WO2022057205A1 - Polycarbonate composition, preparation method therefor, and use thereof - Google Patents
Polycarbonate composition, preparation method therefor, and use thereof Download PDFInfo
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- WO2022057205A1 WO2022057205A1 PCT/CN2021/077426 CN2021077426W WO2022057205A1 WO 2022057205 A1 WO2022057205 A1 WO 2022057205A1 CN 2021077426 W CN2021077426 W CN 2021077426W WO 2022057205 A1 WO2022057205 A1 WO 2022057205A1
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- polycarbonate
- polycarbonate composition
- composition according
- parts
- epoxy equivalent
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 69
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000012763 reinforcing filler Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920000578 graft copolymer Polymers 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
- 229910021487 silica fume Inorganic materials 0.000 claims description 2
- 239000004094 surface-active agent Substances 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
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 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
- 150000002739 metals Chemical class 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
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000000126 substance Substances 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
- 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
- 239000004793 Polystyrene Substances 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
- 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
- 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
- 230000007423 decrease 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 239000004745 nonwoven fabric Substances 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
- 238000005453 pelletization 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
- 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
- 229920002545 silicone oil Polymers 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
- 230000003313 weakening effect Effects 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
- 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) has good comprehensive properties, high mechanical strength, good impact toughness, dimensional stability, good heat resistance, and good electrical insulation. It is widely used in home appliances, digital products, IT products and other fields. As TV sets become thinner and more aesthetically pleasing, the corresponding plastic materials must not only have good mechanical properties, but also have high heat resistance and fluidity, and also require good bonding properties with metals to meet the needs of large-scale non-woven fabrics. Bezel TV needs.
- 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, making it 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.
- the first method is to increase mutual adhesion by surface treatment of the material or metal to be bonded;
- the second is to increase the adhesion between plastic and steel plate by adding an intermediate adhesive layer.
- Adhesion; the last method is to modify the bulk of the material by adding active substances to improve the adhesion.
- the primary object of the present invention is to provide a polycarbonate composition with high interfacial adhesion between the composition and metal and good heat resistance.
- Another object of the present invention is to provide a method for preparing the above polycarbonate composition.
- a polycarbonate composition by weight, comprising the following components:
- controlling the epoxy equivalent in the polycarbonate composition within the range of 5-800 g/eq can improve the surface tension of the polycarbonate material, thereby improving its compatibility with metal substances, so it can significantly improve the surface tension of the polycarbonate material. Improve the adhesion between the polycarbonate composition and the metal interface, and have better heat resistance effect. If the epoxy equivalent in the polycarbonate composition is low, the effect of improving the adhesion between the polycarbonate composition and the metal interface will not be achieved. If the epoxy equivalent in the polycarbonate composition is high, the material will be reduced.
- the epoxy equivalent in the polycarbonate composition is preferably 50-400 g/eq, more preferably 100-280 g/eq, and the epoxy equivalent is based on GB /T 4612-2008 standard test.
- the epoxy equivalent refers to the mass of the epoxy resin containing 1 mol of epoxy groups.
- the polar auxiliary agent is a mixture of one or more of epoxy group-containing surfactants, antistatic agents or compatibilizers, and is specifically selected from propylene oxide copolymers, polyethylene oxides , GMA graft polymer, polyoxyethylene-propylene oxide copolymer or a mixture of several.
- the polycarbonate is selected from one or a mixture of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate, and siloxane copolycarbonate.
- the polycarbonate of the present invention can be prepared by a phosgene method or a transesterification method, or can be obtained by a commercially available method.
- the polycarbonate composition of the present invention also includes 0-30 parts by weight of reinforcing fillers and 0-20 parts by weight 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, fillers, 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 preferably fluorinated polyolefins, such as polytetrafluoroethylene.
- Suitable plasticizers are phthalates.
- 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 colorants include various pigments, dyes such as carbon black and the like.
- the present invention also provides a preparation method of the above-mentioned polycarbonate composition, comprising the following steps:
- the rotation speed of the high-speed mixer is 450 rpm to 500 rpm.
- 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 present invention unexpectedly finds that the epoxy equivalent in the polycarbonate composition is controlled within the range of 5-800 g/eq, which can significantly improve the adhesion between the polycarbonate composition and the metal interface, and has better resistance to The thermal effect further broadens the application of metal and polycarbonate composite products, especially for mobile phones and TV materials.
