CN114231003A - 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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- CN114231003A CN114231003A CN202111503165.7A CN202111503165A CN114231003A CN 114231003 A CN114231003 A CN 114231003A CN 202111503165 A CN202111503165 A CN 202111503165A CN 114231003 A CN114231003 A CN 114231003A
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- CN
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- Prior art keywords
- composite material
- flame retardant
- polycarbonate composite
- transparent
- flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 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
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 74
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 23
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 23
- 239000004611 light stabiliser Substances 0.000 claims abstract description 22
- 238000002834 transmittance Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 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
- 239000012752 auxiliary agent Substances 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
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 32
- 238000002485 combustion reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 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
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000009471 action Effects 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
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 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 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 230000009467 reduction Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 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
- 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
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 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
- 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
- 150000008301 phosphite esters Chemical class 0.000 description 1
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 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
- 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, a preparation method and an 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 a 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 0.1-2 wt%. 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 (PC) is an amorphous thermoplastic with high transparency and is one of five major engineering plastics. According to the difference of carbonate bonds in the molecular structure, PC can be divided into three types of aliphatic, aliphatic aromatic and aromatic, wherein the aromatic PC has the most excellent performance, and the PC is generally called bisphenol A type PC of aromatic. PC has high transparency, and has higher rigidity and modulus, excellent creep resistance, good high temperature resistance and good dimensional stability due to the benzene ring structure. Meanwhile, the PC has good impact toughness due to its carbonate bond structure. Due to the excellent properties of the PC, the PC is widely applied to industries and products such as electronics, electrics, household appliances, OA, electric tools, storage batteries, charging piles, notebook computers and the like, and the application of the PC in the products also puts certain requirements on the flame retardant property of the PC.
Flammability UL94 rating is the flammability performance standard for the most widely used plastic materials. It is used to evaluate the ability of a material to extinguish after being ignited. Among them, the burning rate of the material, the burning time, the anti-dripping ability, and whether or not the droplets (drops) burn affect the flammability rating. The flame retardant rating of the plastic is gradually increased from HB, V-2 and V-1 to V-0, and the higher the UL94 rating, the better the flame retardant property of the material is.
The PC raw material resin has an oxygen index of 21-24%, and although the flame retardant property of the PC raw material resin can reach the UL [email protected] grade, the grade cannot meet the requirement of electronic and electric products on the flame retardant property, so that the PC resin needs to be subjected to flame retardant modification. At present, halogen-free flame retardants used for PC modified products mainly include phosphorus flame retardants, silicon flame retardants, inorganic flame retardants, and the like, but most of these conventional flame retardants solve the problems of how to reduce the combustion speed of materials and how to reduce the combustion time (i.e., how to make materials quickly extinguish after combustion), thereby achieving a flame retardant effect, and some flame retardants need a larger amount of use to effectively exert a flame retardant effect, but the addition of a large amount of flame retardants will seriously affect the transparency of PC, which will limit the application of PC materials in some scenes that require both high transparency and good flame retardancy.
Disclosure of Invention
In order to overcome the defects of 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%, the flame-retardant property is excellent, and the flame-retardant grade of [email protected] in UL94 standard 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 in the glass fiber is 0.1-2 wt%.
Further, the coating comprises the following components in parts by weight:
the titanium content in the glass fiber is 0.2-1 wt%.
Further, the light transmittance of the hindered amine light stabilizer at the wavelength of 425-500nm is more than or equal to 97 percent, and the light transmittance is tested according to the ISO13468-2-2006 standard. The transparency of the polycarbonate resin is affected by the addition of the hindered amine light stabilizer, and the transparency of the polycarbonate resin can be reduced by selecting the hindered amine light stabilizer with the light transmittance of more than or equal to 97%.
In addition, the hindered amine light stabilizer and the glass fiber are compounded for use, so that the effect of synergistically preventing the generation of dripping during the combustion of the material is achieved. The hindered amine light stabilizer can capture carbon free radicals generated in the combustion degradation process of the PC material, and prevents molecular chains from being degraded under the heating condition, so that the phenomenon that the viscosity of the PC material is reduced due to the thermal degradation of the molecular chains, so that the combustion substances drop in the macroscopic effect is fundamentally solved, and the reduction of the dropping phenomenon is favorable for improving the flame retardant grade of the PC material.
