CN119192813A - A fluorine-free flame-retardant PC resin composition and its preparation method and application - Google Patents
A fluorine-free flame-retardant PC resin composition and its preparation method and application Download PDFInfo
- Publication number
- CN119192813A CN119192813A CN202411589438.8A CN202411589438A CN119192813A CN 119192813 A CN119192813 A CN 119192813A CN 202411589438 A CN202411589438 A CN 202411589438A CN 119192813 A CN119192813 A CN 119192813A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- flame retardant
- fluorine
- free flame
- retardant
- 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 78
- 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 76
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000010008 shearing Methods 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 238000005034 decoration Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920000800 acrylic rubber Polymers 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002041 carbon nanotube Substances 0.000 abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000004417 polycarbonate Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920007019 PC/ABS Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- GWSUPDVBFZROIB-UHFFFAOYSA-N 2-methyl-2-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical group C[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)c1ccccc1 GWSUPDVBFZROIB-UHFFFAOYSA-N 0.000 description 2
- 229920000891 common polymer Polymers 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 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 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 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 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种无氟阻燃PC树脂组合物及其制备方法与应用。该树脂组合物包括以下重量份数的各组分：PC树脂85‑92重量份，磷腈阻燃剂5‑8重量份，增韧剂2‑4重量份，气相二氧化硅2‑4重量份，多壁碳纳米管(CNT)1‑3重量份，有机硅阻燃剂0.5‑1.5重量份，助剂0.5‑1.5重量份。将上述原材料在高速混合机内搅拌充分混合后，经双螺杆挤出机在螺杆的输送、剪切和混炼下，物料经过熔化、复合、均化、拉条、冷却、切粒步骤，得到无氟阻燃PC树脂组合物。该树脂组合物不仅具有稳定的阻燃性能，而且具有优异力学性能，非常适合应用于OA(办公设备)，新能源电池、电子电气、家电等领域的黑色零部件。The present invention relates to a fluorine-free flame-retardant PC resin composition and its preparation method and application. The resin composition includes the following components in parts by weight: 85-92 parts by weight of PC resin, 5-8 parts by weight of phosphazene flame retardant, 2-4 parts by weight of toughening agent, 2-4 parts by weight of fumed silica, 1-3 parts by weight of multi-walled carbon nanotubes (CNT), 0.5-1.5 parts by weight of organosilicon flame retardant, and 0.5-1.5 parts by weight of auxiliary agent. After the above raw materials are stirred and fully mixed in a high-speed mixer, the materials are melted, compounded, homogenized, drawn, cooled, and pelletized by a twin-screw extruder under the conveying, shearing, and mixing of the screw to obtain a fluorine-free flame-retardant PC resin composition. The resin composition not only has stable flame retardant properties, but also has excellent mechanical properties, and is very suitable for black parts in the fields of OA (office equipment), new energy batteries, electronic and electrical, and home appliances.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a fluorine-free flame-retardant PC resin composition, and a preparation method and application thereof.
Background
PC resin has excellent flame retardance, can reach the flame retardant standard of UL V-2 grade, has a limiting oxygen index of 21% -24%, is easy to melt in the combustion process, and can reach the flame retardant requirement of V-0 grade only by adding high-molecular-weight Polytetrafluoroethylene (PTFE) as an anti-dripping agent in flame retardant modification. However, PTFE, which is a component of the core flame retardant system, inevitably contains perfluoro and polyfluoroalkyl compounds (PFAS) during polymerization. The chemical structure (C-F bond) is extremely stable and can withstand high temperatures, light, chemical action, microbial action and metabolism by higher vertebrates, known as "permanent chemicals", which can produce permanent accumulation in the human body and pose a direct health threat. At the same time studies have shown that contamination of PFAS is exacerbating the global biodiversity crisis.
With the understanding of the potential impact of PFAS in depth, it is expected that the management of PFAS will become more and more stringent worldwide for the next few years. This will drive the related industry to seek and develop alternative materials for PFAS to ensure environmental sustainability of the product. Scientists are conducting research on new PC/ABS flame retardant systems, and hope that the new PC/ABS flame retardant systems can replace the gaps caused by PTFE. The current successful cases are organosilicon flame-retardant systems such as silicon copolymerized PC, organosilicon flame retardant, etc., but the systems increase the modification cost of the daily amount. Fillers with flame retardant synergistic effect, such as glass fiber, talcum powder, nano montmorillonite, wollastonite and the like, are also used, but the systems can achieve stable flame retardant effect, but have low impact strength and affect the use of terminals.