- Polycarbonate PC Aromatic polycarbonate, PC 1300 10 NP, LG Chem;
- Fiberglass PPG Industries
- Polar additive 1 R-139, the manufacturer is Japan's Mitsui, propylene oxide copolymer
- Polar additive 2 A-316, manufacturer Honeywell, polyethylene oxide
- Lubricant Erucamide, commercially available.
- Measurement method of surface tension use the following ratio to prepare a solution to test the surface tension.
- Level 1 Measure 81mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Level 2 Measure 73.5mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Level 3 Measure 65mL of anhydrous ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Level 4 Measure 57.5mL of absolute ethanol into a 100mL volumetric flask, and dilute to 100mL.
- Level 5 Measure 51.5mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Level 6 Measure 46mL of absolute ethanol into a 100mL volumetric flask and dilute to 100mL.
- Level 7 Take 41mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Level 8 Take 36.5mL of anhydrous ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
- Judgment standard coating a 1cm*1cm area, at 40 °C, 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 energy of the grade is determined by passing the test three times in a row.
- the speed of the high-speed mixer is 450 r/min-500 r/min, add it to a twin-screw extruder, and at a temperature of 240 °C-260 °C
- the polycarbonate composition was obtained by melting and mixing under 100°C, followed by granulation, cooling and drying; the polycarbonate composition was tested, and the data are shown in Table 1.
- the epoxy equivalent in the polycarbonate composition is controlled within the range of 5-800 g/eq, the surface tension of the polycarbonate composition can be increased, so that the polycarbonate composition can be The ester composition and the metal interface have strong adhesion and good heat resistance.
- Comparative Example 1 when the epoxy equivalent in the polycarbonate composition was 0, the surface tension of the polycarbonate composition was low.
- Comparative Example 2 when the epoxy equivalent in the polycarbonate composition is excessive, the surface tension decreases, mainly because the excess epoxy equivalent reacts to lengthen the molecular chain, thereby reducing the polarity of the material and weakening the polar additives to enhance the surface.
- the efficiency of tension in addition the excess epoxy equivalent acts as a plasticizer and reduces the heat resistance parameters of the material.
Abstract
Disclosed are a polycarbonate composition, a preparation method therefor, and the use thereof. The polycarbonate composition contains the following components: 65-85 parts of a polycarbonate and 0.01-5 parts of a polar auxiliary agent. The present invention was unexpectedly discovered through research, such that by controlling the epoxy equivalent in the polycarbonate composition to be within the range of 5-800 g/eq, the binding power between the polycarbonate composition and a metal interface can be significantly improved, and a relatively good heat-resistant effect is achieved, thereby further broadening the applications of metal and polycarbonate composite products. The polycarbonate composition is particularly suitable for materials for mobile phones and televisions.
Description
本发明涉及工程塑料技术领域，特别涉及一种聚碳酸酯组合物及其制备方法和应用。The invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method and application thereof.
聚碳酸酯(PC)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，更要具备高耐热性和流动性，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。Polycarbonate (PC) has good comprehensive properties, high mechanical strength, good impact toughness, dimensional stability, good heat resistance, and good electrical insulation. It is widely used in home appliances, digital products, IT products and other fields. As TV sets become thinner and more aesthetically pleasing, the corresponding plastic materials must not only have good mechanical properties, but also have high heat resistance and fluidity, and also require good bonding properties with metals to meet the needs of large-scale non-woven fabrics. Bezel TV needs. However, 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, making it 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.
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，第一种方法是通过对被粘接材料或金属的表面处理增加彼此粘接性；其次是利用增加中间粘合层提高塑料与钢板的粘附性；最后一种方法是通过添加活性物质对材料本体改性提高粘接性。How to improve the interaction force between metal and plastic interface and how to maintain the interaction force for a long time are the key issues. The research on material bonding at home and abroad mainly focuses on three aspects. The first method is to increase mutual adhesion by surface treatment of the material or metal to be bonded; the second is to increase the adhesion between plastic and steel plate by adding an intermediate adhesive layer. Adhesion; the last method is to modify the bulk of the material by adding active substances to improve the adhesion.
发明内容SUMMARY OF THE INVENTION
本发明的首要目的在于提供一种聚碳酸酯组合物，该组合物与金属界面粘结力高，且耐热性能好。The primary object of the present invention is to provide a polycarbonate composition with high interfacial adhesion between the composition and metal and good heat resistance.
