CN115449207A - Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof - Google Patents
Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof Download PDFInfo
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- CN115449207A CN115449207A CN202211154167.4A CN202211154167A CN115449207A CN 115449207 A CN115449207 A CN 115449207A CN 202211154167 A CN202211154167 A CN 202211154167A CN 115449207 A CN115449207 A CN 115449207A
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- free flame
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 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 49
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004417 polycarbonate Substances 0.000 claims abstract description 85
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 66
- 230000032683 aging Effects 0.000 claims abstract description 56
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000003365 glass fiber Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 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 claims description 11
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 11
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- -1 phosphonic acid diphenylsulfone ester Chemical class 0.000 claims description 10
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 8
- 229920002050 silicone resin Polymers 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 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 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
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- 230000003712 anti-aging effect Effects 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 2
- 239000003607 modifier Substances 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 35
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
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- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
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- 238000012216 screening Methods 0.000 description 2
- RFRBCSAZWNQSRM-UHFFFAOYSA-N CC1=CCC(C=C1)(C)P(=O)(O)O Chemical compound CC1=CCC(C=C1)(C)P(=O)(O)O RFRBCSAZWNQSRM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
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- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
- C08J2485/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant reinforced PC composite material and a preparation method and application thereof. The invention provides a halogen-free flame-retardant reinforced PC composite material, which comprises the following components: polycarbonate, glass fiber, halogen-free flame retardant, CTI improver and aging resistant agent; wherein: the mass A ratio of the halogen-free flame retardant, the CTI improver and the aging resistant agent is (5-10): (6-12): (8-12). The invention also provides a preparation method of the PC composite material with high CTI, aging resistance, halogen-free flame retardance and reinforcement for the connector. The PC composite material obtained by the invention has excellent comprehensive performance, the CTI value is improved to 400V, the aging resistance is strong, and the flame retardant property reaches V-0 level of UL 94.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for a connector and a preparation method thereof.
Background
The connector is used as an indispensable part in the electronic field and is widely applied to the fields of aviation, aerospace, rail transit, industrial automation and the like. In order for the contacts in the connector to maintain proper alignment, good insulation between the contacts and the housing, the material used for the connector must have good electrical, aging, flame retardant, and mechanical properties.
Polycarbonate (PC) is a thermoplastic engineering plastic with excellent comprehensive performance, has the characteristics of excellent electrical insulation, dimensional stability, creep resistance, no toxicity and the like, and is widely used in the fields of electronic and electric appliances, packaging, medical instruments, transportation and the like.
However, PC is generally susceptible to aging, relatively sensitive to notch, low in flame retardancy, low in Comparative Tracking Index (CTI), and the like, and thus has an adverse effect on the scale application in devices and apparatuses such as connectors. The concrete expression is as follows: on one hand, when the surface of a PC (polycarbonate) material is wet and dirty, the surface of the material is locally carbonized under the action of an electric field, so that the Comparative Tracking Index (CTI) value is not high; on the other hand, the organic small molecule assistant in the PC material is also easy to be separated out from the surface of the material, so that a large amount of conductive ions and carbon particle deposits are generated, and the CTI value of the material is also reduced. This is one of the main factors that limit its scale application in devices and apparatuses such as connectors.
CN114149673A discloses a high CTI halogen-free flame retardant polycarbonate material, which has a CTI value of more than 420V by adding a specific modification reinforcing agent, and has good flame retardant effect and good mechanical property. However, in the practical application process, the material is easy to age due to the action of the external environment, the performance of the material is reduced, and the service life of the material is shortened. Therefore, how to ensure the high-efficiency flame retardant property of the PC material and improve the CTI value and the aging resistance of the PC material are difficult points for improving the performance of the existing PC material.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel halogen-free flame-retardant reinforced PC composite material, and a preparation method and application thereof. The material not only has a high CTI value, but also has excellent aging resistance and flame retardance.
In a first aspect, the present invention provides a halogen-free flame retardant reinforced PC composite material, comprising: polycarbonate, glass fiber, halogen-free flame retardant, CTI improver and aging resistant agent; wherein:
the halogen-free flame retardant is any one or more of bisphenol A-bis (diphenyl phosphate) (BDP), resorcinol-bis (diphenyl phosphate) (RDP), a silicone flame retardant, potassium diphenyl Sulfone Sulfonate (SSK) and polyphenyl phosphonic acid diphenyl sulfone ester (PSPPP);
the CTI improver is any one or more of magnesium oxide, calcium oxide and barium oxide;
the aging resistant agent is any one or more of 2-hydroxy-4-octoxy benzophenone, 2-hydroxy-4-methoxy benzophenone or 2,4-dihydroxy benzophenone;
the mass ratio of the halogen-free flame retardant, the CTI improver and the aging resistant agent is (5-10): (6-12): (8-12).
As known to those skilled in the art, the performance of the PC composite material can be improved by selecting an additive with a high degree of matching through adjusting the types of the additives in the halogen-free flame retardant reinforced PC composite material. However, it is also known based on the common general knowledge that the prior art discloses a large amount of functional additives which can be used for PC composite materials, and the specific selection types of the functional additives are numerous, and unpredictable synergistic relationship or antagonistic relationship exists among the additives, for example, the additives with obvious improvement effect have poor compatibility with the system, and the additives with good compatibility have insufficient improvement effect, so that a large amount of time and energy are needed for technicians to prepare the additives in the PC composite materials, and the effect is often difficult to predict.
According to the PC composite material provided by the invention, the specific halogen-free flame retardant, the CTI improver and the anti-aging agent are added, and the proportion relation is optimized, so that the three are better matched with a system formed by polycarbonate and glass fiber, the flame retardant property of the PC material is improved, the non-halogenation of the material for the connector is realized, the CTI value and the aging resistance of the PC material are synergistically improved, and the large-scale application of the PC composite material in devices and equipment such as the connector is promoted.
As one of the specific embodiments of the present invention, the halogen-free flame retardant is bisphenol a-bis (diphenyl phosphate), the CTI improver is magnesium oxide, and the aging-resistant agent is 2-hydroxy-4-octyloxybenzophenone;
or the halogen-free flame retardant is potassium diphenylsulfone sulfonate, the CTI improver is calcium oxide, and the aging-resistant agent is 2-hydroxy-4-methoxybenzophenone;
or the halogen-free flame retardant is a silicone resin flame retardant, the CTI improver is magnesium oxide, and the aging-resistant agent is 2,4-dihydroxy benzophenone;
or the halogen-free flame retardant is resorcinol-bis (diphenyl phosphate), the CTI improver is barium oxide, and the aging-resistant agent is 2,4-dihydroxy benzophenone;
or the halogen-free flame retardant is polyphenyl phosphonic acid diphenyl sulfone ester, the CTI improver is barium oxide, and the aging-resistant agent is 2-hydroxy-4-octyloxy benzophenone;
or the halogen-free flame retardant consists of bisphenol A-bis (diphenyl phosphate) and a silicone resin flame retardant in a mass ratio of 1:1, the CTI improver is calcium oxide, and the aging resistant agent is 2-hydroxy-4-methoxybenzophenone.
Further, the halogen-free flame-retardant reinforced PC composite material also comprises an antioxidant; the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant; wherein the hindered phenol antioxidant is specifically antioxidant 1010, and the phosphite antioxidant is specifically antioxidant 168. The mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 2:1. The antioxidant selected by the invention not only can improve the oxidation resistance of the composite material, but also can generate synergistic effect with the aging resistant agent, thereby further improving the aging resistance of the composite material.
Further, the halogen-free flame-retardant reinforced PC composite material also comprises a lubricant; the lubricant is any one or more of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, natural paraffin or polyethylene wax.
As one of the specific embodiments of the invention, the halogen-free flame-retardant reinforced PC composite material comprises the following components in parts by weight: 45-70 parts of PC resin, 10-20 parts of glass fiber, 5-10 parts of halogen-free flame retardant, 6-12 parts of CTI improver, 8-12 parts of anti-aging agent, 0.1-0.5 part of antioxidant and 0.1-0.5% of lubricant.
In a second aspect, the invention further provides a preparation method of the halogen-free flame-retardant reinforced PC composite material, which comprises the following steps: mixing the components in proportion, mixing uniformly and granulating.
Wherein the PC resin, the halogen-free flame retardant and the glass fiber are dried before being mixed; the drying conditions of the PC resin are as follows: drying for 3-5h at 110-130 ℃; the drying conditions of the halogen-free flame retardant and the glass fiber are as follows: drying for 30-60 min at 70-85 deg.c.
Wherein the granulation is obtained by a twin-screw extruder; the extrusion temperature is 240-290 ℃, and the screw rotation speed is 300-500 rpm.
In a third aspect, the invention also provides application of the halogen-free flame-retardant reinforced PC composite material in the fields of aviation, aerospace, rail transit, industrial automation and the like.
In a fourth aspect, the invention further provides a connector, which adopts the halogen-free flame-retardant reinforced PC composite material.
The beneficial effects of the invention at least comprise:
according to the invention, the PC material is synergistically improved by screening the specific functional auxiliary agent and optimizing the addition proportion, so that the PC material has a higher CTI value, good flame retardance, aging resistance and excellent mechanical properties. In addition, the invention adopts the existing double-screw extruder to extrude and granulate, and the method has simple operation and low cost and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of a preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the prior art, the electrical property, the aging resistance, the flame retardant property, the processing property and the like of the conventional PC material can not meet the requirements of devices or equipment such as a connector and the like on insulating materials.
Aiming at the problems in the prior art, the invention improves the PC material by adding a plurality of functional components in a synergistic manner, provides a high CTI, aging-resistant and halogen-free flame-retardant reinforced PC composite material for a connector and a preparation method thereof, and the invention is described in detail by combining the attached drawings.
As shown in fig. 1, the preparation method of the high CTI, aging-resistant, halogen-free, flame-retardant and reinforced PC composite material for a connector provided by the embodiment of the invention comprises the following steps:
s101, preparing materials: drying the PC resin for 3-5h at the temperature of 110-130 ℃, and drying the halogen-free flame retardant and the glass fiber for 30-60 min at the temperature of 70-85 ℃ for later use;
s102, taking materials: weighing the following raw materials in percentage by weight: 45-70% of PC resin, 10-20% of glass fiber, 5-10% of halogen-free flame retardant, 6-12% of CTI improver, 8-12% of age resister, 0.1-0.5% of antioxidant and 0.1-0.5% of lubricant;
s103, mixing: adding the weighed components into a high-speed mixer, and stirring for 10-30 min to uniformly mix the components;
s104, extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation to obtain a finished product.
The halogen-free flame retardant in step S101 provided in the embodiment of the present invention is any one or more of bisphenol a-bis (diphenyl phosphate) (BDP), resorcinol-bis (diphenyl phosphate) (RDP), silicone flame retardant, potassium diphenyl Sulfone Sulfonate (SSK), and diphenyl sulfone polyphenyl phosphonate (PSPPP).
The CTI improver in step S102 provided in the embodiment of the present invention is any one or a mixture of magnesium oxide, calcium oxide, and barium oxide.
The aging resistant agent in step S102 provided in the embodiment of the present invention is any one of 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone.
The antioxidant in step S102 provided in the embodiment of the present invention is a complex of a hindered phenol antioxidant and a phosphite antioxidant.
The lubricant in step S102 provided by the embodiment of the present invention is any one or a mixture of more of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, natural paraffin, and polyethylene wax.
The extrusion temperature in step S104 provided by the embodiment of the invention is 240-290 ℃, and the screw rotation speed is 300-500 rpm.
Example 1
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 120 deg.C for 4h, and drying bisphenol A-bis (diphenyl phosphate) (BDP) and glass fiber at 70 deg.C for 60min;
(2) Taking materials: weighing the following raw materials in percentage by weight: 70% of PC resin, 10% of glass fiber, 5% of bisphenol A-bis (diphenyl phosphate) (BDP), 6% of magnesium oxide, 8% of 2-hydroxy-4-octoxy benzophenone, 0.5% of antioxidant and 0.5% of stearic acid;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 10min to uniformly mix the components;
(4) And (3) extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 240 ℃, and the screw rotation speed is 500rpm.
Example 2
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 110 ℃ for 5h, and drying potassium diphenyl Sulfone Sulfonate (SSK) and glass fiber at 85 ℃ for 30min for later use;
(2) Taking materials: weighing the following raw materials in percentage by weight: 60% of PC resin, 15% of glass fiber, 8% of potassium diphenylsulfone sulfonate (SSK), 8% of calcium oxide, 8% of 2-hydroxy-4-methoxybenzophenone, 0.5% of antioxidant and 0.5% of butyl stearate;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 20min to uniformly mix the components;
(4) And (3) extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 250 ℃, and the screw rotation speed is 450rpm.
Example 3
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 120 deg.C for 4h, and drying silicone resin flame retardant and glass fiber at 75 deg.C for 50 min;
(2) Taking materials: weighing the following raw materials in percentage by weight: 45 percent of PC resin, 20 percent of glass fiber, 10 percent of silicone resin flame retardant FR-300, 12 percent of magnesium oxide, 12 percent of 2,4-dihydroxy benzophenone, 0.5 percent of antioxidant and 0.5 percent of oleamide;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 30min to uniformly mix the components;
(4) And (3) extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 290 ℃, and the screw rotation speed is 300rpm.
Example 4
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 130 deg.C for 3h, and drying resorcinol-bis (diphenyl phosphate) (RDP) and glass fiber at 85 deg.C for 30 min;
(2) Taking materials: weighing the following raw materials in percentage by weight: 55% of PC resin, 15% of glass fiber, 10% of resorcinol-bis (diphenyl phosphate) (RDP), 10% of barium oxide, 9% of 2,4-dihydroxybenzophenone, 0.5% of antioxidant, 0.5% of ethylene bis stearamide;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 10min to uniformly mix the components;
(4) And (3) extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 270 ℃, and the screw rotation speed is 400rpm.
Example 5
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 110 deg.C for 5h, and drying polyphenyl phosphonic acid diphenyl sulfone ester (PSPPP) and glass fiber at 70 deg.C for 60min;
(2) Taking materials: weighing the following raw materials in percentage by weight: 50% of PC resin, 20% of glass fiber, 7% of polyphenyl phosphonic acid diphenyl sulfone ester (PSPPP), 10% of barium oxide, 12% of 2-hydroxy-4-octoxy benzophenone, 0.5% of antioxidant and 0.5% of natural paraffin;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 30min to uniformly mix the components;
(4) And (3) extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 280 ℃, and the screw rotation speed is 350rpm.
Example 6
The preparation method of the high CTI, aging-resistant, halogen-free and flame-retardant reinforced PC composite material for the connector provided by the embodiment of the invention comprises the following steps:
(1) Preparing materials: drying PC resin at 120 deg.C for 4h, and drying glass fiber, bisphenol A-bis (diphenyl phosphate) (BDP) and silicone resin flame retardant at 80 deg.C for 40 min;
(2) Taking materials: weighing the following raw materials in percentage by weight: 65% of PC resin, 10% of glass fiber, 5% of bisphenol A-bis (diphenyl phosphate) (BDP), 5% of silicone resin flame retardant FR-300, 8% of calcium oxide, 6% of 2-hydroxy-4-methoxybenzophenone, 0.5% of antioxidant and 0.5% of polyethylene wax;
(3) Mixing: adding the weighed components into a high-speed mixer, and stirring for 20min to uniformly mix the components;
(4) Extruding and granulating: and adding the mixture into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 260 ℃ and the screw rotation speed is 400rpm.
Comparative example 1
The comparative example provides a preparation method of a halogen-free flame-retardant reinforced PC composite material, and the difference from the example 1 is that the selection of a halogen-free flame retardant is different, and the halogen-free flame retardant is specifically p-dimethylphenylphosphonate.
Comparative example 2
The comparative example provides a preparation method of a halogen-free flame-retardant reinforced PC composite material, and the difference from the example 1 is that the selection of a CTI improver is different, and the CTI improver is specifically titanium oxide.
Comparative example 3
The comparative example provides a preparation method of a halogen-free flame-retardant reinforced PC composite material, which is different from that of example 1 in the selection of an aging-resistant agent, specifically 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
Comparative example 4
The comparative example provides a preparation method of a halogen-free flame-retardant reinforced PC composite material, which is different from that of example 1 in the following mass ratio of a halogen-free flame retardant, a CTI improver and an anti-aging agent, specifically 15.
Effect verification
The CTI test is IEC 60112:2009 (corresponding to GB/T4207-2012) simulation test items specified in Standard of methods for measuring tracking resistance index and comparative tracking index of solid insulating materials; the flame retardancy test is referred to the us UL94 fire standard; the flexural strength measurement standard is ASTM D790 Standard test method for flexural Properties of unreinforced and reinforced plastics and electrically insulating materials; the ageing resistance test was carried out using standard ISO 4892 "plastics-laboratory light exposure method-part 3: fluorescent ultraviolet lamp (UVlamp).
