CN102911487A - Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof - Google Patents
Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof Download PDFInfo
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- CN102911487A CN102911487A CN2012104606045A CN201210460604A CN102911487A CN 102911487 A CN102911487 A CN 102911487A CN 2012104606045 A CN2012104606045 A CN 2012104606045A CN 201210460604 A CN201210460604 A CN 201210460604A CN 102911487 A CN102911487 A CN 102911487A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and a preparation method thereof. The glass fiber reinforced PBT/ASA alloy material is characterized by comprising raw materials of 5-87.6 wt.% of a PBT resin, 1-30 wt.% of an ASA resin, 0-20 wt.% of a styrene-arcylonitrile (SAN) resin, 10-30 wt.% of glass fiber, 1-8 wt.% of a flexibilizer, 0.1-4 wt.% of a compatilizer, 0.1-1wt.% of an antioxidant, 0.1-1wt.% of a lubricating agent and 0.1-1wt.% of a nucleating agent. The preparation method includes feeding the raw materials into a double-screw extruder, adding the glass fiber from a side feeding port, and extruding produced granules at the temperature of 210-280 DEG C. The glass fiber reinforced PBT/ASA alloy material has an excellent low-warpage performance and size stability and simultaneously has a good processing performance of a glass fiber reinforced PBT material.
Description
Technical field
The invention provides a kind of fiber glass reinforced PBT/ASA alloy material and preparation method thereof, belong to technical field of polymer materials.
Background technology
Polybutylene terephthalate (PBT) is as one of the world's five large-engineering plastics, with its excellent processing characteristics, resistance toheat and insulating property, is widely used in the fields such as electric, automobile, mechanical means.
In recent years, along with the enhancing of people's environmental consciousness and the needs of saving cost, the large thin-wall of plastic part and lightweight become a development trend of modified plastic industry gradually.In the fiber glass reinforced PBT material owing to having the orientation of glass and an anisotropy crystallization property of PBT resin, so that there is comparatively serious warpage issues in fiber glass reinforced PBT when the preparation large-scale thin wall parts, the warpage issues of fiber glass reinforced PBT has become a bottleneck that hinders the PBT Materials, therefore, the exploitation that very large energy hangs down warp glass fiber enhancing PBT material has been dropped in present main flow factory commercial city in the world.
The warpage of improving fiber glass reinforced PBT material mainly contains three approach: one, adopt the glass of special requirement to substitute common glass or mix with common glass PBT is carried out enhancing modified; Two, use sphere, sheet and whisker class filler to mix with glass PBT is carried out modification; Three, PBT and other thermoplastic materials are carried out preparing fiberglass reinforcing PBT alloy material after the blend.
Publication number is to have proposed use magnesium salt whisker and glass in the patent of CN 1563186A to be mixed with low warp glass fiber and to strengthen the PBT material, but the adding of the inorganic materials such as magnesium salt whisker on the mechanical property of fiber glass reinforced PBT material particularly shock strength produced larger impact.
Publication number is to have prepared a kind of fiber glass reinforced PBT/ABS alloy composite materials in the patent of CN 101220198A, but since in the alloy weather resistance of ABS relatively poor, so the range of application of material has been subject to certain restriction.
Publication number is the preparation method who has proposed a kind of PBT/ASA alloy material of good interface compatibility in the patent of CN 101838443A, but the preparation method of not mentioned fiber glass reinforced PBT/ASA alloy material in the patent.
Summary of the invention
The purpose of this invention is to provide a kind of fiber glass reinforced PBT of low warpage/ASA alloy material and preparation method thereof, this material has excellent low warpage properties energy when having the excellent mechanical property of fiber glass reinforced PBT material and weather resistance.
In order to achieve the above object, technical scheme of the present invention provides a kind of fiber glass reinforced PBT/ASA alloy material, it is characterized in that, its raw material comprises:
PBT resin 5-87.6 weight part;
ASA resin 1-30 weight part;
SAN resin 0-20 weight part;
Glass fibre 10-30 weight part;
Toughner 1-8 weight part;
Compatilizer 0.1-4 weight part;
Antioxidant 0.1-1 weight part;
Lubricant 0.1-1 weight part;
Nucleator 0.1-1 weight part.
Preferably, described PBT resin is one or both polymkeric substance that obtain by homopolymerization, copolymerization or homopolymerization and copolyreaction in terephthalic acid or its ester derivative and butyleneglycol or its ester derivative, and its intrinsic viscosity is 0.8-1.3ml/g.
