WO2022001053A1 - 一种聚碳酸酯组合物及其制备方法和应用 - Google Patents
一种聚碳酸酯组合物及其制备方法和应用 Download PDFInfo
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- WO2022001053A1 WO2022001053A1 PCT/CN2020/140806 CN2020140806W WO2022001053A1 WO 2022001053 A1 WO2022001053 A1 WO 2022001053A1 CN 2020140806 W CN2020140806 W CN 2020140806W WO 2022001053 A1 WO2022001053 A1 WO 2022001053A1
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- WIPO (PCT)
- Prior art keywords
- polycarbonate
- polycarbonate composition
- composition according
- parts
- maleic anhydride
- Prior art date
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 75
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000012763 reinforcing filler Substances 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229910021487 silica fume Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 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
- AOYVABWPDDHCDE-UHFFFAOYSA-N (2,3-dimethylphenyl)phosphonic acid Chemical class CC1=CC=CC(P(O)(O)=O)=C1C AOYVABWPDDHCDE-UHFFFAOYSA-N 0.000 description 1
- TYCLKLCKLGCVEZ-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C TYCLKLCKLGCVEZ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- VYGRRCKMMADGBB-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphono hydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O VYGRRCKMMADGBB-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YJLVKRVGSARISS-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(C)=C1OP(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C YJLVKRVGSARISS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-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
- 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Definitions
- the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method and application thereof.
- Polycarbonate (PC) is an engineering plastic with excellent performance. It has good comprehensive properties, high mechanical strength, good impact toughness, dimensional stability, good heat resistance, and good electrical insulation. It is used in home appliances, digital products, IT products, etc. and other fields have a wide range of applications. As TVs become thinner and more aesthetically pleasing, the corresponding plastic materials must not only have good mechanical properties, higher heat resistance and fluidity, but also have good bonding properties with metals to meet the needs of large-size bezel-less TVs. need.
- the polycarbonate material has no active groups on the surface, low surface energy, poor compatibility with metal substances, and a large difference with the linear expansion coefficient of metals, which is difficult to wet, so the interface between the two is weak, resulting in adhesion or bonding. Poor force, with the accumulation of use time, the accumulated stress between plastic and metal due to uneven cold and heat shrinkage is easy to debond, which limits the application of metal and polycarbonate composite products.
- the research on material bonding at home and abroad mainly focuses on three aspects, one is to increase mutual adhesion by surface treatment of the material or metal to be bonded; the other is to increase the adhesion between plastic and steel plate by adding an intermediate adhesive layer; The third is to improve the adhesion by adding active substances to modify the material body.
- the present invention unexpectedly finds that by controlling the acid value of the polycarbonate composition within a specific range, the bonding force between the polycarbonate composition and the metal interface can be significantly improved, and it has better heat resistance effect.
- the primary purpose of the present invention is to provide a polycarbonate composition with high bonding force with the metal interface and good heat resistance.
- Another object of the present invention is to provide a method for preparing the above-mentioned polycarbonate composition.
- a polycarbonate composition in parts by weight, comprising the following components:
- High surface energy additives 1 to 10 parts.
- the present invention finds through research that controlling the acid value of the polycarbonate composition within the range of 0.18% to 0.9% can increase the surface tension of the polycarbonate material, thereby improving its compatibility with metal substances, thus significantly improving the The adhesion between the polycarbonate composition and the metal interface has good heat resistance. If the acid value of the polycarbonate composition is low, the surface tension is low, and the bonding performance with the metal interface is poor; if the acid value of the polycarbonate composition is high, the surface tension decreases due to cross-linking or excessive reaction. On the contrary, it is not conducive to bonding, and an excessively high acid value will lead to a decrease in heat resistance.
- the acid value of the polycarbonate composition is 0.4% to 0.75%. The acid number is determined according to the ASTM 974 method.
- the invention controls the acid value of the polycarbonate composition by adding a specific type of high surface energy auxiliary agent and simultaneously controlling the addition amount of the high surface energy auxiliary agent, so that the acid value of the polycarbonate composition is controlled at 0.18% to 0.9% Within the range, the obtained polycarbonate composition has high interface adhesion force with metal and good heat resistance.