Chinese patent CN107663366a discloses a carbon nanotube reinforced halogen-free flame retardant PC/ABS composite material and a molded article thereof, the composite material comprises PC resin, ABS resin, flame retardant, surface treated carbon nanotubes and reinforcing material according to parts by weight, wherein the reinforcing material comprises silica, the halogen-free flame retardant PC/ABS composite material has excellent mechanical properties, bending strength and flexural modulus can be improved by about 30%, notch impact strength can be improved by more than 20% and has V-0 grade flame retardant properties at the same time, but the composite material cannot effectively cope with PFAS (perfluoroalkyl compound) free requirements.
Disclosure of Invention
The invention aims to provide a fluorine-free flame-retardant PC resin composition, a preparation method and application thereof, and solves the problems of high modification cost, low impact strength, low melt strength and low flame retardant grade of a fluorine-free flame-retardant PC system in the prior art.
The aim of the invention can be achieved by the following technical scheme:
in one aspect, the invention provides a fluorine-free flame retardant PC resin composition, which comprises the following components in parts by weight:
Preferably, the PC resin is a bucket grade PC, and the PC resin has a melt index of 2-5g/10min at 300 ℃ under a 1.2kg load.
Further preferably, the bucket-grade PC resin refers to a polycarbonate PC material that can be used for manufacturing drinking buckets, which is required to meet food contact safety standards, and has excellent transparency, heat resistance, impact resistance, and dimensional stability.
Further preferably, the melt index of the PC resin is 2-3g/10min, so that the melt strength is improved, and the molten drops in the combustion process are reduced.
Preferably, the phosphazene flame retardant has a phosphorus content of greater than 13wt%.
Further preferably, the phosphazene flame retardant comprises hexaphenoxy cyclophosphazene.
Preferably, the fumed silica has a particle size between 150nm and 350 nm.
Preferably, the specific surface area of the fumed silica is between 150 and 400m 2/g.
Preferably, the diameter of the multi-walled carbon nanotubes is 10nm-20nm.
Preferably, the specific surface area of the multi-wall carbon nano tube is 200-400m 2/g.
Preferably, the organosilicon compound is selected from one or more of octaphenyl cyclotetrasiloxane, cage polysilsesquioxane.
Further preferably, the phenyl-substituted methyl ratio of the silicone flame retardant is 80% or more.
Preferably, the toughening agent is a silicon-containing acrylate core-shell toughening agent.
Further preferably, the silicone acrylate rubber is used as the inner core and the content thereof is 50wt% to 65wt%.
Further preferably, the shell of the silicon-containing acrylic acid ester core-shell toughening agent is methyl methacrylate-styrene copolymer.
Further preferably, the silicone acrylate rubber has a particle size of 150nm to 300nm.
Further preferably, the silicone acrylate rubber has a silicon content of 30wt% to 70wt%.
Preferably, the auxiliary agent is selected from one or more of silane coupling agent, titanate coupling agent, hindered phenol antioxidant, phosphite antioxidant, ethylene bisstearamide, polyethylene wax, pentaerythritol stearate, magnesium stearate, calcium stearate and benzotriazole UV absorber.
Further preferably, the silane coupling agent comprises an epoxy silane, a vinyl silane, an amino silane, a methacryloxy silane.
Further preferably, the titanate coupling agent includes a monoalkoxy type titanate coupling agent, a monoalkoxy pyrophosphonate type titanate coupling agent, an integrated type titanate coupling agent, and a ligand type titanate coupling agent.
Further preferably, the hindered phenol antioxidant comprises Irganox 1076,Irganox 1010,Irganox1098,Irganox 300,Irganox 1790,Irganox B900.
Further preferably, the phosphite antioxidant comprises Irgafos 168,Irgafos 626,Irgafos619,Irgafos P-EPQ, irgafos 9228.
Further preferably, the benzotriazole-based UV absorbers include UV-P, UV-329, UV234, UV-326, UV-360, UV-327.
