardant rating of the fibrilia reinforced polypropylene composite material, and the flame retardant rating is improved from a V-1 rating to a V-0 rating, thereby further improving the flame retardant effect of the fibrilia reinforced polypropylene composite material.
Finally, comparing the data of example 1 and comparative example 6 shows that the natural fibrilia without surface treatment can cause poor compatibility and weak interaction force between the fibrilia and the polypropylene resin, and the interfacial strength is poor due to the polarity difference, so that the mechanical properties of the finally obtained composite material are obviously reduced, the tensile strength, the bending strength and the impact strength are greatly reduced, and the application of the fibrilia reinforced polypropylene composite material in the engineering fields of automobiles and the like is limited.
In conclusion, the fiber raw materials, the selection of the flame retardant, the selection of the compatibilizer, the component content and the preparation method have great influence on the product of the invention, and the product can not reach the required performance of the invention due to the excesses of any conditions.
The foregoing description has been directed to specific embodiments of this disclosure. Other embodiments are within the scope of the following claims. In some cases, the actions or steps recited in the claims may be performed in a different order than in the embodiments and still achieve desirable results. In addition, the processes depicted in the specification do not necessarily require the particular order shown, or sequential order, to achieve desirable results. In some embodiments, multitasking and parallel processing may also be possible or may be advantageous.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the spirit of the present disclosure, features from the above embodiments or from different embodiments may also be combined, steps may be implemented in any order, and there are many other variations of different aspects of one or more embodiments of the present description as described above, which are not provided in detail for the sake of brevity.
In addition, where specific details are set forth in order to describe example embodiments of the disclosure, it will be apparent to one skilled in the art that one or more embodiments of the disclosure may be practiced without, or with variation of, these specific details for simplicity of illustration and discussion. Accordingly, the description is to be regarded as illustrative instead of restrictive.
While the present disclosure has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations thereof will be apparent to those skilled in the art in light of the foregoing description.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (10)
1. The high-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material is characterized by comprising the following raw materials in parts by weight:
29-78 parts of polypropylene resin;
8-36 parts of natural fibrilia;
12-28 parts of a flame retardant;
0.8-4.2 parts of a compatibilizer;
0.3-1.2 parts of antioxidant.
2. The fibrilia reinforced polypropylene composite material according to claim 1, wherein: the natural hemp fiber is selected from one or more of ramie, flax, hemp, jute and sisal fiber.
3. The fibrilia reinforced polypropylene composite material according to claim 1, wherein: the flame retardant is a combination of a nitrogen-phosphorus flame retardant and a silicon flame retardant.
4. The fibrilia reinforced polypropylene composite material according to claim 3, wherein: the mass ratio of the nitrogen-phosphorus flame retardant to the silicon flame retardant is 0.5-5.5:1.
5. the fibrilia reinforced polypropylene composite material according to claim 3, wherein: the nitrogen-phosphorus flame retardant is selected from one or more of melamine, ammonium polyphosphate and melamine polyphosphate; the silicon flame retardant is selected from one or more of silicon dioxide and organic silicon flame retardant; preferably, the organic silicon flame retardant is one or more of polysiloxane, polyborosiloxane and silicone oil.
6. The fibrilia reinforced polypropylene composite material according to claim 1, wherein: the compatibilizer is one or more of ethylene-butyl acrylate-glycidyl methacrylate, triglycidyl isocyanurate, triallyl isocyanurate and maleic anhydride grafted polypropylene.
7. The fibrilia reinforced polypropylene composite material according to claim 1, wherein: the antioxidant consists of a main antioxidant and an auxiliary antioxidant.
8. The fibrilia reinforced polypropylene composite material according to claim 7, wherein: the main antioxidant is a hindered phenol antioxidant, and the hindered phenol antioxidant is selected from one or more of an antioxidant 1035, an antioxidant 1010 and an antioxidant 1076; the auxiliary antioxidant is a sulfur-containing antioxidant, and the sulfur-containing antioxidant is one or two of an antioxidant DLTP and an antioxidant DSTP.
9. The fibrilia reinforced polypropylene composite material according to claim 7, wherein: the mass ratio of the main antioxidant to the auxiliary antioxidant is 0.5-2.2.