The glass fiber containing 0.2-1 wt% of titanium can also play a role of a bridge and has a combined action with the hindered amine light stabilizer, so that a tighter grid structure is formed between molecular chains of the PC material, and dripping is not easy to form, so that the glass fiber containing specific titanium content and the hindered amine light stabilizer are compounded to play a role in synergistically reducing the generation of dripping in the combustion process of the material, and the flame retardant property of the PC material is improved.
The flame retardant property of the material can be improved by adding the glass fiber, but the addition of the glass fiber can have adverse effect on the transparency of the polycarbonate resin composite material.
In the scheme, the content of the titanium element in the glass fiber is screened, the refractive index of the glass fiber is adjusted, and when the refractive index of the glass fiber is improved, the polycarbonate resin composite material has better transparency. However, the titanium component has a significant coloring effect, and when the titanium component is added in an inappropriate amount, the glass fiber tends to be yellowish in color, so that the titanium component needs to be added in consideration of not only improvement of the refractive index of the glass fiber but also a balance between transparency and refractive index. In the scheme, researches show that when the content of titanium is 0.1-2 wt%, especially 0.2-1 wt% of glass fiber, 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 larger than 1.580, in this case, the PC material not only has excellent flame retardant property, but also 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 hindered amine light stabilizer is one or more of [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butylmalonic acid bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) ester, sebacic acid bis (1,2,2,6, 6-pentamethylpiperidinol) ester, or a reaction product of a maleic anhydride alpha olefin (C20-24) polymer and 2,2,6, 6-tetramethyl-4-piperidinamine.
Further, the polycarbonate resin is a bis-A 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 and preferably 19000-22000 is selected, a grid structure can be formed among molecular chains of the resin, so that the resin is not easy to form drops when being heated, the flame retardant property of the PC material is improved, and the transparency of the polycarbonate resin cannot be influenced by adding excessive additives.
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 different molecular structures and flame retardant mechanisms.
The phosphorus-based flame retardant includes, but is not limited to, trimethyl phosphate, tricresyl phosphate, tetraphenylresorcinol diphosphate, or ammonium polyphosphate.
The sulfur-based flame retardant includes, but is not limited to, potassium perfluorobutylsulfonate, potassium benzenesulfonylbenzenesulfonate, or sodium trichlorobenzenesulfonate.
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 the combustion, thereby reducing the generation of drops after the combustion of the material and well improving the flame retardant property of the polycarbonate.
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 mold release agent or a lubricant.
The antioxidant is common antioxidant, preferably one or more of antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant B-CAP, antioxidant PEP-36, antioxidant S-680, antioxidant 2246 and antioxidant 245.
The release agent is common release agent, and includes but is not limited to silicone oil, polyethylene wax and other release agents.
The lubricant includes, but is not limited to, stearic acid amide, paraffin, 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 (4) putting the premix obtained 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, and the length-diameter ratio of screws of the twin-screw extruder is (40-48): 1, the barrel temperature of the double-screw extruder is 240-290 ℃, and the screw rotating speed of the double-screw extruder is 300-500 r/min.
The invention also provides application of the transparent flame-retardant polycarbonate composite material in preparation of transparent parts of electronic and electric appliances, such as preparation of 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 0.2-1 wt% of titanium and hindered amine light stabilizer, and the glass fiber and the hindered amine light stabilizer play a synergistic flame-retardant role. Meanwhile, by selecting the glass fiber with the refractive index of 1.580-1.590, the hindered amine light stabilizer with the light transmittance of more than or equal to 97 percent and the polycarbonate resin with the weight-average molecular weight of 15000-30000, the prepared PC composite material 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 products of electronic and electric appliances, such as transparent panels, transparent covers and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the invention, the hindered amine light stabilizer is used together with the glass fiber, and can play a role in synergistically preventing the generation of dropping substances during the combustion of the material. The hindered amine light stabilizer can capture carbon free radicals generated in the combustion degradation process of the PC material, and prevents molecular chains from being degraded under the heating condition, so that the phenomenon that the viscosity of the PC material is reduced due to the thermal degradation of the molecular chains, so that the combustion substances drop in the macroscopic effect is fundamentally solved, and the reduction of the dropping phenomenon is favorable for improving the flame retardant grade of the PC material.
