CN114231003B - Transparent flame-retardant polycarbonate composite material and preparation method and application thereof - Google Patents
Transparent flame-retardant polycarbonate composite material and preparation method and application thereof Download PDFInfo
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- CN114231003B CN114231003B CN202111503165.7A CN202111503165A CN114231003B CN 114231003 B CN114231003 B CN 114231003B CN 202111503165 A CN202111503165 A CN 202111503165A CN 114231003 B CN114231003 B CN 114231003B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 75
- 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 74
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 25
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000012796 inorganic flame retardant Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 claims 1
- 239000006082 mold release agent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 34
- 238000002834 transmittance Methods 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 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 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JCGAFSOOJHZRCB-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methoxycarbonyl]hexanoic acid Chemical compound CCCCC(C(O)=O)C(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JCGAFSOOJHZRCB-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- UZRRXKQUEGPNIK-UHFFFAOYSA-M potassium sulfonatosulfonylbenzene Chemical compound C1(=CC=CC=C1)S(=O)(=O)S(=O)(=O)[O-].[K+] UZRRXKQUEGPNIK-UHFFFAOYSA-M 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- KMFXMUYBJLJRGA-UHFFFAOYSA-M sodium;2,3,4-trichlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl KMFXMUYBJLJRGA-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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
The invention discloses a transparent flame-retardant polycarbonate composite material, and a preparation method and application thereof, wherein the transparent flame-retardant polycarbonate composite material comprises the following components in parts by weight: 60-99 parts of polycarbonate resin; 0.1-15 parts of flame retardant; 5-20 parts of glass fiber; 0.5-2 parts of hindered amine light stabilizer; the titanium content of the glass fiber is 0.1-2wt%. The transparent flame-retardant polycarbonate composite material provided by the invention not only has high transparency, but also has excellent flame-retardant property.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to the field of polycarbonate composite materials, and specifically relates to a transparent flame-retardant polycarbonate composite material, and a preparation method and application thereof.
Background
Polycarbonate (polycarbonate PC) is an amorphous thermoplastic with high transparency and is one of five engineering plastics. PC is classified into three types, aliphatic aromatic and aromatic, according to the differences in carbonate bonds in molecular structures, wherein PC is the most excellent in performance among aromatic type PC, and is generally called bisphenol a type PC of aromatic type. PC itself has high transparency, and has higher rigidity, modulus, excellent creep resistance, good high temperature resistance and good dimensional stability due to its benzene ring structure. Meanwhile, PC has good impact toughness due to the carbonate bond structure. Because of these excellent properties, PC is widely used in industries and products such as electronics and electrical, home appliances, OA, electric tools, storage batteries, charging piles, notebook computers, etc., and PC application in these products also puts a demand on its flame retardant properties.
Flammability UL94 rating is the most widely used plastic material flammability performance standard. It was used to evaluate the ability of a material to extinguish after being ignited. Among these, the burning rate, burning time, anti-drip ability, and whether or not the drip (drip) burns all affect the flammability rating. The flame retardant grade of the plastic is gradually increased from HB, V-2 and V-1 to V-0, and the higher the UL94 grade is, the better the flame retardant property of the material is.
The PC raw material resin has an oxygen index of 21-24%, and the flame retardant performance of the PC raw material resin can reach the UL 94V-2@3.2mm grade, but the grade can not meet the requirement of the electronic and electric devices on the flame retardant performance, so that the PC resin needs to be subjected to flame retardant modification. The existing halogen-free flame retardants for PC modified products mainly comprise phosphorus flame retardants, silicon flame retardants, inorganic flame retardants and the like, but most of the conventional flame retardants solve the problems of reducing the combustion speed of materials and reducing the combustion time (namely, how to quickly extinguish the materials after combustion), so that the flame retardant effect is achieved, moreover, a large amount of flame retardants are required to be used for effectively playing the role of flame retardance, but the addition of a large amount of flame retardants seriously affects the transparency of the PC, so that the PC materials are limited to be applied to scenes requiring high transparency and good flame retardance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a transparent flame-retardant PC material and a preparation method thereof. The transparency of the transparent flame-retardant polycarbonate composite material provided by the invention is up to 80%, and the flame-retardant property is excellent, so that the flame-retardant grade of UL94 standard V-0@0.8mm can be achieved.
The method is realized by the following technical scheme:
The transparent flame-retardant polycarbonate composite material comprises the following components in parts by weight:
The titanium content of the glass fiber is 0.1-2wt%.
Further, the composition comprises the following components in parts by weight:
the titanium content of the glass fiber is 0.2-1wt%.
Further, the light transmittance of the hindered amine light stabilizer at the wavelength of 425-500nm is more than or equal to 97%, and the light transmittance is tested according to ISO13468-2-2006 standard. The addition of the hindered amine light stabilizer affects the transparency of the polycarbonate resin, while the selection of the hindered amine light stabilizer having a light transmittance of 97% or more can reduce the decrease in the transparency of the polycarbonate resin due to the addition of the hindered amine light stabilizer.
In addition, the hindered amine light stabilizer is compounded with the glass fiber to play a role in preventing dripping matters from being generated when the material burns. The hindered amine light stabilizer can capture carbon free radicals generated in the combustion degradation process of the PC material and prevent the molecular chains from being degraded under the condition of being heated, so that the phenomenon that the PC material drops off due to combustion substances on a macroscopic effect caused by low viscosity of the PC material due to the thermal degradation of the molecular chains is fundamentally solved, and the reduction of the dropping phenomenon is beneficial to improving the flame retardant grade of the PC material.
The glass fiber containing 0.2-1wt% of titanium can also play a role of a bridge, and can act together with the hindered amine light stabilizer to form a tighter grid structure among molecular chains of the PC material, so that dripping matters are not easy to form, and the glass fiber containing the specific titanium content and the hindered amine light stabilizer are compounded to play a role of reducing the generation of dripping matters in the combustion process of the material in a synergistic manner, so that the flame retardant property of the PC material is improved.
The addition of glass fibers can improve the flame retardant performance of the material, but the addition of glass fibers can have adverse effects on the transparency of the polycarbonate resin composite material.
In the scheme, the refractive index of the glass fiber is adjusted by screening the content of titanium element in the glass fiber, and when the refractive index of the glass fiber is improved, the polycarbonate resin composite material can have better transparency. However, the titanium component has obvious coloring effect, and when the addition amount is improper, the color of the glass fiber is yellowish, so that the addition amount of the titanium needs to consider the balance of transparency and refractive index besides improving the refractive index of the glass fiber. In the scheme, when the glass fiber with the titanium content of 0.1-2wt%, especially 0.2-1 wt%, is found, the refractive index of the glass fiber can be controlled to be 1.580-1.590, and the refractive index of the polycarbonate resin is generally greater than 1.580, at the moment, the PC material has excellent flame retardant property, and the refractive index of the glass fiber is similar to that of the polycarbonate resin, so that the prepared PC material has high transparency and light color.
Preferably, the method comprises the steps of, the hindered amine light stabilizer is [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butyl malonic acid di (1, 2, 6-pentamethyl-4-piperidyl) ester one or more of bis (1, 2, 6-pentamethylpiperidinol) sebacate or maleic anhydride alpha olefin (C20-24) polymer with 2, 6-tetramethyl-4-piperidinamine.
Further, the polycarbonate resin is a double A-type polycarbonate, and has a weight average molecular weight of 15000 to 30000, preferably 19000 to 22000. The weight average molecular weight of the polycarbonate resin affects the flame retardancy of the PC composite. The polycarbonate resin with the weight average molecular weight of 15000-30000, preferably 19000-22000, can form a grid structure among molecular chains of the resin, so that the resin is not easy to form dripping substances when heated, the flame retardant performance of the PC material is improved, and the transparency of the polycarbonate resin is not affected by adding excessive auxiliary agents.
Further, the flame retardant is one or more of a phosphorus flame retardant, a sulfur flame retardant or an inorganic flame retardant. These flame retardants have different flame retardant characteristics due to their respective different molecular structures and flame retardant mechanisms.
