CN112322014A - Low-temperature-resistant PC alloy material and preparation method thereof - Google Patents
Low-temperature-resistant PC alloy material and preparation method thereof Download PDFInfo
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- CN112322014A CN112322014A CN202011048590.7A CN202011048590A CN112322014A CN 112322014 A CN112322014 A CN 112322014A CN 202011048590 A CN202011048590 A CN 202011048590A CN 112322014 A CN112322014 A CN 112322014A
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- flame retardant
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- toughening agent
- antioxidant
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- 239000000956 alloy Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003063 flame retardant Substances 0.000 claims abstract description 53
- 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 claims abstract description 50
- 239000012745 toughening agent Substances 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 239000004417 polycarbonate Substances 0.000 claims description 32
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 235000013824 polyphenols Nutrition 0.000 claims description 8
- -1 propylene ester Chemical class 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 4
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 125000004001 thioalkyl group Chemical group 0.000 claims description 4
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- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 claims description 2
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 229940075529 glyceryl stearate Drugs 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000005000 thioaryl group Chemical group 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical group CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000004945 silicone rubber Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000003921 oil Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229920006778 PC/PBT Polymers 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WBPYTXDJUQJLPQ-LLMNDNAOSA-N tylosin Chemical compound O=CCC1CC(C)C(=O)\C=C\C(\C)=C\C(COC2C(C(OC)C(O)C(C)O2)OC)C(CC)OC(=O)CC(O)C(C)C1OC(C(C1N(C)C)O)OC(C)C1OC1CC(C)(O)C(O)C(C)O1 WBPYTXDJUQJLPQ-LLMNDNAOSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-temperature-resistant PC alloy material and a preparation method thereof, wherein the low-temperature-resistant PC alloy material comprises the following components in parts by weight: 70.0-90.0 parts of PC resin; 25.0-35.0 parts of PBT resin; 5.0-15.0 parts of a flame retardant; auxiliary flame retardant 2.0-10.0 weight portions; 2.0-15.0 parts of a first toughening agent; 1.0-5.0 parts of a second toughening agent; 0.01-2.0 parts of antioxidant; 0.01 to 1.2 portions of other auxiliary agents. The low-temperature-resistant PC alloy material has excellent low-temperature resistance, and is particularly suitable for occasions with higher requirements on use environments, particularly the fields of household appliances, industrial machines and the like which are in contact with oil stains and solvents and have requirements on low-temperature toughness.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a low-temperature-resistant PC alloy material and a preparation method thereof.
Background
Polycarbonate resin is a general-purpose engineering plastic and has advantages in various aspects such as transparency, impact resistance, heat resistance, dimensional stability, etc., but PC also has problems of large internal stress, solvent intolerance, and difficulty in processing. The PBT resin is a crystalline polymer and has excellent solvent resistance and molding processability. PBT is added into PC resin, so that the processing performance and solvent resistance of PC can be obviously improved; the improvement of the solvent resistance is realized by the fact that the PBT forms an interpenetrating network, and the solvent resistance of the PC/PBT alloy is greatly improved only after the crystallized PBT resin reaches a certain proportion.
When the flame retardant is applied to shells of household appliances, electric appliances or industrial machines, the material is generally required to meet the flame retardant requirement of V-0, in addition, the requirements of high toughness and low temperature resistance are provided for the material when the flame retardant is used outdoors, and the toughness or the low temperature resistance of the material can be greatly reduced by the conventional flame retardant of PC or PBT, so that the application range of the material is limited. In order to compensate the damage of the flame retardant to the toughness of the resin, the toughness is usually improved by adding the toughener, while the flame retardant performance of the resin is seriously influenced by the common toughener MBS for PC or EBA-GMA for PBT, and the contradiction between the flame retardant and the toughness, particularly the low-temperature toughness exists, so that the simultaneous realization is difficult.
Disclosure of Invention
In view of the above, the present invention provides a low temperature resistant PC alloy material and a preparation method thereof, aiming to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a low-temperature-resistant PC alloy material comprises the following components in parts by weight:
preferably, the low-temperature resistant PC alloy material comprises the following components in parts by weight:
preferably, the first toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylic toughening agent, acrylonitrile-styrene-acrylate copolymer and organic silicon rubber graft toughening agent.
More preferably, the first toughening agent is an organic silicon rubber graft toughening agent, and the volume average particle size of the rubber component of the organic silicon rubber graft toughening agent is 150-1500nm, more preferably 200-1200 nm; the content of the rubber component is 5-40%, more preferably 30-40%, and the toughening efficiency can be obviously improved.
