CN110760175A - Toughened PC/SI-PC/PBT alloy material and preparation method thereof - Google Patents
Toughened PC/SI-PC/PBT alloy material and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 229920006778 PC/PBT Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 9
- 239000004417 polycarbonate Substances 0.000 claims abstract description 58
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 45
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 39
- 239000012745 toughening agent Substances 0.000 claims abstract description 22
- 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 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 12
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 239000004611 light stabiliser Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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 3
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 3
- 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 claims description 3
- NJMAFLHPUNGKOD-UHFFFAOYSA-N 1-o-butyl 2-o-decyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC NJMAFLHPUNGKOD-UHFFFAOYSA-N 0.000 claims description 2
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims 1
- 229960001860 salicylate Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 238000005452 bending Methods 0.000 abstract description 13
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 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 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a toughened PC/SI-PC/PBT alloy material, which comprises the following components in parts by weight: 5-40 parts of polycarbonate; 5-40 parts of siloxane copolymerized polycarbonate; 5-40 parts of polybutylene terephthalate; 3-7 parts of a toughening agent; 3-5 parts of a compatilizer; 0.1-0.5 parts of ester exchange inhibitor; 0.1-0.5 part of antioxidant; 0.1-0.3 part of light stabilizer; 0.1-0.4 part of lubricant; 15-40 parts of chopped glass fiber; 8-15 parts of a flame retardant; 0.2 to 0.5 portion of flame retardant synergist. The novel toughened PC/SI-PC/PBT alloy material disclosed by the invention has the advantages of high low-temperature impact resistance, high bending strength and modulus, high flame retardance UL941.5mmV-0 and excellent chemical stability, and the key point is that the material has high impact resistance at-30 ℃, the load deformation temperature of the material is 10-20 ℃ higher than that of the common PC/PBT alloy, and the defects of low load deformation temperature and low bending strength and modulus of the toughened PC/PBT alloy are overcome.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a toughened PC/SI-PC/PBT alloy material and a preparation method thereof.
Background
PC/PBT is a blended material of PC and PBT, and is usually supplied in the form of pellets after being subjected to blend molding. If only two materials are simply mixed and directly injected, the effect is poor and the layering phenomenon can occur. PC has the advantages of rigidity and toughness at room temperature, but has serious thermal deformation at high temperature, and has the disadvantages of stress cracking and high viscosity; the PBT has the advantages that the rigidity is not influenced by temperature, and the deformation is small; the PC/PBT material after blending keeps the advantages of the PC/PBT material and the PBT material, and the PC/PBT material has higher surface hardness, higher rigidity and toughness, higher high-temperature shape resistance and higher stress cracking resistance; the mechanical property of the material is between the two, and the high-temperature deformation resistance has important significance for large-sized shell materials.
PC/PBT is a plastic alloy, which maintains the chemical resistance and easy forming of the crystalline material PBT, and has the toughness and dimensional stability of the amorphous material PC, and the PC/PBT has the comprehensive characteristics of both PC and PBT, such as the high toughness and geometric stability of PC and the chemical stability, thermal stability and lubricating property of PBT.
However, in many cases, the material is required to have higher notched impact strength at normal temperature and higher notched impact strength at low temperature, almost all solutions are solved by adding toughening agents, but almost all toughening agents belong to low-modulus and low-melting-point substances, a large amount of toughening agents are required to be added to ensure that the material still has high notched impact strength at low temperature, and the addition of a large amount of toughening agents greatly reduces the bending strength, the bending modulus and the load deformation temperature of the PC/PBT alloy.
Chinese patent CN101469114A discloses a toughened and reinforced PC/PBT composite material and a preparation method thereof, wherein the toughening method is single, if the material still maintains better notch impact strength at low temperature, the dosage of the toughening agent is more than 10 parts, and the load deformation temperature of the material is 10-15 ℃ lower than that of the material when 5-7 parts of the toughening agent is used.