Preferably, described ASA resin for take SAN as matrix by emulsion method or mass polymerization obtain take the rubber elastomer that contains acrylate group as core, take styrene-acrylonitrile copolymer as shell, the acrylonitrile-styrene-acrylic ester terpolymer that namely has core-shell structure, the weight content that contains the rubber elastomer of acrylate group in this terpolymer is 10-80%.
Preferably, described SAN resin is styrene-acrylonitrile copolymer.
Preferably, described glass fibre is for carrying out the surface-treated glass fibre through the silane coupling agent that contains epoxide group or amido functional group.
Preferably, described toughner is ethene or propylene analog thermoplastic elastomer.
Further, described toughner is any one or the two or more compositions in ethylene-methyl acrylate copolymer, ethylene-methyl acrylate multipolymer, ethylene-vinyl acetate copolymer and the Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
Preferably, described compatilizer is maleic anhydride type compatilizer, epoxy type compatilizer or both compositions.
Further, described maleic anhydride type compatilizer is the multipolymer of maleic anhydride styrol copolymer (SMA), maleic anhydride graft EPDM, maleic anhydride and ABS or the multipolymer of maleic anhydride and ASA.
Further, described epoxy type compatilizer is the graft copolymer of graft copolymer, Resins, epoxy and ABS of bisphenol A type epoxy resin, Resins, epoxy and cinnamic graft copolymer, Resins, epoxy and vinyl cyanide or the graft copolymer of Resins, epoxy and ASA.
Preferably, described antioxidant is any one or the two or more composition in phenols, thioether class and the phosphorous acid esters antioxidant.
Further, described antioxidant is the composition of composition, phenols and phosphorous acid esters antioxidant of phenols and thioether class antioxidant or the composition of phenols, thioether class and phosphorous acid esters antioxidant.
Further; described phenol antioxidant is that four (methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester) methane, N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid or N, N '-two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine.
Further, described thioether class antioxidant is the two lauryl alcohol esters of Pentaerythritols ten dithio propyl ester or thio-2 acid.
Further, described phosphorous acid esters antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, four (2, the 4-di-tert-butylphenol)-4,4 '-xenyl diphosphites or two (2,6-di-tert-butyl-phenyl) pentaerythritol diphosphites or triphenyl phosphite.
Preferably, described nucleator is that grain diameter is less than inorganic nucleator, organic nucleating agent or both compositions of 1 μ m.
Further, described inorganic nucleator is talcum powder, any one in polynite and the calcium carbonate or two or more mixtures.
Further, described organic nucleating agent is any one or the two or more mixture in Sodium Benzoate, sorbyl alcohol dibenzyl ester and the montanate.
Preferably, described lubricant is high molecular polysiloxane, polyethylene wax or pentaerythritol stearate.
In addition, component of the present invention can add additive commonly used, gives material different performances, and addible component also comprises any releasing agent, photostabilizer except above-mentioned antioxidant, anti-electrostatic agent, tinting material etc.
The present invention also provides the preparation method of above-mentioned fiber glass reinforced PBT/ASA alloy material, it is characterized in that, concrete steps are:
The first step: take by weighing in proportion each starting material, with dry good PBT resin, ASA resin, SAN resin, toughner, compatilizer, antioxidant, lubricant and nucleator high-speed mixing are evenly rear stand-by respectively in advance;
Second step: the mixture that the first step is obtained is fed in the twin screw extruder by main feeding hopper, glass fibre is added extruding pelletization in 210-280 ℃ temperature range from the side spout.
The advantage of the fiber glass reinforced PBT of the present invention's preparation/ASA alloy material is:
1, compare low warpage properties energy and the dimensional stability with excellence with traditional fiber glass reinforced PBT, this material also has the good processing characteristics of fiber glass reinforced PBT material simultaneously.
2, compare with existing other fiberglass reinforcing PBT alloy materials, the compatilizer of employing has solved the poor shortcoming of consistency of PBT/ASA, and the alloy material that the present invention is prepared has good mechanical property.
Description of drawings
Fig. 1 is the schematic diagram of the first warpage situation;
Fig. 2 is the schematic diagram of the second warpage situation;
Fig. 3 is the schematic diagram of the third warpage situation.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, and cooperate accompanying drawing to be described in detail below.