Further preferably, the volume average particle size of the rubber component of the organic silicon rubber graft toughening agent is 300-800nm, so that the impact resistance can be obviously improved.
Preferably, the second toughening agent is a reactive toughening agent, specifically at least one of an ethylene-acrylate-glycidyl methacrylate terpolymer, a maleic anhydride functionalized ethylene-vinyl acetate copolymer, and an ethylene-octene-glycidyl methacrylate terpolymer, and preferably an ethylene-octene-glycidyl methacrylate terpolymer.
Preferably, the polycarbonate resin has a viscosity average molecular weight of at least one of 10000-40000 aromatic polycarbonates, more preferably 12000-25000.
Preferably, the flame retardant is a halogen-based flame retardant, a phosphorus-based flame retardant, a siloxane-based flame retardant, a metal salt-based flame retardant or a boron-based flame retardant, more preferably a halogen-based flame retardant, and even more preferably brominated polycarbonate.
Preferably, the auxiliary flame retardant is antimony white, talcum powder or an organic silicon flame retardant synergist, more preferably, the organic silicon flame retardant is an organic silicon flame retardant synergist, so that the use content of the flame retardant and the influence on the toughness, particularly the low-temperature toughness of the material can be effectively reduced.
Preferably, the antioxidant is mixed by mass ratio of 1.0: (0.5-1.0) or only the main antioxidant, wherein the main antioxidant and the auxiliary antioxidant are both selected from one of propylene ester antioxidants, phosphite antioxidants or alkylated monophenol or polyphenol, and alkylated reaction products of polyphenol and diene.
Preferably, the propylene ester antioxidant is octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite antioxidant is tris (nonylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; the alkylated monophenol or polyphenol, the alkylated reaction product of polyphenol and diene are tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinone, hydroxylated thiodiphenyl ether, alkylidene bisphenols, benzyl compounds, esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols, esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols, esters of thioalkyl or thioaryl compounds or amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid.
More preferably, the ester of the thioalkyl or thioaryl compound is distearylthiopropionate, dilaurylthiopropionate, tricosylthiodipropionate, pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further preferably, the primary antioxidant is Chinox1076, and the secondary antioxidant is THANOX 168.
Preferably, the other auxiliary agent is a lubricant and/or an anti-dripping agent. The lubricant is glyceryl stearate, and the anti-dripping agent is PTFE coated with AS.
The invention also provides a preparation method of the low-temperature-resistant PC alloy material, which comprises the following steps:
(1) weighing the raw materials according to the formula, and sequentially putting the raw materials into a mixer to be uniformly blended to obtain a premix;
(2) putting the premix prepared in the step (1) into a double-screw extruder, melting and mixing in the double-screw extruder, extruding and granulating to obtain the premix;
the length-diameter ratio of the screws of the double-screw extruder in the step (2) is (40-45): 1, the temperature of the screw cylinder is 250-280 ℃, and the rotating speed of the screw is 400-500 rpm.
Compared with the prior art, the invention has the following advantages:
according to the invention, PBT is added into PC, so that the solvent resistance of PC is greatly improved, a high-efficiency bromine flame retardant is used, the flame retardant property of the alloy is improved, the V-0 flame retardant level is improved, a special organosilicon synergist is used in a matching manner, the use amount of the bromine flame retardant is reduced, and the influence on the toughness of the alloy, especially on the low-temperature toughness is small. In addition, the first efficient toughening agent organosilicon is used, so that the toughening efficiency is high, the PC phase in the first toughening agent organosilicon is mainly toughened, the addition amount of the first toughening agent organosilicon is less than that of a conventional toughening agent, the influence on the flame retardant property is reduced, and the low-temperature toughness of the material is improved. The second toughening agent ethylene-octene-glycidyl methacrylate has an efficient toughening effect on PBT, compared with ethylene-n-butyl acrylate (EBA) or ethylene-methyl acrylate (EMA), ethylene-octene has a better toughening effect on PC, glycidyl methacrylate has a compatibility effect on a phase interface of PC and PBT, interface voiding is reduced, and the toughness and low-temperature toughness of the PC/PBT alloy are greatly improved by cooperation with the first toughening agent. The alloy material is particularly suitable for occasions with higher requirements on use environments, particularly the fields of household appliances, industrial machines and the like which are in contact with oil stains and solvents and have requirements on low-temperature toughness.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to the following examples.