In a second aspect, the present invention also provides a method for preparing the fluorine-free flame retardant PC resin composition, comprising the steps of:
s1, weighing all the components according to parts by weight, and uniformly mixing the components to obtain a mixed raw material;
S2, shearing and mixing the mixed raw materials obtained in the step S1 through a double-screw extruder, melting, compounding, extruding, bracing, cooling and granulating the mixed raw materials to obtain the fluorine-free flame-retardant PC resin composition, wherein the length-diameter ratio of a screw of the double-screw extruder is (35-50): 1, the rotating speed of the screw is 300-500 r/min, and the extruding temperature is 260-280 ℃.
Preferably, the mixing is performed in a high speed mixer.
Further preferably, the rotating speed of the high-speed mixer is 300-500 rpm.
Further preferably, the twin screw extruder has a screw aspect ratio of 40:1.
Further preferably, the screw speed is 400 rpm.
In a third aspect, the invention also provides application of the fluorine-free flame-retardant PC resin composition in new energy batteries, automobiles, electronic products, furniture decorations and office equipment.
Further preferably, the fluorine-free flame retardant PC resin composition is useful for the manufacture of black specific parts in new energy batteries, automobiles, electronic products, furniture decorations, office equipment.
Further preferably, the fluorine-free flame retardant PC resin composition can be applied to manufacturing of battery chargers for electric automobiles.
Further preferably, the fluorine-free flame retardant PC resin composition can be used for manufacturing black decorative parts such as instrument panels, door panels and the like in automobiles, black parts such as bumpers, hub caps and the like outside automobiles, housings for automobile electronic equipment such as in-vehicle infotainment systems, in-vehicle communication equipment and the like.
Further preferably, the fluorine-free flame retardant PC resin composition can be used in a housing, a base, a keyboard, and other black parts of a smart phone, a tablet computer, a notebook computer, and the like.
Further preferably, the fluorine-free flame retardant PC resin composition is used in the manufacture of frames and support members for tables, chairs, sofas.
Further preferably, the fluorine-free flame retardant PC resin composition is useful in the manufacture of black parts for printers and copiers, such as housings and interior structural parts, providing heat and flame resistance protection.
The invention aims to effectively prevent molten drops in the combustion process through the flame-retardant synergism of the gas phase silicon dioxide and the carbon nano tube and a small amount of organic silicon, and the double nano network structure formed by the gas phase silicon dioxide and the carbon nano tube is particularly remarkable in improving the melt strength, so that a black halogen-free fluorine-free flame-retardant PC solution with specific application with relatively low cost can be realized, and meanwhile, the flame-retardant PC solution has excellent mechanical properties.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention mainly prevents the molten drop phenomenon of PC in the combustion process by the double nano-network structure composed of the gas phase silicon dioxide and the multi-wall carbon nano-tube, and greatly improves the overall flame retardant grade by combining a small amount of organic silicon flame retardant, reduces the modification cost of a fluorine-free flame retardant PC system, and has excellent mechanical property.
(2) The invention can greatly improve the melt strength of the flame-retardant system by the double nano-network structure formed by the gas phase silicon dioxide and the carbon nano-tube, thereby effectively preventing the molten drop phenomenon in the combustion process.
(3) According to the invention, V-0 flame retardant grade can be realized through the synergistic effect between the fumed silica, the carbon nano tube and a small amount of organic silicon flame retardant, and meanwhile, excellent mechanical properties are maintained, so that the flame retardant has better impact strength.
(4) The invention provides a halogen-free fluorine-free flame-retardant PC solution for black specific application (carbon nano tube with black attribute) with relatively low cost, which is suitable for being applied to the fields of new energy batteries, office equipment, electronic and electric appliances, household appliances, automobiles and the like.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The components and properties involved in the examples and comparative examples of the present invention are as follows:
PC resin, M7027, mitsubishi, with a melt index of 3g/10min;
phosphazene flame retardant WSFR-5101, zhejiang Wansheng;
toughening agent, MR01, japan brillouin chemistry;
Fumed silica, M-5, cabot, specific surface area 200M 2/g;
CNT,210T, korea brocade lake, specific surface area 250-280m 2/g;
Organosilicon flame retardant-1:FR800, octaphenyl cyclotetrasiloxane, common polymer;
Organosilicon flame retardant-2:FR300, methyl phenyl cyclotetrasiloxane, phenyl substitution rate lower than 80%, common polymer;
Talcum powder, 3CA, yirui stone;
Antioxidant, irganox B900, basf;
lubricants, PETS, AHS, italian hair base.