- the high surface energy auxiliary agent is selected from one or more mixtures of unsaturated polymers containing oxidized polyethylene, maleic anhydride polymer or acrylic copolymer structure; One or several mixtures of lyric anhydride grafted PS, maleic anhydride grafted PP, maleic anhydride grafted PE, maleic anhydride grafted ABS, ethylene-methyl acrylate copolymer, and ethylene-butyl acrylate copolymer .
- Described polycarbonate is selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate, siloxane copolycarbonate one or a mixture of several , preferably an aromatic polycarbonate with a viscosity-average molecular weight of 13,000-40,000; wherein, the viscosity-average molecular weight is calculated by using dichloromethane as a solvent and the solution viscosity at a test temperature of 25°C. When the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained, and an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000 is more preferable.
- the polycarbonate of the present invention can be prepared by a phosgene method or a transesterification method, and can also be obtained by a commercially available method.
- the polycarbonate composition of the present invention also includes 0-30 parts of reinforcing fillers and 0-20 parts of other auxiliary agents.
- the reinforcing filler is selected from one or more of glass fiber, talc, wollastonite, kaolin, and silica fume.
- the other auxiliary agents are selected from one or more of stabilizers, flame retardants, anti-drip agents, lubricants, mold release agents, plasticizers, and colorants.
- Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylphenylphosphonic acid esters, trimethyl phosphate, etc., pentaerythritol diphosphate (such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate), organic phosphites, alkylated monohydric phenols or Polyphenols, alkylation products of polyphenols and dienes, butylation products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, One or more combinations of alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones.
- organic phosphites such
- Suitable flame retardants are selected from halogen-based flame retardants or halogen-free flame retardants; the halogen-based flame retardants are selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A epoxy resin, Brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromodiphenyl, brominated polycarbonate, perbromotricyclopentadecane or One or more of brominated aromatic cross-linked polymers, preferably brominated polystyrene; the halogen-free flame retardant is selected from nitrogen-containing flame retardants, phosphorus-containing flame retardants or nitrogen- and phosphorus-containing flame retardants; One or more of the fuels.
- Suitable anti-drip agents are fluorinated polyolefins, such as polytetrafluoroethylene.
- the lubricant is one or a mixture of two or more of ethylenebisstearamide EBS, erucamide, zinc stearate, silicone oil, and PETS.
- Suitable release agents include metal stearate, alkyl stearate, pentaerythritol stearate, paraffin wax, montan wax, and the like.
- Suitable plasticizers are phthalates.
- Suitable colorants include various pigments, dyes, such as carbon black, and the like.
- the present invention also provides the above-mentioned preparation method of the polycarbonate composition, which includes the following steps: according to the proportioning, mixing the components uniformly in a high-speed mixer, and the rotation speed of the high-speed mixer is 450 rpm to 500 rpm/min. minutes, added to a twin-screw extruder, melted and mixed at a temperature of 240° C. to 260° C., and then pelletized, cooled, and dried to obtain a polycarbonate composition.
- the present invention also provides the application of the above-mentioned polycarbonate composition in a mobile phone or a TV set.
- the present invention has the following beneficial effects:
- the invention unexpectedly finds that the acid value of the polycarbonate composition is controlled within the range of 0.18% to 0.9%, which can significantly improve the adhesion between the polycarbonate composition and the metal interface, and has better heat resistance.
- the effect further broadens the application of metal and polycarbonate composite products, especially for mobile phones and TV materials.
- Polycarbonate PC Aromatic polycarbonate, PC 1300 10NP, LG Chemical, viscosity average molecular weight 25000;
- Fiberglass PPG Industries
- High surface energy additive 1 maleic anhydride grafted PS, HW-320, the manufacturer is HUAWEN;
- High surface energy additive 2 maleic anhydride grafted PS, SMA 1000, the manufacturer is CRY VALLRY;
- High surface energy additive 3 oxidized polyethylene wax, W140, manufacturer CRY VALLRY;
- High surface energy additive 4 ethylene-methyl acrylate copolymer, 4170, manufacturer dupont.