10. The process for preparing the high modulus, halogen free, flame retardant, fibrilia reinforced polypropylene composite of any of claims 1-9, comprising the steps of:
1) Cutting natural fibrilia into 2-8mm short-cut fibrilia, soaking the short-cut fibrilia in 1.5-9wt% alkaline solution for 15-90min for modification treatment, filtering, washing with 0.03-0.3wt% acetic acid deionized water solution to neutrality, and drying the modified short-cut fibrilia; or
Cutting natural fibrilia into 2-8mm short-cut fibrilia, soaking the short-cut fibrilia in 10-40wt% of silane coupling agent ethanol solution for 90-240min for modification treatment, filtering, and drying the short-cut fibrilia treated by the coupling agent;
2) Drying the modified chopped fibrilia, the polypropylene resin, the flame retardant, the compatibilizer and the antioxidant at 40-70 ℃ for 4-10h; mechanically mixing the polypropylene resin, the surface-modified chopped jute fiber, the flame retardant, the compatibilizer and the antioxidant in a high-speed mixer for 10-30min according to the formula amount, uniformly mixing, adding into an internal mixer for melt blending for 5-25min, cooling and granulating after mixing is finished to obtain the high-modulus, halogen-free and flame-retardant jute fiber reinforced polypropylene composite material;
preferably, in the step 1), the temperature of the drying treatment is 30-70 ℃, and the time of the drying treatment is 6-72h;
preferably, the rotating speed of the high-speed mixer is 500-1000rpm; the banburying temperature of the banbury mixer is 170-220 ℃, and the rotor speed is 35-120rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565332.5A CN115873344A (en) | 2022-12-07 | 2022-12-07 | High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565332.5A CN115873344A (en) | 2022-12-07 | 2022-12-07 | High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115873344A true CN115873344A (en) | 2023-03-31 |
Family
ID=85766358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211565332.5A Pending CN115873344A (en) | 2022-12-07 | 2022-12-07 | High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115873344A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146054A (en) * | 2013-02-21 | 2013-06-12 | 合肥杰事杰新材料股份有限公司 | Modified jute fiber reinforced polypropylene and its preparation method |
| CN106674741A (en) * | 2016-12-26 | 2017-05-17 | 重庆普利特新材料有限公司 | High heat-resistant, halogen-free and flame-retardant type jute fiber-reinforced polypropylene composite material and preparation method thereof |
| CN108530760A (en) * | 2018-04-25 | 2018-09-14 | 上海金发科技发展有限公司 | A kind of light-weight environment-friendly flame retardant type jute fiber reinforced polypropylene composite material and preparation method |
| CN114015122A (en) * | 2021-11-23 | 2022-02-08 | 广东富强科技股份有限公司 | Automobile ceiling base material and preparation method thereof |
-
2022
- 2022-12-07 CN CN202211565332.5A patent/CN115873344A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146054A (en) * | 2013-02-21 | 2013-06-12 | 合肥杰事杰新材料股份有限公司 | Modified jute fiber reinforced polypropylene and its preparation method |
| CN106674741A (en) * | 2016-12-26 | 2017-05-17 | 重庆普利特新材料有限公司 | High heat-resistant, halogen-free and flame-retardant type jute fiber-reinforced polypropylene composite material and preparation method thereof |
| CN108530760A (en) * | 2018-04-25 | 2018-09-14 | 上海金发科技发展有限公司 | A kind of light-weight environment-friendly flame retardant type jute fiber reinforced polypropylene composite material and preparation method |
| CN114015122A (en) * | 2021-11-23 | 2022-02-08 | 广东富强科技股份有限公司 | Automobile ceiling base material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112126201B (en) | Halogen-free flame-retardant reinforced PET composite material and preparation method thereof | |
| CN101418100B (en) | Halogen-free flame retardant long glass fibre reinforcement polypropylene composite material and preparation method thereof | |
| CN106674741A (en) | High heat-resistant, halogen-free and flame-retardant type jute fiber-reinforced polypropylene composite material and preparation method thereof | |
| CN102534855B (en) | Method for preparing halogen-free flame-retarding polyester fibers with durability and droplet resistance | |
| CN111484739A (en) | Flame-retardant reinforced polyamide composition and preparation method thereof | |
| CN101117426B (en) | Mass acrylonitrile-butadiene-phenylethene and polyterephthalic acid butanediol fat compound and preparation method thereof | |
| CN108276664B (en) | Flame-retardant continuous long glass fiber reinforced PP (polypropylene) material for wall switch and preparation method thereof | |
| CN114806156B (en) | Flame-retardant smoke-inhibiting reinforced nylon composite material and preparation method thereof | |
| CN102558784A (en) | Anti-impact polyethylene glycol terephthalate composite material and preparation method thereof | |
| CN115873344A (en) | High-modulus halogen-free flame-retardant fibrilia-reinforced polypropylene composite material and preparation method thereof | |
| CN110527259A (en) | A kind of good fiber reinforcement PBT/ASA alloy material of weldability and preparation method thereof | |
| CN113583343A (en) | Regenerated flame-retardant engineering plastic and preparation method thereof | |
| CN116144158B (en) | High-temperature-resistant flame-retardant PC/ABS composite material and preparation method thereof | |
| CN111363318B (en) | Flame-retardant smoke-suppressing PTT polyester composite material and preparation method therefor | |
| CN111793338B (en) | Compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and preparation method thereof | |
| CN113061302B (en) | Halogen-free flame-retardant long glass fiber reinforced PP composite material for bottom guard plate of automobile fuel tank | |
| CN115873401A (en) | Carbon fiber reinforced polyamide composition, preparation method and application | |
| CN114591567A (en) | Glass fiber reinforced flame-retardant polypropylene composite material and preparation method and application thereof | |
| CN101481479B (en) | Polypropylene modified material and production method thereof | |
| CN106279968A (en) | A kind of fiber glass reinforced polypropylene reclaimed materials and preparation method thereof | |
| CN113462129A (en) | Flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| CN109810408B (en) | Modification method of retired composite insulator silicone rubber and application of retired composite insulator silicone rubber in polypropylene composite | |
| CN108467545B (en) | Sound-insulation noise-reduction flame-retardant polypropylene material and preparation method thereof | |
| CN113372471A (en) | Phosphorus-oxidized epoxy elastomer and flame-retardant composite material | |
| CN103450647B (en) | A kind of polybutylene terephthalate matrix material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |