CN106589844B - PBT/ASA alloy material and preparation method thereof - Google Patents
PBT/ASA alloy material and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 41
- 239000003063 flame retardant Substances 0.000 claims abstract description 41
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004793 Polystyrene Substances 0.000 claims abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002223 polystyrene Polymers 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 60
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 13
- 229920000638 styrene acrylonitrile Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 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 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 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 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 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 3
- 230000007547 defect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 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 description 2
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 Polybutylene terephthalate Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- 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
-
- 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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- 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
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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 discloses a PBT/ASA alloy material and a preparation method thereof, wherein the alloy material comprises the following components in parts by weight: 20-65 parts of PBT resin, 20-50 parts of ASA resin, 10-35 parts of glass fiber, 15-25 parts of flame retardant, 0.5-5.0 parts of compatilizer 1, 1.0-3.0 parts of compatilizer 2, 0.5-5.0 parts of flow assistant and 0.1-3.0 parts of assistant, wherein the flame retardant is obtained by compounding main flame retardant brominated polystyrene and flame retardant synergist sodium antimonate according to the mass ratio of (10-20) to (4-5), the compatilizer 1 is styrene copolymer, and the compatilizer 2 is bisphenol A type epoxy resin with the epoxy value of 0.5-1.5. The PBT/ASA alloy material prepared by the invention has the flame retardant and impact resistance performances, is not easy to warp and has excellent comprehensive mechanical properties.
Description
Technical Field
The invention relates to the field of polymer composite engineering materials, in particular to a PBT/ASA alloy material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is a semi-crystalline polymer with excellent performance, has the characteristics of high strength, good electrical property, stable dimension, good heat resistance, low water absorption, easiness in molding and processing and the like, is widely applied to the industries of automobiles, electronic and electric products and mechanical manufacturing, and is the fifth major engineering plastic at present. However, the PBT resin has lower notch impact strength and larger molding shrinkage, and the development and application of the PBT resin in certain fields are limited to a certain extent.
In order to overcome the problem of low strength of the PBT resin, the mechanical property of the PBT resin can be obviously improved by reinforcing and modifying the PBT resin by the common glass fiber. However, the glass fiber reinforced PBT resin has the defect of excessive warping, and the application of the PBT is also limited.
The styrene-acrylonitrile-acrylate rubber (ASA) has mechanical properties of balanced toughness and rigidity, good dimensional stability, surface gloss, low temperature resistance and coloring resistance, and excellent weather resistance, so that the styrene-acrylonitrile-acrylate rubber is compounded with PBT resin to prepare a PBT/ASA alloy material, and the glass fiber reinforced PBT/ASA resin is not easy to warp and has excellent mechanical properties.
The prior art discloses a high-performance anti-warping glass fiber reinforced PBT/ASA alloy material which can be applied to workpieces such as truck exterior trim strips and the like which are easy to warp and have high aging requirements. The prior art also discloses a glass fiber reinforced PBT/ASA alloy material with excellent low-warpage performance, dimensional stability and excellent processability and a preparation method thereof. However, the existing PBT/ASA alloy material has the defect of insufficient flame retardance. For interior and exterior decorations of automobiles such as horn covers, grilles and the like, products need to meet the requirements of flame retardance and high temperature resistance, and in general, when a flame retardant and glass fibers are added into a PBT/ASA alloy material, the impact resistance of the material is remarkably reduced, and the PBT/ASA alloy material is difficult to meet the requirements of flame retardance and impact resistance at the same time.
Disclosure of Invention
Based on the PBT/ASA alloy material, the defects of the prior art are overcome, and the PBT/ASA alloy material has the flame-retardant and impact-resistant properties, is not easy to warp and has excellent comprehensive mechanical properties.
The invention also aims to provide a preparation method of the PBT/ASA alloy material.
The technical scheme is as follows:
the PBT/ASA alloy material comprises the following components in parts by weight:
the flame retardant is obtained by compounding a main flame retardant brominated polystyrene and a flame retardant synergist sodium antimonate according to a mass ratio of (10-20) to (4-5), wherein the compatilizer 1 is a vinyl monomer multipolymer, and the compatilizer 2 is bisphenol A type epoxy resin with an epoxy value of 0.5-1.5.
The inventor finds through experiments that when brominated polystyrene is selected as a main flame retardant and sodium antimonate is selected as a flame-retardant synergist, the brominated polystyrene is compounded according to the mass ratio of (10-20) to (4-5), and then the flame-retardant synergist is matched with bisphenol A epoxy resin with a specific epoxy value for use, the obtained PBT/ASA alloy material meets excellent flame-retardant performance, and meanwhile, the impact resistance of the PBT/ASA alloy material is not reduced due to the addition of the flame retardant. The reason is that: the bisphenol A epoxy resin and the ASA resin have good compatibility, in the extrusion process, an upper epoxy group of the bisphenol A epoxy resin can perform nucleophilic substitution reaction with a terminal hydroxyl group and a terminal carboxyl group on the PBT, the epoxy value of the bisphenol A epoxy resin influences the reaction degree of the bisphenol A epoxy resin and the PBT, when the epoxy value is within a certain range, the effect of the bisphenol A epoxy resin serving as a compatilizer between the PBT and the ASA is optimal, the influence of a flame retardant on the shock resistance of an alloy material can be compensated, sodium antimonate is selected as a flame-retardant synergist, the PBT decomposition caused by antimony trioxide at the PBT processing temperature can be avoided, and the mechanical property deterioration caused by the reduction of the molecular weight of the PBT is avoided.
In one embodiment, the PBT/ASA alloy material comprises the following components in parts by weight:
in one embodiment, the PBT resin has an Izod notched impact strength of 2 to 7KJ/m2。
In one embodiment, the PBT resin is in a cantilever beam notch punching modeThe impact strength is 2-7KJ/m2The relative density is 1.29-1.35 g/cm3The melting temperature is 220-230 ℃.
In one embodiment, the ASA resin has an Izod notched impact strength of 9 to 15KJ/m2。
In one embodiment, the ASA resin has an Izod notched impact strength of 9 to 15KJ/m2The relative density is 1.03-1.07 g/cm3The melting temperature is 210-240 ℃.
In one embodiment, the flow aid is SAN having a molecular weight of no more than 60000. The SAN is a styrene-acrylonitrile copolymer, and the inventor finds that when the molecular weight of the flow additive SAN is not more than 60000, the prepared PBT/ASA alloy material does not have a fiber floating phenomenon, the appearance quality of a product is remarkably improved, the melt index of the material is higher, and the processing flowability is good.
In one embodiment, the compatibilizer 1 is one or more of a styrene-maleic anhydride copolymer, an ethylene-methyl acrylate-glycidyl methacrylate copolymer, and a styrene-acrylonitrile-glycidyl methacrylate copolymer.
In one embodiment, the glass fiber is short glass fiber with the length of 3-5 mm.
In one embodiment, the auxiliary agent is a coupling agent, a lubricant and an antioxidant.
In one embodiment, the auxiliary agent comprises 0.1-1.0 part of coupling agent, 0.3-1.0 part of lubricant and 0.1-0.5 part of antioxidant.
In one embodiment, the coupling agent is a titanate coupling agent and/or a silane coupling agent.
In one embodiment, the lubricant is one or more of PETs, EBS, PE wax.
In one embodiment, the antioxidant is one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076.
The preparation method of the PBT/ASA alloy material comprises the following steps:
s1, drying the PBT and the ASA;
s2, weighing the raw materials according to the proportion, uniformly mixing, delivering to a double-screw extruder for melting, mixing and extruding, adding the glass fiber from the double-screw lateral feeding system while extruding, cooling, granulating, drying and packaging to obtain the PBT/ASA alloy material, wherein the temperature of each section of screw is 210-270 ℃.
In one embodiment, the step S1 is: PBT was dried at 110 ℃ for 2 hours and ASA resin was dried at 90 ℃ for 2 hours.