PC resin is PC S-2000F (Mitsubishi, Japan) with viscosity average molecular weight of 22000; the PBT resin is selected from medium-viscosity PBT GX121 (characterized by petrifaction); RDT-7 (chemical industry of Weidong) is selected as a flame retardant; other flame retardants are F-2100(ICL) and FP-600 (Adeca); the first toughening agent is S-170H (the volume average particle size is 350nm, and the rubber content is 32%) in the Tylon chemical industry; the other first toughening agent is selected from S-2001 of Mitsubishi Yang; the second toughening agent is preferably and easily SOG-03; other second toughening agents are PTW of DuPont; the antioxidant is Chinox1076, namely beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (CAS No.: 2082-79-3); the lubricant of other adjuvants is selected from UNISTER-M9676 (Nissan day oil), and the anti-dripping agent is selected from A3800 (Mitsubishi Yang).
Weighing polycarbonate resin, PBT resin, a flame retardant, a synergistic flame retardant, a toughening agent, an antioxidant and other auxiliaries according to the use amounts of the raw materials in the formula shown in Table 1, and then sequentially putting the raw materials into a mixer to blend uniformly to obtain a premix; and then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to obtain the low-temperature-resistant PC/PBT alloy material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 40:1, the temperature of the screw cylinder is 230-250 ℃, and the rotating speed of the screw is 400-500 rpm.
The obtained low-temperature resistant PC/PBT alloy material is respectively tested for the notch cantilever beam impact strength, the heat resistance and the 60-degree gloss, and the reference standard or the method for testing is as follows.
(1) Solvent resistance: according to ASTM D543, the test piece for tensile strength test (test piece thickness 3.2mm) was coated with peanut oil in a 1.0% strain jig and then observed for change in appearance, and the test piece was classified into grades A (no crack), B (crack), C (severe crack) to D (fracture) according to the weight of crack occurrence.
(2) Method for measuring Izod impact Strength (Normal temperature): notched izod impact strength was measured using a 4.0mm thick molded notched izod impact bar. Notched Izod impact strength measured in kJ/m according to ISO 1802Recording the results, testingAt room temperature (23 ℃).
(3) Method for measuring Izod impact Strength (Low temperature): notched izod impact strength was measured using a 4.0mm thick molded notched izod impact bar. Notched Izod impact strength measured in kJ/m according to ISO 1802The results were recorded and the test was performed at room temperature (-40 ℃).
(4) UL94 flame retardancy test method:
the flammability test was carried out according to the protocol "flammability test of plastic materials, UL 94". Flame retardant ratings were derived based on the burn rate, extinguishing time, ability to resist dripping, and whether dripping (drip) was burning. Samples used for the test: bars having dimensions of 125mm length x 13mm width x no greater than 13mm thickness, the thickness of the bars when tested according to the invention being selected to be 2.0 mm. According to the UL94 protocol, and based on the test results obtained for five samples, the material flame retardant rating can be classified as (UL 94-HB): v0, V1, V2, 5VA and/or 5 VB; in the present invention, however, only the flame retardant rating of the material is classified as: v0, V1 and V2, and the classification criteria for each flame retardant rating are:
v0: in a sample placed so that its long axis is 180 degrees with respect to the flame, the period of burning and/or smoldering does not exceed 10 seconds after the ignition flame is removed, and the vertically placed sample does not produce dripping of combustion particles that ignite cotton wool. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the flame holding time for the first light (t1) and the flame holding time for the second light (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 50 seconds.
V1: in a sample placed so that its long axis is 180 degrees relative to the flame, the period of burning and/or smoldering does not exceed 30 seconds after the ignition flame is removed, and the vertically placed sample does not produce dripping of burning particles that ignite cotton wool. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the first lit flame holding time (t1) and the second lit flame holding time (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 250 seconds.
V2: in a sample placed so that its long axis is 180 degrees relative to the flame, the average period of burning and/or smoldering after removal of the ignition flame does not exceed 30 seconds, but a vertically placed sample produces dripping of burning particles that ignite cotton. The flame holding time for the fifth bar is the flame holding time for the five bars, each lit twice, wherein the sum of the first lit flame holding time (t1) and the second lit flame holding time (t2), i.e. the maximum flame holding time (t1+ t2), is less than or equal to 250 seconds.
The results of the above tests are shown in Table 1.