In the raw material that embodiment 1-11 adopts, PBT is that density 1.30, intrinsic viscosity are the polybutylene terephthalate (the PBT 1200-211M of Changchun, Taiwan chemical industry) of 0.8ml/g; The ASA resin is commercial resins (XC-180 of bright and beautiful lake Ri Li company, the weight content that wherein contains the rubber elastomer of acrylate group is 10-80%); The SAN resin is styrene-acrylonitrile copolymer (the strange beautiful PN-106 in Taiwan); Toughner is Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (the Elvoloy PTW of U.S. Dupont company); The epoxy compatilizer is commercially available bisphenol A type epoxy resin (German BASF E-20); Maleic anhydride type compatilizer is U.S. SARTOMER company fire resistant resin maleic anhydride styrol copolymer; Oxidation inhibitor is four [β (3.5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox 1010 of Ciba company); Lubricant is the PETS of U.S. Long Sha company, and nucleator is 3000 commercially available purpose superfine talcum powders.Described glass fibre is that the glass fibre trade mark is ER13-2000-988A, the chopped glass fiber that megalith group produces, and it carries out surface treatment through () silane coupling agent.
Embodiment 1
Learn from else's experience 120 ℃ dry polybutylene terephthalate 87.6 weight parts, ASA resin 1 weight part, toughner 1 weight part, maleic anhydride type compatilizer 0.1 weight part, antioxidant 1010 0.1 weight part, lubricant 0.1 weight part, nucleator 0.1 weight part behind the 4h, in super mixer, mix after, drop into the main feeder of twin screw extruder, chopped glass fiber with 10 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 2
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 69.2 weight parts, ASA resin 5 weight parts, SAN resin 10 weight parts, toughner 1 weight part, maleic anhydride type compatilizer 0.5 weight part, antioxidant 1010 0.1 weight part, lubricant 0.1 weight part, nucleator 0.1 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 3
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 26 weight parts, ASA resin 30 weight parts, SAN resin 20 weight parts, toughner 2 weight parts, maleic anhydride type compatilizer 0.5 weight part, epoxy type compatilizer 0.5 weight part, irgasfos 168 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 4
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 66 weight parts, ASA resin 15 weight parts, toughner 3 weight parts, irgasfos 168 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 5
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 46 weight parts, ASA resin 15 weight parts, SAN resin 5 weight parts, toughner 3 weight parts, antioxidant 1010 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 6
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 36 weight parts, ASA resin 15 weight parts, SAN resin 15 weight parts, toughner 3 weight parts, irgasfos 168 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 7
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 45 weight parts, ASA resin 15 weight parts, SAN resin 5 weight parts, toughner 3 weight parts, maleic anhydride type compatilizer 1 weight part, antioxidant 1010 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, will mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 8
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 45 weight parts, ASA resin 15 weight parts, SAN resin 5 weight parts, toughner 3 weight parts, epoxy type compatilizer 1 weight part, irgasfos 168 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 9
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 45 weight parts, ASA resin 15 weight parts, SAN resin 5 weight parts, toughner 3 weight parts, maleic anhydride type compatilizer 0.5 weight part, epoxy type compatilizer 0.5 weight part, irgasfos 168 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 10
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 35 weight parts, ASA resin 15 weight parts, SAN resin 15 weight parts, toughner 3 weight parts, maleic anhydride type compatilizer 0.5 weight part, epoxy type compatilizer 0.5 weight part, antioxidant 1010 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, after in super mixer, mixing, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Embodiment 11
Learn from else's experience 120 ℃ and dry polybutylene terephthalate 36 weight parts, ASA resin 30 weight parts, toughner 2 weight parts, maleic anhydride type compatilizer 0.5 weight part, epoxy type compatilizer 0.5 weight part, antioxidant 1010 0.3 weight part, lubricant 0.3 weight part, nucleator 0.4 weight part behind the 4h, in super mixer, mix, drop into the main feeder of twin screw extruder, chopped glass fiber with 30 weight parts is fed by the side feeder simultaneously, granulation behind twin-screw extrusion obtains fiber glass reinforced PBT/ASA alloy material.Complete processing is: 230 ℃ of district's temperature, 250 ℃ of two district's temperature, 250 ℃ of three district's temperature, 250 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature, 240 ℃ of seven district's temperature, 230 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; 300 rev/mins of engine speeds.
Method for testing performance of the present invention and standard are:
Tensile strength is tested according to the ISO527-2 standard; Flexural strength and modulus in flexure are tested according to the ISO178 standard; Notched Izod impact strength is tested according to the ISO179 standard; The warpage performance is tested according to self-defined standard, and sample is injection molded into 60 * 60 * 1mm side plate, apart from the distance D between the reference plane, three kinds of warpage situations occur, as Figure 1-3 with the top after the side's of the measurement slab warping of secondary element image instrument.The performance test results is as shown in the table:
Table 1
As can be seen from Table 1, fiber glass reinforced PBT prepared in accordance with the present invention/ASA alloy material not only has good mechanical property, and have excellent low warpage properties energy, can be widely used in the field that electric, automobile, mechanical means etc. are had relatively high expectations to dimension stability and warpage performance.