In one embodiment, the step S2 is: uniformly mixing PBT, ASA and a coupling agent in a high-speed stirrer, adding other powder materials into the mixture, continuously stirring and uniformly mixing at a high speed, conveying the mixture to a double-screw extruder for melting, mixing and extruding, adding glass fibers from a double-screw lateral feeding system while extruding, and distributing the temperature from a feeding section to a machine head as follows: 210 ℃, 245 ℃, 240 ℃, 235 ℃, 230 ℃, 220 ℃, 210 ℃, die: and cooling, granulating, drying and packaging at 245 ℃ to obtain the PBT/ASA alloy material.
The PBT/ASA alloy material is applied to the preparation of automotive interior and exterior trim products.
The invention has the beneficial effects that: according to the invention, brominated polystyrene is used as a main flame retardant, sodium antimonate is used as a flame retardant synergist, the flame retardant is compounded according to the mass ratio of (10-20) to (4-5), and the flame retardant is matched with bisphenol A epoxy resin with a specific epoxy value for use, so that the obtained PBT/ASA alloy material meets excellent flame retardant performance, the impact resistance of the PBT/ASA alloy material is not reduced due to the addition of the flame retardant, the alloy material has excellent flame retardant and impact resistance, and meanwhile, the alloy material is not easy to warp and has excellent comprehensive mechanical properties.
The invention can further ensure that the prepared PBT/ASA alloy material does not have fiber floating phenomenon by using the flow additive SAN with specific molecular weight, the appearance quality of the product is obviously improved, the melt index of the material is higher, and the processing fluidity is good.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The following examples used the following raw material types and manufacturers:
PBT: model 1100-211M, notched Izod impact Strength 5.0KJ/M2Taiwan Changchun Corp;
PBT: model 6129, notched Izod impact Strength 10KJ/m2Dupont company;
ASA: model PW-957, notched Izod impact Strength 14KJ/m2Qimei corporation;
ASA: model 003L, notched Izod impact Strength 25KJ/m2Aclo Inc.;
bisphenol a type epoxy resin: type CYD-127, epoxy value 1.1-1.3, Yueyangbailing petrochemical;
SAN, model EMI-200, molecular weight 4.2 million, Niesl;
SAN model SA-20, molecular weight 15 ten thousand, Zhonghai oil Lejin company;
glass fiber: length 4mm, boulder corporation;
other raw materials which are not particularly noted are all common commercial products.
Example 1
The PBT/ASA alloy material comprises the following formula: 65kg of PBT1100-211M, 20kg of ASA PW-957, 10kg of glass fiber, 15kg of flame retardant, 5kg of compatilizer styrene-acrylonitrile-glycidyl methacrylate copolymer, 1kg of compatilizer bisphenol A epoxy resin, 0.1kg of titanate coupling agent, 0.5kg of flow additive SAN EMI-200, 0.5kg of lubricant EBS, 0.5kg of lubricant PETs and 0.1kg of antioxidant 1010, wherein the flame retardant is prepared by compounding 10kg of decabromodiphenylethane and 5kg of sodium antimonate.
The preparation method of the PBT/ASA alloy material comprises the following steps:
s1, drying PBT at 110 ℃ for 2 hours, and drying ASA resin at 90 ℃ for 2 hours;
s2, uniformly mixing PBT, ASA and a coupling agent in a high-speed stirrer, adding other powder materials, continuously stirring at a high speed, uniformly mixing, sending to a double-screw extruder for melting, mixing and extruding, adding glass fibers from a double-screw lateral forced feeding system while extruding, and distributing the temperature from a feeding section to a machine head as follows: 210 ℃, 245 ℃, 240 ℃, 235 ℃, 230 ℃, 220 ℃, 210 ℃, die: and cooling, granulating, drying and packaging at 245 ℃ to obtain the PBT/ASA alloy material.
Example 2
The PBT/ASA alloy material comprises the following formula: 20kg of PBT1100-211M, 50kg of ASAPW-957, 35kg of glass fiber, 25kg of flame retardant, 0.5kg of compatilizer styrene-maleic anhydride copolymer, 3kg of compatilizer bisphenol A epoxy resin, 1kg of titanate coupling agent, 5kg of flow additive SAN EMI-200, 0.3kg of lubricant EBS, 0.3kg of antioxidant 1010 and 0.2kg of antioxidant 168, wherein the flame retardant is prepared by compounding 20kg of decabromodiphenylethane and 5kg of sodium antimonate.