The phosphorus-based flame retardant includes, but is not limited to, trimethyl phosphate, tricresyl phosphate, tetraphenyl resorcinol diphosphate, or ammonium polyphosphate.
The sulfur-based flame retardant includes, but is not limited to, potassium perfluorobutyl sulfonate, potassium benzenesulfonyl sulfonate, or sodium trichlorobenzene sulfonate.
The inorganic flame retardant includes, but is not limited to, aluminum hydroxide, magnesium sulfate heptahydrate, or antimony trioxide.
Preferably, the flame retardant is a phosphorus-based flame retardant. The phosphorus flame retardant can promote the formation of a carbonized layer of the polycarbonate resin during combustion, so that the generation of drips after the material is combusted can be reduced, and the flame retardant property of the polycarbonate can be well improved.
Further, the transparent flame-retardant polycarbonate composite material also comprises 0-1 part of other auxiliary agents.
Preferably, the other auxiliary agent is one or more of an antioxidant, a release agent or a lubricant.
The antioxidant is one or more of common antioxidant, preferably antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant B-CAP, antioxidant PEP-36, antioxidant S-680, antioxidant 2246 and antioxidant 245.
The release agent is a common release agent including, but not limited to, silicone oil, polyethylene wax, and the like.
The lubricant includes, but is not limited to, stearic acid amide, paraffin wax, silicone, or polydiethylsiloxane.
The invention also provides a preparation method of the transparent flame-retardant polycarbonate composite material, which comprises the following steps:
s1, weighing the components according to the proportion, and premixing to obtain a premix;
S2: and (3) putting the premix in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the transparent flame-retardant polycarbonate composite material.
Further, the extruder is a twin screw extruder having a screw aspect ratio of (40-48): 1, the screw cylinder temperature of the double-screw extruder is 240-290 ℃, and the screw rotating speed of the double-screw extruder is 300-500r/min.
The invention also provides application of the transparent flame-retardant polycarbonate composite material in preparing transparent parts of electronic and electric appliances, such as preparing transparent panels, transparent covers and the like.
Compared with the prior art, the invention has the beneficial effects that:
The invention discloses a transparent flame-retardant polycarbonate composite material, which uses glass fiber containing 0.2-1wt% of titanium and hindered amine light stabilizer, and the glass fiber and the hindered amine light stabilizer have synergistic flame-retardant effect. Meanwhile, the PC composite material prepared by selecting glass fiber with the refractive index of 1.580-1.590, hindered amine light stabilizer with the light transmittance of more than or equal to 97 percent and polycarbonate resin with the weight average molecular weight of 15000-30000 not only has high transparency, but also has excellent mechanical properties such as flame resistance, bending deformation resistance and the like, and is very suitable for preparing transparent parts of electronic appliances, such as transparent panels, transparent covers and the like.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, the hindered amine light stabilizer is used together with the glass fiber, and can play a role in preventing dripping matters from generating when the material burns. The hindered amine light stabilizer can capture carbon free radicals generated in the combustion degradation process of the PC material and prevent the molecular chains from being degraded under the condition of being heated, so that the phenomenon that the PC material drops off due to combustion substances on a macroscopic effect caused by low viscosity of the PC material due to the thermal degradation of the molecular chains is fundamentally solved, and the reduction of the dropping phenomenon is beneficial to improving the flame retardant grade of the PC material.
The glass fiber containing 0.2-1wt% of titanium can also play a role of a bridge, and can act together with the hindered amine light stabilizer to form a tighter grid structure between molecular chains of the PC material, so that dripping matters are not easy to form, and the glass fiber containing the specific titanium content and the hindered amine light stabilizer are compounded to play a role of reducing the dripping matters generated in the combustion process of the material in a synergistic manner, so that the flame retardant property of the PC material is improved, and in addition, the transparency of the PC composite material is not influenced, and the PC composite material has high transparency.