However, in many cases, the material is required to have high notched impact strength at normal temperature and high notched impact strength at low temperature, almost all solutions are solved by adding a large amount of toughening agent, but almost all toughening agents belong to low-modulus and low-melting-point substances, a large amount of toughening agent is required to be added to ensure that the material still has high notched impact strength at low temperature, and the bending strength, the bending modulus and the load deformation temperature of the PC/PBT alloy are greatly reduced by adding the large amount of toughening agent.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a toughened PC/SI-PC/PBT alloy material and a preparation method thereof, the toughened PC/SI-PC/PBT alloy material has high low-temperature impact resistance, high bending strength and modulus, high flame retardance and excellent chemical stability, has high impact resistance at-30 ℃ and a load deformation temperature which is 10-20 ℃ higher than that of the common PC/PBT alloy, and overcomes the defects of low load deformation temperature, low bending strength and modulus of the toughened PC/PBT alloy.
The technical scheme of the invention is as follows:
the invention relates to a toughened PC/SI-PC/PBT alloy material, which comprises the following components in parts by weight:
the melt index of the polycarbonate is 8-20 g/10 min; the siloxane copolycarbonate has a silicon content greater than 8%; the melt index of the polybutylene terephthalate is 5-130 g/10min (preferably PBT resin with the melt index of 20g/10min and 120g/10min is matched for use).
In the invention, the siloxane polycarbonate is a copolymer of polycarbonate and siloxane, and the siloxane polycarbonate is also polycarbonate in nature and has excellent low-temperature toughness, and the PC/SI-PC/PBT alloy obtained by blending the polycarbonate with PC and PBT also has excellent low-temperature toughness, so that the novel toughened PC/SI-PC/PBT alloy can greatly reduce a toughening agent which must be added in the traditional toughened PC/PBT alloy, and avoids the bending strength and modulus brought by the addition of the toughening agent and the great reduction of load deformation temperature.
Further, the toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene terpolymer (MBS), ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-acrylate-glycidyl methacrylate copolymer (E-MA-GMA) and methyl methacrylate-organic silicon copolymer. Preferably, the toughening agent is MBS, and the toughening agent has low price and good toughening effect.
Further, the compatilizer is one or more of ethylene-methyl acrylate-maleic anhydride copolymer EMA-g-MAH, POE-g-MAH, EVA-g-MAH, EBA-g-MAH and PC/PBT transesterification product. A preferred compatibilizer is a PC/PBT transesterification product PC-PBT copolymer that has been twin screw blended at 280 ℃. The compatilizer has better compatibility with PC and PBT.
Further, the ester exchange inhibitor is one or more of alkyl phosphate ester exchange inhibitor, sodium dihydrogen phosphate (MSP), phosphite ester, anhydrous sodium dihydrogen phosphate (AMSP) and triphenyl phosphite (TPPI). The preferred transesterification inhibitor is anhydrous sodium dihydrogen phosphate.
Further, the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098).
Further, the light stabilizer is selected from one or more of salicylic acid esters, benzoic acid esters, benzophenones, benzotriazole, substituted acrylonitrile, oxamides, organic nickel complexes and hindered amine light stabilizers.
Further, the lubricant is selected from one or more of polyethylene wax, calcium stearate and silicone.
Further, the chopped glass fiber is selected from chopped fibers with the length of 3-4.5 mm, the fiber diameter of 7-13 mu m and silane surface treatment.
Further, the flame retardant is selected from one or more of antimony trioxide, decabromodiphenylethane, a flame retardant plasticizer RDP and a flame retardant plasticizer BDP; the flame-retardant synergist is polyphenyl ether and/or polytetrafluoroethylene.
Preferably, the toughened PC/SI-PC/PBT alloy material comprises the following components in parts by weight:
the invention also provides a preparation method of the toughened PC/SI-PC/PBT alloy material, which comprises the following steps:
mixing the dried components at a certain proportion, and mixing the obtained mixture
Extruding and granulating in a double-screw extruder, wherein the extrusion temperature of each area of the double-screw extruder is 220-265 ℃, the feeding speed is 30-100kg/h, and the rotating speed of a screw is 160-250 rpm; and cooling to obtain the toughened PC/SI-PC/PBT alloy material.