The glass fiber containing 0.2-1 wt% of titanium can also play a role of a bridge and has a combined action with the hindered amine light stabilizer, so that a tighter grid structure is formed between molecular chains of the PC material, and dripping is not easy to form, so that the glass fiber containing specific titanium content and the hindered amine light stabilizer are compounded to play a role in synergistically reducing the generation of dripping in the combustion process of the material, improve the flame retardant property of the PC material, and in addition, the transparency of the PC composite material is not influenced, so that the PC composite material has high transparency.
< preparation of examples and comparative examples >
The raw materials used in the examples of the present invention and the comparative examples are commercially available, but are not limited to these materials:
bis-a type polycarbonate resin a: weight average molecular weight 15000, designation FN1500, purchased from a commercial light;
bis-a type polycarbonate resin B: a weight average molecular weight of 19000, designation H-2000F, available from Mitsubishi, Japan;
bis-a type polycarbonate resin C: weight average molecular weight 22000, designation S-2000F, available from Mitsubishi, Japan;
bis-a type polycarbonate resin D: weight average molecular weight 30000, designation 130003 NP, available from LG in Korea;
bis-a type polycarbonate resin E: weight average molecular weight 10000, commercially available;
bis-a type polycarbonate resin F: weight average molecular weight 35000, designation 7030PJ, available from Mitsubishi, Japan;
flame retardant A: (phosphorus flame retardant), BDP, brand WSFR-BDP-N2, was purchased from Wansheng chemical;
and (3) a flame retardant B: (inorganic flame retardant), antimony white, brand S-12N, available from Hangzhou Koley Co., Ltd;
and (3) a flame retardant C: (flame retardant of sulfur series), potassium perfluorobutylsulfonate, trade designation FR-2025, available from mitsubishi;
glass fiber 1 #: titanium content 0.1 wt%, grade ECS13-3.0-T436W, available from the boulder group;
glass fiber 2 #: 0.2 wt% of titanium, and the mark ECS303W-3-K, which is purchased from Chongqing International;
glass fiber 3 #: 1 wt% of titanium, and a mark HMG538-10-4.5 purchased from giant rock glass fiber;
glass fiber 4 #: 2 wt% titanium content, and a mark HMG436S-10-4.0, available from Taishan glass fiber Co., Ltd;
glass fiber 5 #: 0.05 wt% of titanium, commercially available;
glass fiber 6 #: 2.5 wt% of titanium, and is commercially available;
the method for measuring the titanium content in the glass fiber 1# -6# comprises the following steps: the glass fiber was subjected to acidolysis and then tested for titanium content using an ICP instrument.
Hindered amine light stabilizer a: [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butyl malonic acid bis (1,2,2,6, 6-pentamethyl-4-piperidyl) ester, the light transmittance is 97 percent, the light transmittance is measured at the wavelength of 425nm, and the mark is G15-144, which is purchased from highland barley new technology;
hindered amine light stabilizer B: bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate having a light transmission of 98%, measured at a wavelength of 425nm, and having the brand name TINUVIN 292, available from basf;
hindered amine light stabilizer C: the reaction product of a maleic anhydride alpha olefin (C20-24) polymer and 2,2,6, 6-tetramethyl-4-piperidylamine, had a light transmittance of 99%, measured at a wavelength of 425nm, and was available from Basf under the designation Uninul 5050H;
antioxidant: a phosphite ester antioxidant; brand antioxidant 168 available from basf corporation;
releasing agent: polyethylene wax, designation A-C613, available from Honeywell;
lubricant: silicone lubricant, designation MB50-002, was purchased 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 mixture ratio of the table 1 and the table 2, and premixing to obtain a premix;
s2: and (4) putting the premix obtained in the step S1 into a double-screw extruder, carrying out melt blending and extrusion granulation to obtain the transparent flame-retardant polycarbonate composite material with the thickness of 0.8 mm.
The length-diameter ratio of the screws of the double-screw extruder is 45: 1, the temperature of a screw cylinder of the double-screw extruder is 250 ℃, and the screw rotating speed of the double-screw extruder is 400 r/min.
In the present specification, the term "part(s)" means "part(s) by weight" unless otherwise specified.