- Test method of acid value measure according to ASTM 974 method
- Judgment standard coating a 1cm*1cm area, if it does not shrink within 3 seconds, it is judged as the surface tension of this level. If it shrinks within 3 seconds, the next level of coating is used. The surface tension of the grade is determined after three consecutive measurements are passed.
- Table 2 Concrete proportioning (by weight) and performance test result of each component in each embodiment and comparative example
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种聚碳酸酯组合物及其制备方法和应用，包括组分：聚碳酸酯62份～94份；高表面能助剂1份～10份。本发明经研究意外的发现，将聚碳酸酯组合物的酸值控制在0.18％～0.9％范围内，可以明显提高聚碳酸酯组合物与金属界面的粘结力，且具有较好的耐热效果，进一步拓宽了金属与聚碳酸酯复合产品的应用，特别适用于手机和电视机材料。
Description
本发明涉及工程塑料技术领域，具体涉及一种聚碳酸酯组合物及其制备方法和应用。
聚碳酸酯(PC)是性能优异的工程塑料，具有良好的综合性能，机械强度高、耐冲击韧性好、尺寸稳定、耐热较好、电绝缘性好，在家电、数码产品、IT产品等等领域具有广泛的应用。随着电视机轻薄化和美学要求提升，相应的塑料材料不仅要具备良好的力学性能、更高耐热性和流动性，还要求具有与金属良好的粘结性能，以满足大尺寸无边框电视需求。但是聚碳酸酯材料表面没有活性基团，表面能低，与金属物质相容性差，且与金属线性膨胀系数存在较大差异，难以润湿，因此两者界面相互作用弱，导致附着或粘接力差，随着使用时间的累积，塑料与金属间由于冷热收缩不均而不断积累起来的应力，很容易脱粘，限制了金属和聚碳酸酯复合产品的应用。
如何提高金属与塑料界面间作用力，以及如何持久保持相互作用力是关键问题。国内外对材料粘接的研究主要集中三个方面，一是通过对被粘接材料或金属的表面处理增加彼此粘接性；二是利用增加中间粘合层提高塑料与钢板的粘附性；三是通过添加活性物质对材料本体改性提高粘接性。
本发明经研究意外的发现，将聚碳酸酯组合物的酸值控制在特定范围内，可以明显提高聚碳酸酯组合物与金属界面的粘结力，且具有较好的耐热效果。
发明内容
为了克服上述现有技术存在的不足，本发明的首要目的是提供一种聚碳酸酯组合物，与金属界面粘结力高，且耐热性能好。
本发明的另一目的是提供上述聚碳酸酯组合物的制备方法。
本发明是通过以下技术方案实现的：
一种聚碳酸酯组合物，按重量份数计，包括以下组分：
聚碳酸酯 62份～94份；
高表面能助剂 1份～10份。
本发明通过研究发现，将聚碳酸酯组合物的酸值控制在0.18％～0.9％范围内，可以提高聚碳酸酯材料的表面张力，进而提高其与金属物质的相容性，因此能明显提高聚碳酸酯组合物与金属界面的粘结力，且具有较好的耐热效果。若聚碳酸酯组合物的酸值较低，则表面张 力低，与金属界面的粘结性能差；若聚碳酸酯组合物的酸值较高，则由于交联或过量反应导致表面张力下降，反而不利于粘接，且过高的酸值会导致耐热性能下降。优选的，所述聚碳酸酯组合物的酸值为0.4％～0.75％。所述酸值根据ASTM 974方法测定。
本发明通过加入特定种类的高表面能助剂，同时控制高表面能助剂的加入量来控制聚碳酸酯组合物的酸值，使聚碳酸酯组合物的酸值控制在0.18％～0.9％范围内，从而得到的聚碳酸酯组合物与金属界面粘结力高，且耐热性能好。
优选的，所述高表面能助剂选自含有氧化聚乙烯、马来酸酐聚合物或丙烯酸共聚物结构的不饱和聚合物中的一种或几种混合；具体选自氧化聚乙烯蜡、马来酸酐接枝PS、马来酸酐接枝PP、马来酸酐接枝PE、马来酸酐接枝ABS、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物中的一种或几种混合。
所述的聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或几种的混合，优选为粘均分子量13000～40000的芳香族聚碳酸酯；其中，粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。当粘均分子量在上述范围内，机械强度良好并且能保持优异的成型性，更优选为粘均分子量16000～28000的芳香族聚碳酸酯。