TABLE 2 amounts (unit: parts by weight) of examples 1 to 2 and comparative examples 1 to 6 and results of performance test
As can be seen, compared with the composite materials prepared by comparative examples 1-7, in comparative example 1, the PBT conventional toughening agent PTW is used, so that the normal temperature toughness is good, but the low temperature toughness is lower; comparative example 2 adding conventional silicon toughening agent, the toughening efficiency is lower, and the notch impact strength at minus 30 ℃ is lower than 20kJ/m2(ii) a When the content of the toughening agent is more, the low-temperature toughness is improved, but the flame retardant performance is seriously reduced, as shown in a comparative example 3; the comparative example 4 uses the common antimony white synergistic flame retardant, antimony white has no oxide, has great influence on the toughness of the material, especially the low-temperature toughness, has relatively poor flame retardant synergistic effect, and has the flame retardant only in V-1 level; comparative example 5, using other bromine flame retardants, the flame retardant efficiency was lower, and the higher content of PBT in the PC/PBT alloy only achieved V-2 flame retardant rating; similarly, the halogen-free flame retardant FP-600 has lower flame retardant efficiency (comparative example 6), and V-0 flame retardance can be realized in PC/PBT with lower PBT content, but the performances such as low-temperature toughness, solvent resistance and the like are poorer.
The low-temperature-resistant PC/PBT alloy material product prepared by the invention can be widely applied to household appliances, charging pile shells, electric vehicle parts, housing materials, automobile materials, materials for manufacturing parts in other industrial fields and the like, and is particularly suitable for the fields of household appliances, industrial machines and the like which are in contact with oil stains and solvents and have requirements on low-temperature toughness.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. A low-temperature-resistant PC alloy material is characterized in that: the composition comprises the following components in parts by weight:
2. the low temperature resistant PC alloy material of claim 1 wherein: the low-temperature-resistant PC alloy material comprises the following components in parts by weight:
3. the low temperature resistant PC alloy material of claim 1 or 2 wherein: the first toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylic toughening agent, acrylonitrile-styrene-acrylate copolymer and organic silicon rubber graft toughening agent; more preferably, the first toughening agent is an organic silicon rubber graft toughening agent, and the volume average particle size of the rubber component of the organic silicon rubber graft toughening agent is 150-1500nm, more preferably 200-1200 nm; the rubber component content is 5 to 40%, more preferably 30 to 40%; further preferably, the volume average particle size of the rubber component of the silicone rubber graft toughening agent is 300-800 nm.
4. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the second toughening agent is a reactive toughening agent, specifically at least one of an ethylene-acrylate-glycidyl methacrylate terpolymer, a maleic anhydride functionalized ethylene-vinyl acetate copolymer and an ethylene-octene-glycidyl methacrylate terpolymer, and preferably an ethylene-octene-glycidyl methacrylate terpolymer.
5. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the polycarbonate resin has a viscosity average molecular weight of 10000-40000 and is more preferably 12000-25000.
6. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the flame retardant is a halogen flame retardant, a phosphorus flame retardant, a siloxane flame retardant, a metal salt flame retardant or a boron-based flame retardant, more preferably a halogen flame retardant, and further preferably brominated polycarbonate; the auxiliary flame retardant is antimony white, talcum powder or an organic silicon flame retardant synergist, and more preferably an organic silicon flame retardant.
7. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the antioxidant is prepared from the following components in a mass ratio of 1.0: (0.5-1.0) or only the main antioxidant, wherein the main antioxidant and the auxiliary antioxidant are both selected from one of propylene ester antioxidants, phosphite antioxidants or alkylated monophenol or polyphenol, and alkylated reaction products of polyphenol and diene; preferably, the propylene ester antioxidant is octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite antioxidant is tris (nonylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; the alkylated monophenol or polyphenol, the alkylated reaction product of polyphenol and diene are tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinone, hydroxylated thiodiphenyl ether, alkylidene bisphenols, benzyl compounds, esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols, esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols, esters of thioalkyl or thioaryl compounds or amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid; more preferably, the ester of the thioalkyl or thioaryl compound is distearylthiopropionate, dilaurylthiopropionate, tricosylthiodipropionate, pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
8. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the primary antioxidant is Chinox1076, and the secondary antioxidant is THANOX 168.
9. The low temperature resistant PC alloy material of claim 1 or 2 wherein: the other auxiliary agent is a lubricant and/or an anti-dripping agent. The lubricant is glyceryl stearate, and the anti-dripping agent is PTFE coated with AS.
10. The method for preparing the low temperature resistant PC alloy material according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) weighing the raw materials according to the formula, and sequentially putting the raw materials into a mixer to be uniformly blended to obtain a premix;
(2) putting the premix prepared in the step (1) into a double-screw extruder, melting and mixing in the double-screw extruder, extruding and granulating to obtain the premix;
the length-diameter ratio of the screws of the double-screw extruder in the step (2) is (40-45): 1, the temperature of the screw cylinder is 250-280 ℃, and the rotating speed of the screw is 400-500 rpm.
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