The procedure was the same as in example 1.
Example 3
The PBT/ASA alloy material comprises the following formula: 50kg of PBT1100-211M, 30kg of ASA PW-957, 25kg of glass fiber, 18kg of flame retardant, 4kg of compatilizer styrene-maleic anhydride copolymer, 2kg of compatilizer bisphenol A epoxy resin, 0.2kg of titanate coupling agent, 2kg of flow assistant SANEMI-200, 0.3kg of lubricant EBS, 0.3kg of antioxidant 1076 and 0.2kg of antioxidant 168, wherein the flame retardant is prepared by compounding 14kg of brominated polystyrene and 4kg of sodium antimonate.
The procedure was the same as in example 1.
Example 4
The PBT/ASA alloy material comprises the following formula: 40kg of PBT1100-211M, 40kg of ASA PW-957, 20kg of glass fiber, 16kg of flame retardant, 5kg of compatilizer styrene-maleic anhydride copolymer, 2.5kg of compatilizer bisphenol A epoxy resin, 0.3kg of silane coupling agent, 4kg of flow assistant SANEMI-200, 0.3kg of lubricant EBS, 0.3kg of antioxidant 1076 and 0.2kg of antioxidant 168, wherein the flame retardant is prepared by compounding 12kg of brominated polystyrene and 4kg of sodium antimonate.
The procedure was the same as in example 1.
Example 5
The formulation and preparation are similar to example 1, except that PBT6129 is used instead of PBT 1100-211M.
Example 6
The formulation and preparation were similar to example 1 except ASAPW957 was replaced with ASA 003L.
Example 7
The formulation and preparation method were similar to example 1 except that SAN from brocade lake petrochemical production having a molecular weight of 8.5 ten thousand was substituted for SAN EMI-200 from example 1.
Example 8
The PBT/ASA alloy material comprises the following formula: 40kg of PBT1100-211M, 50kg of ASA PW-957, 15kg of glass fiber, 25kg of flame retardant, 5kg of compatilizer styrene-maleic anhydride copolymer, 2.5kg of compatilizer bisphenol A epoxy resin, 0.3kg of silane coupling agent, 4kg of flow assistant SANEMI-200, 0.3kg of lubricant EBS, 0.3kg of antioxidant 1076 and 0.2kg of antioxidant 168, wherein the flame retardant is prepared by compounding 12kg of brominated polystyrene and 4kg of sodium antimonate.
The procedure was the same as in example 1.
Example 9
The PBT/ASA alloy material comprises the following formula: 65kg of PBT1100-211M, 35kg of ASA PW-957, 25kg of glass fiber, 15kg of flame retardant, 5kg of compatilizer styrene-maleic anhydride copolymer, 2.5kg of compatilizer bisphenol A epoxy resin, 0.3kg of silane coupling agent, 4kg of flow assistant SANEMI-200, 0.3kg of lubricant EBS, 0.3kg of antioxidant 1076 and 0.2kg of antioxidant 168, wherein the flame retardant is prepared by compounding 12kg of brominated polystyrene and 4kg of sodium antimonate.
The procedure was the same as in example 1.
Comparative example 1
The formulation and preparation were similar to those of example 1, except that the bisphenol A type epoxy resin (type CYD-127) of example 1 was replaced with a bisphenol A type epoxy resin (type E-35) having an epoxy value of 0.3 to 0.4.
Comparative example 2
The formulation and preparation method are similar to example 1, except that antimony trioxide is used to replace the flame retardant synergist sodium antimonate.