Preferably, the preparation method of the toughened PC/SI-PC/PBT alloy material comprises the following steps:
the method comprises the following steps: dehumidifying and drying PC and SI-PC at 120 ℃ for 2-4 h, dehumidifying and drying PBT at 110 ℃ for 2-4 h, and weighing the granular materials (PC, SI-PC, PBT and compatilizer), the powder materials (flexibilizer, ester exchange inhibitor, antioxidant, light stabilizer, lubricant, flame retardant and flame retardant synergist) and the chopped glass fibers according to the proportion;
step two: adding the granules and the powder weighed in the step one into respective high-speed mixing machines, mixing at the speed of 250-1000 r/min for 5-10 min, feeding until the granules and the powder are weighed to be weight-loss, and adding short glass fibers into the glass fiber scale;
step three: setting the feeding proportion of a weight loss scale according to the weight parts of the aggregate, the powder and the glass fiber, wherein the extrusion temperature is 220-265 ℃, and the screw rotation speed is 160-250 rpm;
step four: and cooling the melt output extruded by the die head of the double-screw extruder to prepare granules, namely the PC/SI-PC/PBT alloy material.
By the scheme, the invention at least has the following advantages:
1. polycarbonate (PC) and polybutylene terephthalate (PBT) are taken as base materials, and completely compatible siloxane copolymerization polycarbonate (SI-PC) and a toughening agent are added, so that the material has extremely high notched impact strength of a cantilever beam at normal temperature and low temperature, the notched impact strength of the cantilever beam at 23 ℃ is more than or equal to 500J/m, and the notched impact strength of the cantilever beam at 30 ℃ is more than or equal to 300J/m;
2. according to the invention, by adding the ester exchange inhibitor, when the use amount of PC and PBT is 1:1, the ester exchange reaction degree is still very low, and the blended material can keep higher mechanical property and chemical resistance;
3. according to the invention, the siloxane copolymerized polycarbonate and the toughening agent are effectively matched, so that the dosage of the toughening agent is effectively reduced on the premise of ensuring higher toughness of the material at normal temperature and low temperature, and the bending strength, the bending modulus and the load deformation temperature of the material are kept at a very high level;
4. the flame-retardant material has high flame-retardant and environment-friendly performance, meets the relevant environment-friendly regulations such as European Union RoSH standard and REACH regulation (meets the limit requirement of the European Union number 1907/2006 REACH regulation, European Union RoHS instruction 2011/65/correction instruction (EU)2015/863 of EU annex II and meets the requirement of the European Union standard EN 50620), and the flame-retardant index of the material reaches the level of UL940.8mmV-0;
in conclusion, the novel toughened PC/SI-PC/PBT alloy material disclosed by the invention has the characteristics of high tensile strength, high bending strength and modulus, high cantilever beam notch impact strength at the normal temperature of 23 ℃ and at the low temperature of-30 ℃, high load deformation temperature and the like, and is suitable for scenes of low-temperature impact toughness performance and high load deformation temperature which cannot be met by conventional PC/PBT materials.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The novel toughened PC/SI-PC/PBT alloy material comprises the following components in parts by weight:
the flame retardant is a compound product of antimonous oxide and decabromodiphenylethane (antimonous oxide: decabromodiphenylethane weight ratio is 5:8), and the flame retardant synergist is polyphenyl ether.
The preparation method of the novel toughened PC/SI-PC/PBT alloy material comprises the following steps:
the method comprises the following steps: PC and SI-PC are dried for 2-4 h at 120 ℃ and PBT is dried for 2-4 h at 110 ℃, and the granular materials (PC, SI-PC, PBT and compatilizer), the powder materials (flexibilizer, ester exchange inhibitor, antioxidant, light stabilizer, lubricant, flame retardant and flame retardant synergist) and the chopped glass fibers are weighed separately according to the weight parts;
step two: adding the granules and the powder weighed in the step one into respective high-speed mixing machines, mixing at the speed of 250-1000 r/min for 5-10 min, feeding until the granules and the powder are weighed to be weight-loss, and adding short glass fibers into the glass fiber scale;
step three: setting the feeding proportion of a weight loss scale according to the weight parts of the aggregate, the powder and the glass fiber, wherein the extrusion temperature is 220-265 ℃, and the screw rotation speed is 160-250 rpm;
step four: and cooling the melt output extruded by the die head of the double-screw extruder to prepare granules, namely the novel PC/SI-PC/PBT alloy material.