< Preparation of examples and comparative examples >
The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:
Double a-type polycarbonate resin a: weight average molecular weight 15000, trade name FN1500, purchased from bench top luminescence;
double a-type polycarbonate resin B: weight average molecular weight 19000, trade name H-2000F, purchased from Mitsubishi, japan;
Double a-type polycarbonate resin C: weight average molecular weight 22000, brand S-2000F, commercially available from Mitsubishi, japan;
double a-type polycarbonate resin D: weight average molecular weight 30000, trade designation 1300 03NP, available from LG in korea;
double a-type polycarbonate resin E: weight average molecular weight 10000, commercially available;
double a-type polycarbonate resin F: weight average molecular weight 35000, trade name 7030PJ, available from mitsubishi japan;
flame retardant a: (phosphorus flame retardant), BDP, trade name WSFR-BDP-N2 is purchased from Wansheng chemical industry;
flame retardant B: (inorganic flame retardant), antimony white, brand S-12N, available from Hangzhou Kohli Co., ltd;
Flame retardant C: (sulfur-based flame retardant), potassium perfluorobutyl sulfonate, brand FR-2025, commercially available from Mitsubishi;
Glass fiber # 1: titanium content 0.1wt%, trade mark ECS13-3.0-T436W, purchased from giant stone group;
glass fiber # 2: titanium content 0.2wt%, trade mark ECS303W-3-K, purchased from Chongqing International;
glass fiber 3#: titanium content 1wt%, brand HMG538-10-4.5, purchased from boulder glass fiber;
Glass fiber # 4: titanium content 2wt%, brand HMG436S-10-4.0, available from Taishan glass fiber Co., ltd;
glass fiber # 5: titanium content 0.05wt%, commercially available;
Glass fiber # 6: titanium content 2.5wt%, commercially available;
The method for measuring the titanium content in the glass fiber 1# -6# comprises the following steps: after acidolysis of the glass fibers, the titanium content was measured with an ICP instrument.
Hindered amine light stabilizer a: [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butylmalonate bis (1, 2, 6-pentamethyl-4-piperidinyl) having a light transmittance of 97%, measured at a wavelength of 425nm, of the brand G15-144, purchased from highland barley new material technology;
Hindered amine light stabilizer B: bis (1, 2, 6-pentamethylpiperidinol) sebacate, 98% transmittance, measured at a wavelength of 425nm, brand TINUVIN 292, available from basf;
hindered amine light stabilizer C: the reaction product of maleic anhydride alpha olefin (C20-24) polymer with 2, 6-tetramethyl-4-piperidylamine, light transmittance 99%, measured at a wavelength of 425nm, brand Uninul, 5050H, available from Basf;
an antioxidant: phosphite antioxidants; brand antioxidant 168, available from basf corporation;
and (3) a release agent: polyethylene wax, trade designation A-C613, available from Honiswell;
And (3) a lubricant: silicone lubricant, trade name MB50-002, available from Dow Corning.
The preparation methods of the examples and comparative examples of the present invention are as follows:
s1, weighing the components according to the proportion of the table 1 and the table 2, and premixing to obtain a premix;
S2: and (3) putting the premix in the step (S1) into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain the transparent flame-retardant polycarbonate composite material with the thickness of 0.8 mm.
The aspect ratio of the screws of the twin-screw extruder was 45:1, the screw cylinder temperature of the double-screw extruder is 250 ℃, and the screw rotating speed of the double-screw extruder is 400r/min.
In the present specification, "parts" means "parts by weight" unless specifically stated otherwise.
< Test Standard >
The performance test criteria for each of the examples and comparative examples of the present invention are as follows:
Titanium content: the method for measuring the titanium content in the glass fiber comprises the following steps: acidolysis of glass fiber, and testing titanium content by ICP instrument;
Flame retardancy: testing according to UL94, and observing whether dripping occurs in the material in the testing process by naked eyes;
Transmittance: the test was performed according to ISO13468-2-2006, the thickness of the sample being 2.0mm, the test equipment being a transmittance/haze meter WGT-S of Shanghai precision, the transmittance being used to indicate the transparency of the material.