Claims (10)
1. fiber glass reinforced PBT/ASA alloy material is characterized in that, its raw material comprises:
PBT resin 5-87.6 weight part;
ASA resin 1-30 weight part;
SAN resin 0-20 weight part;
Glass fibre 10-30 weight part;
Toughner 1-8 weight part;
Compatilizer 0.1-4 weight part;
Antioxidant 0.1-1 weight part;
Lubricant 0.1-1 weight part;
Nucleator 0.1-1 weight part.
2. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material, it is characterized in that, described PBT resin is one or both polymkeric substance that obtain by homopolymerization, copolymerization or homopolymerization and copolyreaction in terephthalic acid or its ester derivative and butyleneglycol or its ester derivative, and its intrinsic viscosity is 0.8-1.3ml/g.
3. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material, it is characterized in that, described ASA resin for take SAN as matrix by emulsion method or mass polymerization obtain take the rubber elastomer that contains acrylate group as core, take styrene-acrylonitrile copolymer as shell, the acrylonitrile-styrene-acrylic ester terpolymer that namely has core-shell structure, the weight content that contains the rubber elastomer of acrylate group in this terpolymer is 10-80%.
4. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described glass fibre is for carrying out the surface-treated glass fibre through the silane coupling agent that contains epoxide group or amido functional group.
5. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described toughner is ethene or propylene analog thermoplastic elastomer.
6. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described compatilizer is maleic anhydride type compatilizer, epoxy type compatilizer or both compositions.
7. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described antioxidant is any one or the two or more composition in phenols, thioether class and the phosphorous acid esters antioxidant.
8. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described nucleator is that grain diameter is less than inorganic nucleator, organic nucleating agent or both compositions of 1 μ m.
9. fiber glass reinforced PBT as claimed in claim 1/ASA alloy material is characterized in that, described lubricant is high molecular polysiloxane, polyethylene wax or pentaerythritol stearate.
10. the preparation method of fiber glass reinforced PBT claimed in claim 1/ASA alloy material is characterized in that, concrete steps are:
The first step: take by weighing in proportion each starting material, with dry good PBT resin, ASA resin, SAN resin, toughner, compatilizer, antioxidant, lubricant and nucleator high-speed mixing are evenly rear stand-by respectively in advance;
Second step: the mixture that the first step is obtained is fed in the twin screw extruder by main feeding hopper, and extruding pelletization in 210-280 ℃ temperature range adds glass fibre from the side spout, last tie rod, pelletizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104606045A CN102911487A (en) | 2012-08-23 | 2012-11-15 | Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210303434.X | 2012-08-23 | ||
| CN201210303434 | 2012-08-23 | ||
| CN2012104606045A CN102911487A (en) | 2012-08-23 | 2012-11-15 | Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102911487A true CN102911487A (en) | 2013-02-06 |
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| CN2012104606045A Pending CN102911487A (en) | 2012-08-23 | 2012-11-15 | Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof |
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| CN103319862A (en) * | 2013-06-24 | 2013-09-25 | 苏州新区佳合塑胶有限公司 | Halogen-free flame-retardant PBT/ASA (Polybutylece Terephthalate/Acrylonitrile-Styrene-Acrylate) alloy |
| CN104098878A (en) * | 2014-07-30 | 2014-10-15 | 苏州威瑞成新材料有限公司 | High-rigidity weather-proof PBT/ASA alloy |
| CN105273374A (en) * | 2015-11-18 | 2016-01-27 | 上海俊尓新材料有限公司 | High-performance anti-warping glass fiber reinforced PBT/ASA alloy material |
| CN105924876A (en) * | 2016-06-13 | 2016-09-07 | 上海金山锦湖日丽塑料有限公司 | Glass fiber reinforced ASA (acrylonitrile-styrene-acrylate copolymer)/PETG (polyethylene terephthalate glycol) alloy material and preparation method thereof |
| CN106009376A (en) * | 2016-06-17 | 2016-10-12 | 金发科技股份有限公司 | Self-enhancement profiled material and preparation method and application thereof |
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| CN106090593A (en) * | 2016-06-17 | 2016-11-09 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