The composite materials obtained in the above examples 1 to 6 and comparative example were subjected to the performance test according to the above test method, and the results were as follows:
TABLE 1
| CTI value | Flame retardancy | Flexural strength | Aging resistance | |
| Example 1 | 405V | V-0 | 135MPa | No visible obvious aging |
| Example 2 | 410V | V-0 | 131MPa | No visible obvious aging |
| Example 3 | 405V | V-0 | 142MPa | No visible obvious aging |
| Example 4 | 408V | V-0 | 139MPa | No visible obvious aging |
| Example 5 | 405V | V-0 | 140MPa | No visible obvious aging |
| Example 6 | 400V | V-0 | 133MPa | No visible obvious aging |
| Comparative example 1 | 400V | V-1 | 133MPa | No visible obvious aging |
| Comparative example 2 | 275V | V-0 | 135MPa | No visible obvious aging |
| Comparative example 3 | 405V | V-0 | 131MPa | Aging occurs |
| Comparative example 4 | 400V | V-0 | 130MPa | No visible obvious aging |
The CTI value of the PC composite material obtained in the embodiments 1-6 of the invention is improved to 400V, the ageing resistance is excellent, and the flame retardant property reaches V-0 level of UL 94. And the composite material obtained by the comparative example has poor performance due to improper selection of the auxiliary agent or improper dosage proportion. Therefore, the unexpected technical effect of the invention on the screening of each auxiliary agent and the limitation of the dosage relation is demonstrated.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A halogen-free flame-retardant reinforced PC composite material is characterized by comprising: polycarbonate, glass fiber, halogen-free flame retardant, CTI improver and aging resistant agent;
the halogen-free flame retardant is any one or more of bisphenol A-bis (diphenyl phosphate), resorcinol-bis (diphenyl phosphate), a silicone flame retardant, potassium diphenylsulfone sulfonate and polyphenyl phosphonic acid diphenylsulfone ester;
the CTI improver is any one or more of magnesium oxide, calcium oxide and barium oxide;
the aging resistant agent is any one or more of 2-hydroxy-4-octoxy benzophenone, 2-hydroxy-4-methoxy benzophenone or 2,4-dihydroxy benzophenone;
the mass ratio of the halogen-free flame retardant to the CTI improver to the aging resistant agent is (5-10): (6-12): (8-12).
2. The halogen-free flame retardant reinforced PC composite material of claim 1, wherein the halogen-free flame retardant is bisphenol A-bis (diphenyl phosphate), the CTI modifier is magnesium oxide, and the aging resistor is 2-hydroxy-4-octyloxybenzophenone;
or the halogen-free flame retardant is potassium diphenylsulfone sulfonate, the CTI improver is calcium oxide, and the aging-resistant agent is 2-hydroxy-4-methoxybenzophenone;
or the halogen-free flame retardant is a silicone resin flame retardant, the CTI improver is magnesium oxide, and the aging-resistant agent is 2,4-dihydroxy benzophenone;
or the halogen-free flame retardant is resorcinol-bis (diphenyl phosphate), the CTI improver is barium oxide, and the aging-resistant agent is 2,4-dihydroxy benzophenone;
or the halogen-free flame retardant is polyphenyl phosphonic acid diphenyl sulfone ester, the CTI improver is barium oxide, and the aging-resistant agent is 2-hydroxy-4-octyloxy benzophenone;
or the halogen-free flame retardant consists of bisphenol A-bis (diphenyl phosphate) and a silicone resin flame retardant in a mass ratio of 1:1, the CTI improver is calcium oxide, and the aging resistant agent is 2-hydroxy-4-octyloxy benzophenone.
3. The halogen-free flame retardant reinforced PC composite material according to claim 1 or 2, wherein the halogen-free flame retardant reinforced PC composite material further comprises an antioxidant;
the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant; wherein the hindered phenol antioxidant is specifically antioxidant 1010, and the phosphite ester antioxidant is specifically antioxidant 168.
4. The halogen-free flame-retardant reinforced PC composite material according to claim 3, wherein the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 2:1.
5. The halogen-free, flame-retardant, reinforced PC composite of any one of claims 1-4, wherein the halogen-free, flame-retardant, reinforced PC composite further comprises a lubricant;
the lubricant is any one or more of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, natural paraffin or polyethylene wax.
6. The halogen-free flame retardant reinforced PC composite material according to any one of claims 1 to 5, wherein the halogen-free flame retardant reinforced PC composite material comprises the following components in parts by weight: 45-70 parts of PC resin, 10-20 parts of glass fiber, 5-10 parts of halogen-free flame retardant, 6-12 parts of CTI improver, 8-12 parts of anti-aging agent, 0.1-0.5 part of antioxidant and 0.1-0.5% of lubricant.
7. The method for preparing the halogen-free flame-retardant reinforced PC composite material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps: mixing the components in proportion, mixing uniformly and granulating.
8. The method according to claim 7, wherein the PC resin, the halogen-free flame retardant and the glass fiber are dried before mixing;
the drying conditions of the PC resin are as follows: drying for 3-5h at 110-130 ℃;
the drying conditions of the halogen-free flame retardant and the glass fiber are as follows: drying at 70-85 deg.c for 30-60 min;
the granulation is obtained by a twin-screw extruder; the extrusion temperature is 240-290 ℃, and the screw rotation speed is 300-500 rpm.
9. The use of the halogen-free flame-retardant reinforced PC composite material according to any of claims 1 to 6 in the fields of aviation, aerospace, rail transportation, industrial automation.
10. A connector, characterized in that the halogen-free flame retardant reinforced PC composite material according to any of claims 1 to 6 is used.
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