< test standards >
The performance test standards of the examples of the present invention and the comparative examples are as follows:
titanium content: the method for measuring the titanium content in the glass fiber comprises the following steps: carrying out acidolysis on the glass fiber, and testing the titanium content by using an ICP instrument;
flame retardancy: testing according to UL94, and observing whether the material has dripping during the testing process by naked eyes;
light transmittance: the test is carried out according to the ISO13468-2-2006 standard, the thickness of a test sample is 2.0mm, the test equipment is a light transmittance/haze meter WGT-S of Shanghaineco, and the light transmittance is used for indicating the transparency of the material.
TABLE 1 formulations and performance test results for examples 1-11
TABLE 2 formulations and performance test results for comparative examples 1-5
Comparative examples 1 and 2 compared with example 1, since the molecular weight of the polycarbonate resin is too small, dripping is more likely to occur during burning; too large a molecular weight affects the dispersibility of the glass fiber, thereby affecting transparency, and increasing the risk of generation of drips, and too large a molecular weight of the polycarbonate resin affects flowability, thereby deteriorating flowability and affecting moldability. The molecular weight is in the range of 15000-30000, and no dripping of the PC resin material occurs during the flame-retardant test, which means that the flame-retardant grade of the PC resin is excellent and the transparency of the PC resin is not affected.
In comparative examples 3 and 4, the titanium content of the glass fiber is not in the range of 0.1 to 2 wt% compared to example 4, the titanium content of the glass fiber of comparative example 3 is too small, the glass fiber of comparative example 3 has a weak effect of reducing the generation of the dripping with the synergistic effect of the light stabilization of the hindered amine compared to example 2, and the titanium content of the glass fiber of comparative example 4 is too large, which affects the transparency of the PC composite material, so that it can be demonstrated that the titanium content of the glass fiber seriously affects the transparency and the flame retardant property of the PC composite material. Comparative example 5 using a hindered amine light stabilizer having a light transmittance of less than 97% as compared to example 1, the transparency of the finally obtained PC resin material is far inferior to that of example 1 because the use of a hindered amine light stabilizer having a light transmittance of less than 97% affects the transparency of the PC resin.
Example 12
The transparent flame-retardant polycarbonate composite material prepared in example 1 was prepared into a transparent panel, and the light transmittance and flame retardancy of the transparent panel were measured, with the results that: the transparent panel has the light transmittance of 85 percent, does not have the phenomenon of generation of dripping objects, has the flame retardant grade of V-0, and also has 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 and electric appliances with high requirements on transparency and flame retardancy.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The transparent flame-retardant polycarbonate composite material is characterized by comprising the following components in parts by weight:
the titanium content in the glass fiber is 0.1-2 wt%.
2. The transparent flame-retardant polycarbonate composite material according to claim 1, which comprises the following components in parts by weight:
the titanium content in the glass fiber is 0.2-1 wt%.
3. The transparent flame-retardant polycarbonate composite material as claimed in claim 1 or 2, wherein the light transmittance of the hindered amine light stabilizer at a wavelength of 425 and 500nm is greater than or equal to 97%, and the light transmittance is measured according to ISO13468-2-2006 standard.
4. The transparent flame-retardant polycarbonate composite material according to claim 1 or 2, wherein the polycarbonate resin is a bis-A type polycarbonate and has a weight-average molecular weight of 15000 to 30000.
5. The transparent flame-retardant polycarbonate composite material according to claim 4, wherein the polycarbonate resin has a weight-average molecular weight of 19000 to 22000.
6. The transparent flame retardant polycarbonate composite material according to claim 1 or 2, wherein the flame retardant is one or more of a phosphorus flame retardant, a sulfur flame retardant or an inorganic flame retardant, preferably a phosphorus flame retardant.
7. The transparent flame retardant polycarbonate composite of claim 1 or 2, further comprising 0-1 part of an auxiliary agent.
8. The transparent flame retardant polycarbonate composite of claim 7, wherein the auxiliary agent is one or more of an antioxidant, a mold release agent, or a lubricant.
9. A method for preparing the transparent flame retardant polycarbonate composite material according to any one of claims 1 to 8, comprising the steps of:
s1: weighing the components according to the proportion, and premixing to obtain a premix;
s2: and (4) putting the premix obtained in the step S1 into an extruder, carrying out melt blending, extruding and granulating to obtain the transparent flame-retardant polycarbonate composite material.
10. Use of the transparent flame retardant polycarbonate composite material according to any one of claims 1 to 8 or the transparent flame retardant polycarbonate composite material prepared by the method according to claim 9 for preparing a transparent part of an electronic or electric appliance.
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