Table 1 composition of examples 1 to 5 and comparative examples 1 to 8
Examples 1 to 5 and comparative examples 1 to 8
The PC resin, the phosphazene flame retardant, the toughening agent, the fumed silica, the CNT, the organosilicon flame retardant and the auxiliary agent are weighed according to the weight parts of the table 1, are stirred and fully mixed in a high-speed mixer, are sent into a double-screw extruder through a metering device, and are melted, compounded, homogenized, bracing, cooled and granulated under the conditions of conveying, shearing and mixing of screws, so that the fluorine-free flame retardant PC resin composition is obtained.
The length-diameter ratio of the screws of the double-screw extruder is 40:1, and the double-screw extruder is provided with a temperature control device and a vacuumizing device. The extrusion temperature of the double-screw extruder is 260-280 ℃, and the screw rotating speed is 400 rpm.
The fluorine-free flame retardant PC resin compositions prepared in examples 1 to 5 and comparative examples 1 to 8 were subjected to performance test, and the test results are shown in Table 2.
The test methods of each example and comparative example are described below:
The tensile strength test was carried out according to ASTM D638 at a test speed of 50mm/min.
Notched impact strength testing was performed according to ASTM D256.
Melt index testing was conducted according to ASTM D1238, 5kg load, test temperature 240 ℃.
Flame retardant testing was performed according to UL94 standards.
Table 2 Properties of examples 1 to 5 and comparative examples 1 to 8
From examples 1-5 of tables 1 and 2, it can be known that the invention adopts fumed silica and CNT to generate a double nano-network structure in the flame-retardant matrix, greatly enhances the melt strength of the system, can generate good flame-retardant synergistic effect with high-phenyl siloxane flame retardant, can effectively control the melt-dripping phenomenon of flame-retardant PC in the combustion process, plays a role in resisting dripping similar to PTFE, realizes V-0 flame-retardant grade, and simultaneously maintains excellent mechanical properties. Thus, comparative examples 1 to 6 revealed that when fumed silica and CNT are used alone to form a single network structure or not in cooperation with a high-phenyl siloxane flame retardant, they would substantially deteriorate flame retardancy, and stable V-0 flame retardancy grade could not be achieved. From comparative examples 7 and 8, it is known that when talc is used instead of fumed silica or methyl phenyl cyclotetrasiloxane having a low substitution rate of phenyl groups is used, a good synergistic flame retardant effect is not achieved.
The fluorine-free flame-retardant PC resin composition not only has excellent mechanical properties, but also has excellent flame-retardant stability, realizes V-0 grade flame retardance, and is very suitable for being applied to the fields of new energy batteries, office equipment, electronic and electric appliances, home appliances, automobiles and the like.
Claims (10)
1. The fluorine-free flame-retardant PC resin composition is characterized by comprising the following components in parts by weight:
2. The fluorine-free flame retardant PC resin composition according to claim 1, wherein the PC resin is a bucket grade PC having a melt index of 2-5g/10min under a load of 1.2kg at 300 ℃.
3. A fluorine-free flame retardant PC resin composition according to claim 1, wherein the phosphorus content of the phosphazene flame retardant is more than 13wt%, the phosphazene flame retardant comprising hexaphenoxy cyclophosphazene.
4. A fluorine-free flame retardant PC resin composition according to claim 1, wherein the fumed silica has a particle size of between 150nm and 350nm and a specific surface area of between 150 and 400m 2/g.
5. The fluorine-free flame retardant PC resin composition according to claim 1, wherein the diameter of the multi-walled carbon nanotube is 10nm to 20nm and the specific surface area is 200 to 400m 2/g.
6. A fluorine-free flame retardant PC resin composition according to claim 1, wherein the silicone flame retardant is selected from one or more of octaphenyl cyclotetrasiloxane, cage polysilsesquioxane.
7. The fluorine-free flame retardant PC resin composition according to claim 1, wherein the toughening agent is a silicon-containing acrylic core-shell toughening agent, wherein the content of the organic silicon acrylic rubber is 50-65wt% as an inner core, the particle size is 150-300 nm, and the silicon content is 30-70wt%.
8. A fluorine-free flame retardant PC resin composition according to claim 1, wherein the auxiliary agent is selected from one or more of silane coupling agent, titanate coupling agent, hindered phenol antioxidant, phosphite antioxidant, ethylene bis-stearamide, polyethylene wax, pentaerythritol stearate, magnesium stearate, calcium stearate, benzotriazole UV absorber.