本发明的再一目的是提供上述聚碳酸酯组合物的制备方法。Another object of the present invention is to provide a method for preparing the above polycarbonate composition.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种聚碳酸酯组合物，按重量份计，包括以下组份：A polycarbonate composition, by weight, comprising the following components:
聚碳酸酯 65份-85份；Polycarbonate 65-85 parts;
极性助剂 0.01-5份。Polar additives 0.01-5 parts.
本发明通过研究发现，将聚碳酸酯组合物中环氧当量控制在5-800g/eq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。若聚碳酸酯组合物中环氧当量较低，则起不到提高聚碳酸酯组合物与金属界面的粘结力的效果，若聚碳酸酯组合物中环氧当量较高，则会降低材料的耐热性能，且影响材料的加工性能，因此，优选的，所述聚碳酸酯组合物中 环氧当量优选为50-400g/eq，更优选为100-280g/eq，环氧当量根据GB/T 4612-2008标准测试。环氧当量是指含有1mol环氧基的环氧树脂的质量。It is found through research in the present invention that controlling the epoxy equivalent in the polycarbonate composition within the range of 5-800 g/eq can improve the surface tension of the polycarbonate material, thereby improving its compatibility with metal substances, so it can significantly improve the surface tension of the polycarbonate material. Improve the adhesion between the polycarbonate composition and the metal interface, and have better heat resistance effect. If the epoxy equivalent in the polycarbonate composition is low, the effect of improving the adhesion between the polycarbonate composition and the metal interface will not be achieved. If the epoxy equivalent in the polycarbonate composition is high, the material will be reduced. Therefore, preferably, the epoxy equivalent in the polycarbonate composition is preferably 50-400 g/eq, more preferably 100-280 g/eq, and the epoxy equivalent is based on GB /T 4612-2008 standard test. The epoxy equivalent refers to the mass of the epoxy resin containing 1 mol of epoxy groups.
优选的，所述极性助剂为含有环氧基团的表面活性剂、抗静电剂或相容剂中的一种或几种的混合，具体选自环氧丙烷共聚合物、聚氧化乙烯、GMA接枝聚合物、聚氧化乙烯-环氧丙烷共聚合物中的一种或几种的混合。Preferably, the polar auxiliary agent is a mixture of one or more of epoxy group-containing surfactants, antistatic agents or compatibilizers, and is specifically selected from propylene oxide copolymers, polyethylene oxides , GMA graft polymer, polyoxyethylene-propylene oxide copolymer or a mixture of several.
所述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。The polycarbonate is selected from one or a mixture of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate, and siloxane copolycarbonate.
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，也可以通过是市购方式获得。The polycarbonate of the present invention can be prepared by a phosgene method or a transesterification method, or can be obtained by a commercially available method.
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重量份的增强填料、0-20重量份的其它助剂。According to actual performance requirements, the polycarbonate composition of the present invention also includes 0-30 parts by weight of reinforcing fillers and 0-20 parts by weight of other auxiliary agents.
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。The reinforcing filler is selected from one or more of glass fiber, talc, wollastonite, kaolin, and silica fume.
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、填料、着色剂的一种或几种。The other auxiliary agents are selected from one or more of stabilizers, flame retardants, anti-drip agents, lubricants, mold release agents, plasticizers, fillers, and colorants.
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。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.
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。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.
合适的抗滴落剂为优选为氟化聚烯烃，如聚四氟乙烯。Suitable anti-drip agents are preferably fluorinated polyolefins, such as polytetrafluoroethylene.
合适的增塑剂为邻苯二甲酸酯。Suitable plasticizers are phthalates.
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。The lubricant is one or a mixture of two or more of ethylenebisstearamide EBS, erucamide, zinc stearate, silicone oil, and PETS.
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 煤蜡等等。Suitable release agents include metal stearate, alkyl stearate, pentaerythritol stearate, paraffin wax, montan wax and the like.
合适的着色剂包括各种颜料，染料，如炭黑等。Suitable colorants include various pigments, dyes such as carbon black and the like.
本发明还提供了上述的聚碳酸酯组合物的制备方法，包括如下步骤：The present invention also provides a preparation method of the above-mentioned polycarbonate composition, comprising the following steps:
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。Mix the components uniformly in a high-speed mixer according to the ratio. The rotation speed of the high-speed mixer is 450 rpm to 500 rpm. Add it to a twin-screw extruder and carry out the process at a temperature of 240°C to 260°C. Melt mixing, followed by pelletizing, cooling, and drying yields the polycarbonate composition.