The PBT/ASA alloy materials prepared in the above examples and comparative examples were dried at 110 ℃ for 2 hours, and injection-molded bars were prepared according to the same injection-molding conditions: the injection molding temperature is 240-: 35-60 mm/s. And (3) carrying out performance test on the injection-molded sample strip, wherein the detection standards are as follows: the tensile strength and the elongation at break adopt GB/T1040.2-2006; the bending strength is GB/T9341-2008; the impact strength of the cantilever beam notch is GB/T1843-2008; the thermal deformation temperature adopts GB/T1634.2-2004 and the load is 1.8 MPa; the flame retardant rating is UL-94, 1.60 mm; the melt index is GB/T3682-2000,265 ℃, and 2.16 kg; the appearance was visually observed.
The results of the performance tests of the examples and comparative examples are shown in tables 1 and 2.
Table 1 results of performance testing of examples
Table 2 comparative example performance test results
The performance test results show that the PBT/ASA alloy material prepared by the invention has the performances of flame retardance and impact resistance, is not easy to warp and has excellent comprehensive mechanical properties.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The PBT/ASA alloy material is characterized by comprising the following components in parts by weight:
the flame retardant is obtained by compounding a main flame retardant brominated polystyrene and a flame retardant synergist sodium antimonate according to a mass ratio of (10-20) to (4-5), wherein the compatilizer 1 is a vinyl monomer multipolymer, and the compatilizer 2 is bisphenol A type epoxy resin with an epoxy value of 0.5-1.5;
the flow aid is SAN with molecular weight not more than 60000.
2. The PBT/ASA alloy material of claim 1, wherein the PBT resin has an Izod notched impact strength of 2-7KJ/m2。
3. The PBT/ASA alloy material of claim 1, wherein the ASA resin has an Izod notched impact strength of 9-15KJ/m2。
4. The PBT/ASA alloy material according to claim 1, wherein the compatibilizer 1 is one or more of styrene-maleic anhydride copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, and styrene-acrylonitrile-glycidyl methacrylate copolymer.
5. The PBT/ASA alloy material according to claim 1, wherein the glass fiber is chopped glass fiber with a length of 3-5 mm.
6. The PBT/ASA alloy material of claim 1, wherein the additive is one or more of a coupling agent, a lubricant, and an antioxidant.
7. The method for preparing the PBT/ASA alloy material according to any one of claims 1 to 6, wherein the method comprises the following steps:
s1, drying the PBT and the ASA;
s2, weighing the raw materials according to the proportion, uniformly mixing, delivering to a double-screw extruder for melting, mixing and extruding, adding the glass fiber from the double-screw lateral forced feeding system while extruding, wherein the temperature of each section of screw is 210-270 ℃, and then cooling, granulating, drying and packaging to obtain the PBT/ASA alloy material.
8. Use of the PBT/ASA alloy material according to any one of claims 1 to 6 for the preparation of automotive interior and exterior trim articles.
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| WO2019167292A1 (en) * | 2018-03-01 | 2019-09-06 | 三菱エンジニアリングプラスチックス株式会社 | Molding of polybutylene terephthalate resin composition |
| JP7065680B2 (en) * | 2018-03-01 | 2022-05-12 | 三菱エンジニアリングプラスチックス株式会社 | Polybutylene terephthalate resin composition |
| CN108530850B (en) * | 2018-04-28 | 2019-08-02 | 吉林恒辉新材料有限公司 | A kind of fire retardant PBT with no halogen/ASA alloy and preparation method thereof |
| CN108485214B (en) * | 2018-04-28 | 2019-08-02 | 吉林恒辉新材料有限公司 | A kind of glass fiber reinforcement PBT/ASA alloy and preparation method thereof |
| CN109836783A (en) * | 2018-12-29 | 2019-06-04 | 太仓市华鼎塑料有限公司 | A kind of antistatic fiber glass reinforced PBT/ASA composite material and preparation method thereof |
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| CN102911487A (en) * | 2012-08-23 | 2013-02-06 | 上海金发科技发展有限公司 | Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof |
| CN103724953A (en) * | 2014-01-16 | 2014-04-16 | 厦门市天宇塑料工业有限公司 | Special low-warpage flame-retardant reinforced PBT (polybutylene terephthalate) material for relay and application of material |
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| CN102911487A (en) * | 2012-08-23 | 2013-02-06 | 上海金发科技发展有限公司 | Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof |
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