| CN106084541A (en) * | 2016-06-17 | 2016-11-09 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
| CN107083030A (en) * | 2017-06-02 | 2017-08-22 | 浙江华杰材料科技有限公司 | A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials and preparation method thereof |
| WO2017215570A1 (en) * | 2016-06-17 | 2017-12-21 | 金发科技股份有限公司 | Reinforced profile, preparation method therefor and application thereof |
| CN108948686A (en) * | 2018-07-19 | 2018-12-07 | 广东顺德顺炎新材料股份有限公司 | Fiberglass reinforced ASA/PBT alloy automobile base of headlight material and preparation method thereof |
| CN109401221A (en) * | 2018-09-30 | 2019-03-01 | 金旸（厦门）新材料科技有限公司 | Weather-proof low warp glass fiber enhancing PBT/AS/ASA material of one kind and preparation method thereof |
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| CN110819080A (en) * | 2018-08-07 | 2020-02-21 | 中国石油化工股份有限公司 | Flame-retardant reinforced PBT (polybutylene terephthalate) material composition, flame-retardant reinforced PBT material and preparation method thereof |
| CN111073233A (en) * | 2019-12-30 | 2020-04-28 | 浙江新力新材料股份有限公司 | High-toughness PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof |
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| CN103319862A (en) * | 2013-06-24 | 2013-09-25 | 苏州新区佳合塑胶有限公司 | Halogen-free flame-retardant PBT/ASA (Polybutylece Terephthalate/Acrylonitrile-Styrene-Acrylate) alloy |
| CN104098878A (en) * | 2014-07-30 | 2014-10-15 | 苏州威瑞成新材料有限公司 | High-rigidity weather-proof PBT/ASA alloy |
| CN104098878B (en) * | 2014-07-30 | 2016-03-30 | 苏州威瑞成新材料有限公司 | The weather-proof PBT/ASA alloy of high rigidity |
| CN105273374A (en) * | 2015-11-18 | 2016-01-27 | 上海俊尓新材料有限公司 | High-performance anti-warping glass fiber reinforced PBT/ASA alloy material |
| CN105924876B (en) * | 2016-06-13 | 2018-09-28 | 上海金山锦湖日丽塑料有限公司 | Fiberglass reinforced ASA/PETG alloy materials and preparation method thereof |
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| CN106009376A (en) * | 2016-06-17 | 2016-10-12 | 金发科技股份有限公司 | Self-enhancement profiled material and preparation method and application thereof |
| CN106084541A (en) * | 2016-06-17 | 2016-11-09 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
| CN106090593B (en) * | 2016-06-17 | 2019-05-31 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
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| CN106065137A (en) * | 2016-06-17 | 2016-11-02 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
| CN106084541B (en) * | 2016-06-17 | 2019-01-22 | 金发科技股份有限公司 | A kind of self-reinforcing profile shapes and its preparation method and application |
| CN109844023A (en) * | 2016-10-14 | 2019-06-04 | 三井化学株式会社 | Resin combination and formed body |
| EP3527622A4 (en) * | 2016-10-14 | 2020-03-18 | Mitsui Chemicals, Inc. | Resin composition and molded article |
| CN106589844B (en) * | 2016-12-01 | 2021-02-05 | 广州科苑新型材料有限公司 | PBT/ASA alloy material and preparation method thereof |
| CN107083030A (en) * | 2017-06-02 | 2017-08-22 | 浙江华杰材料科技有限公司 | A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials and preparation method thereof |
| CN108948686A (en) * | 2018-07-19 | 2018-12-07 | 广东顺德顺炎新材料股份有限公司 | Fiberglass reinforced ASA/PBT alloy automobile base of headlight material and preparation method thereof |
| CN108948686B (en) * | 2018-07-19 | 2020-08-11 | 广东顺德顺炎新材料股份有限公司 | Glass fiber reinforced ASA/PBT alloy automobile lamp base material and preparation method thereof |
| CN110819080A (en) * | 2018-08-07 | 2020-02-21 | 中国石油化工股份有限公司 | Flame-retardant reinforced PBT (polybutylene terephthalate) material composition, flame-retardant reinforced PBT material and preparation method thereof |
| CN109401221A (en) * | 2018-09-30 | 2019-03-01 | 金旸（厦门）新材料科技有限公司 | Weather-proof low warp glass fiber enhancing PBT/AS/ASA material of one kind 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 |
| CN111073233A (en) * | 2019-12-30 | 2020-04-28 | 浙江新力新材料股份有限公司 | High-toughness PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof |
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| CN112210172B (en) * | 2020-10-13 | 2023-05-30 | 上海金发科技发展有限公司 | Creep-resistant glass fiber reinforced styrene compound and preparation method thereof |
| CN112430383A (en) * | 2020-11-19 | 2021-03-02 | 中广核俊尔（上海）新材料有限公司 | High-fluidity reinforced PET/ASA material and preparation method thereof |
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