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。The present invention also provides the application of the above-mentioned polycarbonate composition in a mobile phone or a TV set.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明经研究意外的发现，将聚碳酸酯组合物中环氧当量控制在5-800g/eq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。The present invention unexpectedly finds that the epoxy equivalent in the polycarbonate composition is controlled within the range of 5-800 g/eq, which can significantly improve the adhesion between the polycarbonate composition and the metal interface, and has better resistance to The thermal effect further broadens the application of metal and polycarbonate composite products, especially for mobile phones and TV materials.
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The present invention will be further described below through specific embodiments. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.
聚碳酸酯PC：芳香族聚碳酸酯，PC 1300 10 NP，LG化学；Polycarbonate PC: Aromatic polycarbonate, PC 1300 10 NP, LG Chem;
玻璃纤维：PPG工业公司；Fiberglass: PPG Industries;
极性助剂1：R-139，厂家为日本三井，环氧丙烷共聚合物；Polar additive 1: R-139, the manufacturer is Japan's Mitsui, propylene oxide copolymer;
极性助剂2：A-316，厂家霍尼韦尔，聚氧化乙烯；Polar additive 2: A-316, manufacturer Honeywell, polyethylene oxide;
润滑剂：芥酸酰胺，市购。Lubricant: Erucamide, commercially available.
各性能的测试标准或方法：Test standards or methods for each performance:
环氧当量的测试方法：GB/T 4612-2008标准；Test method for epoxy equivalent: GB/T 4612-2008 standard;
表面张力的测定方法：采用下表比例配制溶液，测试表面张力。Measurement method of surface tension: use the following ratio to prepare a solution to test the surface tension.
具体操作方法：Specific operation method:
级别1量取81mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 1 Measure 81mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
级别2量取73.5mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 2 Measure 73.5mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
级别3量取65mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 3 Measure 65mL of anhydrous ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
级别4量取57.5mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 4 Measure 57.5mL of absolute ethanol into a 100mL volumetric flask, and dilute to 100mL.
级别5量取51.5mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 5 Measure 51.5mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
级别6量取46mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 6 Measure 46mL of absolute ethanol into a 100mL volumetric flask and dilute to 100mL.
级别7量取41mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 7 Take 41mL of absolute ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
级别8量取36.5mL无水乙醇置于100mL容量瓶中，定容至100mL。Level 8 Take 36.5mL of anhydrous ethanol and place it in a 100mL volumetric flask, and dilute to 100mL.
判定标准：涂覆1cm*1cm区域，在40℃下，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能。Judgment standard: coating a 1cm*1cm area, at 40 °C, 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 energy of the grade is determined by passing the test three times in a row.
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δ0，耐热参数K，K＝δ/δ0；K大于0.5判定为OK。Test method for heat resistance parameter K: the tensile strength at 90°C is recorded as δ, the tensile strength at 23°C is recorded as δ0, the heat resistance parameter K, K=δ/δ0; if K is greater than 0.5, it is judged as OK.
实施例1-11及对比例1-2：聚碳酸酯组合物的制备Examples 1-11 and Comparative Examples 1-2: Preparation of Polycarbonate Compositions
按表1的配方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；对聚碳酸酯组合物进行测试，数据见表1。Mix the components uniformly in a high-speed mixer according to the formula in Table 1. The speed of the high-speed mixer is 450 r/min-500 r/min, add it to a twin-screw extruder, and at a temperature of 240 ℃-260 ℃ The polycarbonate composition was obtained by melting and mixing under 100°C, followed by granulation, cooling and drying; the polycarbonate composition was tested, and the data are shown in Table 1.
表1实施例1-11及对比例1-2的具体配比(重量份)及其测试性能结果Table 1 Specific proportions (parts by weight) of Examples 1-11 and Comparative Examples 1-2 and their test performance results
续表1：Continued from Table 1:
从表1的实施例和对比例的比较可以看出：将聚碳酸酯组合物中环氧当量控制在5-800g/eq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环氧当量为0时，聚碳酸酯组合物的表面张力较低。对比例2中，当聚碳酸酯组合物中的环氧当量过量时，表面张力出现下降，主要是由于过量环氧当量反应加长分子链，从而降低材料极性，削弱了极性助剂提升表面张力的效率，此外过量的环氧当量起到增塑的作用使材料耐热参数下降。It can be seen from the comparison between the examples and comparative examples in Table 1: the epoxy equivalent in the polycarbonate composition is controlled within the range of 5-800 g/eq, the surface tension of the polycarbonate composition can be increased, so that the polycarbonate composition can be The ester composition and the metal interface have strong adhesion and good heat resistance. In Comparative Example 1, when the epoxy equivalent in the polycarbonate composition was 0, the surface tension of the polycarbonate composition was low. In Comparative Example 2, when the epoxy equivalent in the polycarbonate composition is excessive, the surface tension decreases, mainly because the excess epoxy equivalent reacts to lengthen the molecular chain, thereby reducing the polarity of the material and weakening the polar additives to enhance the surface. The efficiency of tension, in addition the excess epoxy equivalent acts as a plasticizer and reduces the heat resistance parameters of the material.