Table 1 formulations of examples 1-11 and results of performance testing
TABLE 2 formulations of comparative examples 1-5 and results of Performance test
Comparative examples 1 and 2 are more likely to cause drips during combustion because the molecular weight of the polycarbonate resin is too small compared with example 1; too large molecular weight affects the dispersibility of the glass fibers, thereby affecting the transparency and increasing the risk of the generation of drips, and at the same time, too large molecular weight of the polycarbonate resin affects the fluidity, which deteriorates the fluidity and affects the molding performance. The molecular weight is in the range of 15000-30000, and the PC resin material has no dripping during the flame-retardant test, which means that the PC resin has excellent flame-retardant grade at this time and does not influence the transparency of the PC resin.
In both comparative examples 3 and 4, the titanium content of the glass fiber was not in the range of 0.1 to 2wt% as compared with example 4, the titanium content of the glass fiber of comparative example 3 was too small, the effect of the glass fiber of comparative example 3 in light stabilization with hindered amine to reduce the generation of drips was weak as compared with example 2, and in comparative example 4, too much titanium content of the glass fiber affected the transparency of the PC composite, so that it could be demonstrated that the titanium content of the glass fiber would seriously affect the transparency and flame retardant properties of the PC composite. Comparative example 5 compared with example 1, the use of a hindered amine light stabilizer having a light transmittance of less than 97% resulted in a PC resin material having a much lower transparency than that of example 1, since the use of a hindered amine stabilizer having a light transmittance of less than 97% affected the transparency of the PC resin.
Example 12
The transparent flame-retardant polycarbonate composite material prepared in example 1 is prepared into a transparent panel, and the transmittance and flame-retardant performance of the transparent panel are tested, so that the result is that: the transparent panel has light transmittance of 85%, no phenomenon of dropping, flame retardant grade of V-0, and high transparency and good flame retardant grade, so that the transparent flame retardant polycarbonate composite material provided by the invention can be considered to be suitable for transparent parts of electronic appliances with high requirements on transparency and flame retardance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The transparent flame-retardant polycarbonate composite material is characterized by comprising the following components in parts by weight:
60-99 parts of polycarbonate resin
0.1-15 Parts of flame retardant
5-20 Parts of glass fiber
0.5-2 Parts of hindered amine light stabilizer;
the titanium content in the glass fiber is 0.2-1wt%;
the refractive index of the glass fiber is 1.580-1.590;
The hindered amine light stabilizer is any one of [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butyl malonic acid bis (1, 2, 6-pentamethyl-4-piperidinyl) ester, sebacic acid bis (1, 2, 6-pentamethylpiperidinol) ester and Uvinul 5050H;
the polycarbonate resin is bisphenol A type polycarbonate, and the weight average molecular weight is 15000-30000.
2. The transparent flame retardant polycarbonate composite material of claim 1, comprising the following components in parts by weight:
70-90 parts of polycarbonate resin
3-12 Parts of flame retardant
6-18 Parts of glass fiber
1-1.5 Parts of hindered amine light stabilizer;
the titanium content of the glass fiber is 0.2-1wt%.
3. The transparent flame retardant polycarbonate composite of claim 2, wherein the polycarbonate resin has a weight average molecular weight of 19000 to 22000.
4. The transparent flame retardant polycarbonate composite of claim 1 or 2, wherein the flame retardant is one or more of a phosphorus based flame retardant, a sulfur based flame retardant, or an inorganic flame retardant.
5. The transparent flame retardant polycarbonate composite of claim 1 or 2, further comprising 0-1 parts of an auxiliary agent.
6. The transparent flame retardant polycarbonate composite of claim 5, wherein the auxiliary agent is one or more of an antioxidant, a mold release agent, or a lubricant.
7. A method of preparing a transparent flame retardant polycarbonate composite according to any one of claims 1-6, comprising the steps of:
s1: weighing the components according to the proportion, and premixing to obtain a premix;
S2: and (3) putting the premix in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the transparent flame-retardant polycarbonate composite material.
8. Use of a transparent flame retardant polycarbonate composite according to any one of claims 1 to 6 or a transparent flame retardant polycarbonate composite prepared according to the method of preparation of a transparent flame retardant polycarbonate composite of claim 7 for the preparation of a transparent article of an electronic and electrical appliance.
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