本发明所述的聚碳酸酯可以采用光气法或酯交换法制备得到，也可以通过市购方式获得。
根据实际性能需要，本发明所述的聚碳酸酯组合物还包括0～30份的增强填料、0～20份的其它助剂。
所述增强填料选自玻璃纤维、滑石粉、硅灰石、高岭土、硅粉中的一种或几种。
所述其它助剂选自稳定剂、阻燃剂、抗滴落剂、润滑剂、脱模剂、增塑剂、着色剂中的一种或几种。
合适的稳定剂包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等，季戊四醇双磷酸酯(如双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)，有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类，苯并三唑类，二苯甲酮类的一种或者多种组合。
合适的阻燃剂选自卤系阻燃剂或无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合 物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种。
合适的抗滴落剂为氟化聚烯烃，如聚四氟乙烯。
所述润滑剂为乙撑双硬脂酰胺EBS、芥酸酰胺、硬脂酸锌、硅油、PETS中的一种或者两种及以上的混合物。
合适的脱模剂包括硬脂酸金属盐类，硬脂酸烷基酯类，硬脂酸季戊四醇酯类，石蜡，褐煤蜡等。
合适的增塑剂为邻苯二甲酸酯。
合适的着色剂包括各种颜料、染料，如炭黑等。
本发明还提供了上述的聚碳酸酯组合物的制备方法，包括以下步骤：按照配比，将各组分在高混机中混合均匀，高混机的转速为450转/分钟～500转/分钟，加入到双螺杆挤出机中，在240℃～260℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物。
本发明还提供了上述聚碳酸酯组合物在手机或电视机中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明经研究意外的发现，将聚碳酸酯组合物的酸值控制在0.18％～0.9％范围内，可以明显提高聚碳酸酯组合物与金属界面的粘结力，且具有较好的耐热效果，进一步拓宽了金属与聚碳酸酯复合产品的应用，特别适用于手机和电视机材料。
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
现对实施例及对比例所用的原材料做如下说明，但不限于这些材料：
聚碳酸酯PC：芳香族聚碳酸酯，PC 1300 10NP，LG化学，粘均分子量25000；
玻璃纤维：PPG工业公司；
高表面能助剂1：马来酸酐接枝PS，HW-320，厂家为HUAWEN；
高表面能助剂2：马来酸酐接枝PS，SMA 1000，厂家为CRY VALLRY；
高表面能助剂3：氧化聚乙烯蜡，W140，厂家CRY VALLRY；
高表面能助剂4：乙烯-丙烯酸甲酯共聚物，4170，厂家dupont。
各性能的测试标准或方法：
(1)酸值的测试方法：根据ASTM 974方法测定；
(2)表面张力的测定方法：
按照表1比例配制各级别的溶液：量取一定体积的无水乙醇置于100mL容量瓶中，用纯水定容至100mL；测试表面张力。
判定标准：涂覆1cm*1cm区域，3秒内不收缩则判定为该级别的表面张力，如果3秒内收缩，则采用下一级别涂覆。连续测三次都通过则确定级别表面张力。
表1：
(3)耐热参数K的测试方法：在90℃测试拉伸强度记为δ，23℃的拉伸强度记为δ
0，耐热参数K，K＝δ/δ
0；K大于0.5判定为OK。
实施例和对比例聚碳酸酯组合物的制备：
按照表2配比，将各组分在高混机中混合均匀，高混机的转速为450转/分钟～500转/分钟，加入到双螺杆挤出机中，在240℃～260℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物。
表2：各实施例及对比例中各组份的具体配比(按重量份计)和性能测试结果
由实施例和对比例的比较可以看出：将聚碳酸酯组合物中的酸值控制在0.18％～0.9％的范围内，可以提高聚碳酸酯组合物的表面张力，从而使聚碳酸酯组合物与金属界面具有较强的粘结力，且具有较好的耐热效果。
对比例1中，当聚碳酸酯组合物中的酸值为0时，聚碳酸酯的表面张力低，耐热性能差。
对比例2中，当聚碳酸酯组合物中的酸值过高时，由于交联或过量反应导致表面张力下降，不利于与金属粘接，且过高的酸值会导致耐热性能下降。
Claims (9)
- 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组分：聚碳酸酯 62份～94份；高表面能助剂 1份～10份。