Examples 2 to 6
The toughened PC/SI-PC/PBT alloy materials of the embodiments 2 to 6 have basically the same raw materials and preparation methods as those of the embodiment 1, except that the specific components and proportions are slightly different, which are specifically listed in Table 1:
TABLE 1 composition and dosage tables for examples 1-6
Comparative example 1
The alloy material of this comparative example was substantially the same as the raw materials and components of example 1, except that: siloxane copolymerized polycarbonate is not added in the alloy material, and only 5 parts of toughening agent MBS are added. A PC/PBT alloy material was obtained by the same production method as in example 1.
Comparative example 2
The alloy material of this comparative example was substantially the same as the raw materials and components of example 1, except that: siloxane copolymerized polycarbonate is not added in the alloy material, and only 13 parts of toughening agent MBS are added. A PC/PBT alloy material was obtained by the same production method as in example 1.
Comparative example 3
The alloy material of this comparative example was substantially the same as the raw materials and components of example 1, except that: the alloy material does not contain a compatilizer or a transesterification inhibitor. A PC/SI-PC/PBT alloy material was obtained by the same production method as in example 1.
The alloy materials prepared in the above examples 1 to 6 and comparative examples 1 to 3 were subjected to performance tests, and the specific test methods and test results are shown in table 2.
Table 2 table of performance test results
Therefore, the toughened PC/SI-PC/PBT alloy material disclosed by the invention has high tensile strength, high bending strength and modulus, high load deformation temperature, high izod notched impact strength at the low temperature of-30 ℃ and UL94 flame retardant V-0 grade, and has more stable high-low temperature toughness, mechanical strength and load deformation temperature compared with the traditional PC/PBT material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The toughened PC/SI-PC/PBT alloy material is characterized by comprising the following components in parts by weight:
the melt index of the polycarbonate is 8-20 g/10 min; the siloxane copolycarbonate has a silicon content greater than 8%; the melt index of the polybutylene terephthalate is 5-130 g/10 min.
2. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene terpolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate copolymer and methyl methacrylate-organic silicon copolymer.
3. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the compatilizer is one or more of EMA-g-MAH, POE-g-MAH, EVA-g-MAH, EBA-g-MAH and PC/PBT transesterification products.
4. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the ester exchange inhibitor is one or more of alkyl phosphate ester exchange inhibitor, sodium dihydrogen phosphate, phosphite ester, anhydrous sodium dihydrogen phosphate and triphenyl phosphite.
5. The toughened PC/SI-PC/PBT alloy material according to claim 1, wherein the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
6. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the light stabilizer is selected from one or more of salicylate, benzoate, benzophenone, benzotriazole, substituted acrylonitrile, oxamide, organic nickel complex and hindered amine light stabilizer.
7. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the lubricant is selected from one or more of polyethylene wax, calcium stearate and silicone.
8. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the chopped glass fiber is selected from chopped fibers which are 3-4.5 mm in length, 7-13 mu m in fiber diameter and subjected to silane surface treatment.
9. The toughened PC/SI-PC/PBT alloy material of claim 1, wherein: the flame retardant is selected from one or more of antimony trioxide, decabromodiphenylethane, a flame retardant plasticizer RDP and a flame retardant plasticizer BDP; the flame-retardant synergist is polyphenyl ether and/or polytetrafluoroethylene.
10. A method for preparing a toughened PC/SI-PC/PBT alloy material according to any one of claims 1-9, comprising the steps of:
uniformly mixing the dried components in proportion, and then extruding and granulating the obtained mixture in a double-screw extruder, wherein the extrusion temperature of each area of the double-screw extruder is 220-265 ℃, the feeding speed is 30-100kg/h, and the rotating speed of a screw is 110-250 rpm; and cooling to obtain the toughened PC/SI-PC/PBT alloy material.
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