9. A method for preparing the fluorine-free flame retardant PC resin composition according to any one of claims 1 to 8, comprising the steps of:
s1, weighing all the components according to parts by weight, and uniformly mixing the components to obtain a mixed raw material;
S2, shearing and mixing the mixed raw materials obtained in the step S1 through a double-screw extruder, melting, compounding, extruding, bracing, cooling and granulating the mixed raw materials to obtain the fluorine-free flame-retardant PC resin composition, wherein the length-diameter ratio of a screw of the double-screw extruder is (35-50): 1, the rotating speed of the screw is 300-500 r/min, and the extruding temperature is 260-280 ℃.
10. Use of the fluorine-free flame retardant PC resin composition according to any one of claims 1-8 in new energy batteries, automobiles, electronic products, furniture decorations, office equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411589438.8A CN119192813A (en) | 2024-11-08 | 2024-11-08 | A fluorine-free flame-retardant PC resin composition and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411589438.8A CN119192813A (en) | 2024-11-08 | 2024-11-08 | A fluorine-free flame-retardant PC resin composition and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN119192813A true CN119192813A (en) | 2024-12-27 |
Family
ID=94052782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411589438.8A Pending CN119192813A (en) | 2024-11-08 | 2024-11-08 | A fluorine-free flame-retardant PC resin composition and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119192813A (en) |
-
2024
- 2024-11-08 CN CN202411589438.8A patent/CN119192813A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367991B (en) | Method of manufacturing polycarbonate/vinyl cyanide-butadiene-styrol copolymer alloy | |
| CN101982500B (en) | Polyphenyl ether alloy resin material for processing photovoltaic connector | |
| EP2287243B1 (en) | High flow polyester composition | |
| KR101328296B1 (en) | Polycarbonate retardant resin composition comprising glass fiber | |
| CN101709142B (en) | A high-toughness halogen-free flame-retardant polycarbonate recycled material compound and its preparation method | |
| CN101362857B (en) | Non-halogen flame-retarding high performance polycarbonate engineering plastics and preparation method thereof | |
| CN101121816B (en) | Anti-flaming polycarbonate/acrylonitrile-butadiene-styrene resin mixing material and preparation method thereof | |
| CN108624006B (en) | High-fluidity glass fiber reinforced flame-retardant PC/PBT alloy material and preparation method thereof | |
| CN102134386B (en) | Polyphenyl ether resin alloy material for processing liquid crystal television shell and bracket | |
| CN101429331A (en) | High-impact resistant halogen-free flame-proof polycarbonate and vinyl cyanide-butadiene-styrene resin alloy and method of producing the same | |
| KR102114531B1 (en) | Thermoplastic resin composition and article produced therefrom | |
| CN101649094A (en) | Flame retarding ABS/PVC/PETG alloy with low cost and high performance and preparation method thereof | |
| CN104086970A (en) | High-efficiency bromine-silicon flame-retardant weather-resistant polycarbonate composite material and preparation method thereof | |
| CN104725797B (en) | Method for preparing flame-retardant plastic composite material | |
| CN107418197B (en) | Heat-conducting nylon engineering plastic and preparation method thereof | |
| CN114274639A (en) | Multilayer co-extrusion transparent high-impact-resistance antistatic polycarbonate composite material and preparation method thereof | |
| CN106633748A (en) | Polycarbonate composite and product thereof | |
| JP2016094614A (en) | Connection structure for solar power generation module | |
| CN112724573A (en) | Polyester alloy composition with good heat resistance and preparation method and application thereof | |
| CN119192813A (en) | A fluorine-free flame-retardant PC resin composition and its preparation method and application | |
| CN113969048B (en) | Bio-based flame-retardant wear-resistant polycarbonate composite material and preparation method and application thereof | |
| CN110551379A (en) | Halogen-free flame-retardant conductive material and product thereof | |
| EP1702008B1 (en) | Polyphenylene sulfide thermoplastic resin composition | |
| CN119286225A (en) | A fluorine-free flame-retardant PC/ABS resin composition and its preparation method and application | |
| CN114525026A (en) | Wear-resistant high-rigidity polycarbonate composite material and preparation method thereof |
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 |