- 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯组合物中酸值为0.18％～0.9％；优选为0.4％～0.75％；所述酸值根据ASTM 974方法测定。
- 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述高表面能助剂选自含有氧化聚乙烯、马来酸酐聚合物或丙烯酸共聚物结构的不饱和聚合物中的一种或几种混合。
- 根据权利要求3所述的聚碳酸酯组合物，其特征在于，所述高表面能助剂选自氧化聚乙烯蜡、马来酸酐接枝PS、马来酸酐接枝PP、马来酸酐接枝PE、马来酸酐接枝ABS、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物中的一种或几种混合。
- 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述的聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或几种的混合，优选为粘均分子量13000～40000的芳香族聚碳酸酯，更优选为粘均分子量16000～28000的芳香族聚碳酸酯。
- 根据权利要求1～5任一项所述的聚碳酸酯组合物，其特征在于，按重量份计，所述聚碳酸酯组合物还包括0～30份的增强填料、0～20份的其它助剂。
- 根据权利要求6所述的聚碳酸酯组合物，其特征在于，所述增强填料选自玻璃纤维、滑石粉、硅灰石、高岭土、硅粉中的一种或几种；所述其它助剂选自稳定剂、阻燃剂、抗滴落剂、润滑剂、脱模剂、增塑剂、着色剂的一种或几种。
- 根据权利要求1～7任一项所述的聚碳酸酯组合物的制备方法，其特征在于，包括以下步骤：按照配比，将各组分在高混机中混合均匀，高混机的转速为450转/分钟～500转/分钟，加入到双螺杆挤出机中，在240℃～260℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物。
- 根据权利要求1～7任一项所述的聚碳酸酯组合物在手机或电视机中的应用。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2710276B2 (ja) * | 1995-10-30 | 1998-02-10 | 工業技術院長 | 高分子成形材料 |
| KR101154388B1 (ko) * | 2009-12-07 | 2012-06-15 | 금호석유화학 주식회사 | 저온충격성이 우수한 내열 내후성 열가소성 수지 조성물 |
| CN105153662A (zh) * | 2015-07-23 | 2015-12-16 | 深圳华力兴新材料股份有限公司 | 一种玻璃纤维增强的聚碳酸酯复合材料及其制备方法 |
| CN110804295A (zh) * | 2019-10-15 | 2020-02-18 | 金发科技股份有限公司 | 一种聚碳酸酯组合物及其制备方法与应用 |
| CN111073244A (zh) * | 2019-12-03 | 2020-04-28 | 天津金发新材料有限公司 | 一种聚碳酸酯组合物及其制备方法 |
| CN111286181A (zh) * | 2019-12-27 | 2020-06-16 | 重庆会通科技有限公司 | 一种增强pc/abs合金材料及其制备方法 |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2710276B2 (ja) * | 1995-10-30 | 1998-02-10 | 工業技術院長 | 高分子成形材料 |
| KR101154388B1 (ko) * | 2009-12-07 | 2012-06-15 | 금호석유화학 주식회사 | 저온충격성이 우수한 내열 내후성 열가소성 수지 조성물 |
| CN105153662A (zh) * | 2015-07-23 | 2015-12-16 | 深圳华力兴新材料股份有限公司 | 一种玻璃纤维增强的聚碳酸酯复合材料及其制备方法 |
| CN110804295A (zh) * | 2019-10-15 | 2020-02-18 | 金发科技股份有限公司 | 一种聚碳酸酯组合物及其制备方法与应用 |
| CN111073244A (zh) * | 2019-12-03 | 2020-04-28 | 天津金发新材料有限公司 | 一种聚碳酸酯组合物及其制备方法 |
| CN111286181A (zh) * | 2019-12-27 | 2020-06-16 | 重庆会通科技有限公司 | 一种增强pc/abs合金材料及其制备方法 |
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