Claims (9)
- 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组份：A polycarbonate composition, characterized in that, in parts by weight, comprising the following components:聚碳酸酯 65份-85份；Polycarbonate 65-85 parts;极性助剂 0.01-5份。Polar additives 0.01-5 parts.
- 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环氧当量为5-800g/eq，优选为50-400g/eq，更优选为100-280g/eq，环氧当量根据GB/T 4612-2008标准测试。The polycarbonate composition according to claim 1, wherein the epoxy equivalent in the polycarbonate composition is 5-800 g/eq, preferably 50-400 g/eq, more preferably 100-280 g/eq eq, epoxy equivalent is tested according to GB/T 4612-2008 standard.
- 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述极性助剂为含有环氧基团的表面活性剂、抗静电剂或相容剂中的一种或几种的混合。The polycarbonate composition according to claim 1, wherein the polar auxiliary agent is a mixture of one or more of a surfactant containing an epoxy group, an antistatic agent or a compatibilizer .
- 根据权利要求3所述的聚碳酸酯组合物，其特征在于，所述极性助剂选自环氧丙烷共聚合物、聚氧化乙烯、GMA接枝聚合物、聚氧化乙烯-环氧丙烷共聚合物中一种或几种的混合。The polycarbonate composition according to claim 3, wherein the polar auxiliary agent is selected from the group consisting of propylene oxide copolymer, polyethylene oxide, GMA graft polymer, polyethylene oxide-propylene oxide copolymer A mixture of one or more of the polymers.
- 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。The polycarbonate composition according to claim 1, wherein the polycarbonate is selected from the group consisting of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate , a mixture of one or more of siloxane copolycarbonate.
- 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，所述聚碳酸酯组合物还包括0-30重量份的增强填料、0-20重量份的其它助剂。The polycarbonate composition according to any one of claims 1-5, characterized in that, the polycarbonate composition further comprises 0-30 parts by weight of reinforcing fillers and 0-20 parts by weight of other auxiliary agents.
- 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、填料、着色剂的一种或几种。The polycarbonate composition according to claim 6, wherein the reinforcing filler is selected from one or more of glass fiber, talc, wollastonite, kaolin, and silica fume; the other auxiliary One or more selected from stabilizers, flame retardants, anti-drip agents, lubricants, mold release agents, plasticizers, fillers, and colorants.
- 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，包括如下步骤：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。The method for preparing a polycarbonate composition according to any one of claims 1-7, characterized in that it comprises the steps of: uniformly mixing each component in a high-mixer according to the proportioning, and the high-mixer rotating speed is 450 rev/min-500 rev/min, add to a twin-screw extruder, melt and mix at a temperature of 240°C-260°C, then pelletize, cool, and dry to obtain a polycarbonate composition.
- 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。Application of the polycarbonate composition according to any one of claims 1-7 in a mobile phone or a TV set.
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| CN101787188A (en) * | 2009-02-06 | 2010-07-28 | 深圳市科聚新材料有限公司 | Flame-retardant PC/HIPS composite material and preparation method thereof |
| CN104761878A (en) * | 2015-04-08 | 2015-07-08 | 中国科学院化学研究所 | Polycarbonate composite material and preparation method thereof |
| TWI706990B (en) * | 2016-02-18 | 2020-10-11 | 南韓商Ｌｇ化學股份有限公司 | Polycarbonate resin composition and optical molded article using the same |
| CN106674963A (en) * | 2016-12-26 | 2017-05-17 | 上海普利特化工新材料有限公司 | Microporous foamed PC (polycarbonate)-ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN112226059A (en) * | 2020-09-18 | 2021-01-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
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| CN112226059A (en) | 2021-01-15 |
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