CN108530850A - A kind of fire retardant PBT with no halogen/ASA alloys and preparation method thereof - Google Patents
A kind of fire retardant PBT with no halogen/ASA alloys and preparation method thereof Download PDFInfo
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- CN108530850A CN108530850A CN201810408931.3A CN201810408931A CN108530850A CN 108530850 A CN108530850 A CN 108530850A CN 201810408931 A CN201810408931 A CN 201810408931A CN 108530850 A CN108530850 A CN 108530850A
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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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
A kind of fire retardant PBT with no halogen/ASA alloys of present invention offer and preparation method thereof.Fire retardant PBT with no halogen provided by the invention/ASA alloys include polybutylene terephthalate (PBT) 30~55%,Acrylonitrile styrene acrylic ester copolymer 10~20%,Halogen-free flame retardants 15~20%,Glass fibre 10~20%,Polymethyl methacrylate 3~8%,Antioxidant 0.3~1% and processing aid 0.4~1%,Flame retardant property is improved by halogen-free flame retardants,UL94 (1.6mm) is V0 grades,Intensity is improved by the cooperation between glass fibre and PBT and ASA simultaneously,Tensile strength is up to 107.3MPa,Bending strength is up to 155.8MPa,Improve the interface compatibility between each component using polymethyl methacrylate as compatilizer,Toughness is improved while proof strength improves,Notch impact strength is up to 6.9kJm2。
Description
Technical field
The present invention relates to Technology For Polymer Alloy field, more particularly to a kind of fire retardant PBT with no halogen/ASA alloys and its preparation
Method.
Background technology
Polybutylene terephthalate (PBT) (PBT) is a kind of semi-crystalline polymer of function admirable, has intensity high, electrical
Can good, dimensionally stable, it is heat-resist, water absorption rate is low and is easy to processing and forming the features such as, be widely used in automobile, electronic apparatus with
And machine industry, the fifth-largest engineering plastics are had become at present.However, the notch impact strength of PBT resin is relatively low, molding is received
It contracts larger, these problems limit development and application of the PBT resin in certain fields to a certain extent.
Acrylonitrile-styrene-acrylic ester terpolymer (ASA) is similar with the structure of ABS, with without unsaturated double-bond
Acrylic rubber instead of the butadiene rubber containing unsaturated double-bond in ABS.It remains ABS is had as engineering plastics
The splendid mechanical and physical performance having, while degradation, aging, colour fading caused by ultraviolet radiation resisting can be not only supported, while to big
It is decomposed caused by the high temperature in oxidation process in gas or discoloration has strong guarantee, be thus greatly improved material
Anti-aging and weathering performance, is suitable for exterior material.
The PBT/ASA alloys that PBT and ASA are blended are taken full advantage of into the crystallinity of PBT and the amorphism of ASA, both
PBT impact strengths can be overcome relatively low, the big disadvantage of molding shrinkage, while the not high disadvantage of ASA heat resistances is compensated for again, have
There are excellent mechanical property, dimensional stability, molding processibility and chemical-resistant, weatherability etc., is a kind of excellent engineering
Plastic alloy, but the anti-flammability of PBT/ASA alloys is bad.
Its anti-flammability can be effectively improved by adding fire retardant into co-mixing system.For a long time, PBT/ASA systems continue to use
Fire retardant be mostly halogenated flame retardant, with the development of society, people to environmental protection requirement it is higher and higher, in view of halogenated flame retardant
Various drawbacks, European Union discloses WEEE and ROHS two instructions for 2003, by the toxicity of halogen flame and environmental problem
Arguement is pushed to a new high, and selects halogen-free flame retardants that halogenated flame retardant is replaced to become trend of the times.
At the same time, the type of fire retardant not only affects the flame retardant property of co-mixing system, to the mechanical property of co-mixing system
Can also have a great impact.Studies have shown that a variety of fire retardants can reduce the intensity of co-mixing system while improving flame retardant property
Or toughness.
Invention content
The purpose of the present invention is to provide a kind of fire retardant PBT with no halogen/ASA alloys and preparation method thereof.It is provided by the invention
Fire retardant PBT with no halogen/ASA alloys have good mechanical property and flame retardant property.
The present invention provides a kind of fire retardant PBT with no halogen/ASA alloys, include the component of following mass content：
Polybutylene terephthalate (PBT) 30~55%
Acrylonitrile-styrene-acrylic ester copolymer 10~20%
Halogen-free flame retardants 15~20%
Glass fibre 10~20%
Polymethyl methacrylate 3~8%
Antioxidant 0.3~1%
Processing aid 0.4~1%.
Preferably, the fire retardant PBT with no halogen/ASA alloys include the component of following mass content：
Polybutylene terephthalate (PBT) 35~50%
Acrylonitrile-styrene-acrylic ester copolymer 12~18%
Halogen-free flame retardants 16~19%
Glass fibre 12~18%
Polymethyl methacrylate 4~7%
Antioxidant 0.4~0.9%
Processing aid 0.5~0.8%.
Preferably, the inherent viscosity of the polybutylene terephthalate (PBT) is 0.98~1.1.
Preferably, the mass content of acrylonitrile is 15~45% in the acrylonitrile-styrene-acrylic ester copolymer,
The mass content of styrene is 40~60%, and the mass content of acrylate is 5~30%.
Preferably, the halogen-free flame retardants is hypophosphites based flame retardant.
Preferably, the glass fibre is alkali-free glass fibre.
Preferably, the glass fibre is a diameter of 9~14 μm of continuous long fiber.
Preferably, the antioxidant include four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and
Three (2,4- di-tert-butylphenols) phosphite esters.
Preferably, the processing aid includes cyclic butylene terephthalate.
The present invention also provides a kind of preparation methods of fire retardant PBT with no halogen described in above-mentioned technical proposal/ASA alloys, including
Following steps：
(1) by polybutylene terephthalate (PBT), acrylonitrile-styrene-acrylic ester copolymer, poly-methyl methacrylate
Ester, antioxidant and processing aid mixing, obtain matrix material；
(2) it is squeezed out after mixing the matrix material that the step (1) obtains with halogen-free flame retardants and glass fibre, obtains Halogen
Flame-retardant PBT/ASA alloys.
The present invention provides a kind of fire retardant PBT with no halogen/ASA alloys, include the component of following mass content：Poly- terephthaldehyde
Sour butanediol ester 30~55%, acrylonitrile-styrene-acrylic ester copolymer 10~20%, halogen-free flame retardants 15~20%, glass
Glass fiber 10~20%, polymethyl methacrylate 3~8%, antioxidant 0.3~1% and processing aid 0.4~1%.The present invention
The fire retardant PBT with no halogen of offer/ASA alloys improve flame retardant property by halogen-free flame retardants, at the same by glass fibre and PBT and
Cooperation between ASA improves intensity, improves the interface compatibility between each component using polymethyl methacrylate as compatilizer,
Toughness is improved while proof strength improves.The experimental results showed that fire retardant PBT with no halogen provided by the invention/ASA alloy tensiles
Intensity is up to 107.3MPa, and bending strength is up to 155.8MPa, and notch impact strength is up to 6.9kJm2, UL94 (1.6mm) is
V0 grades.
Specific implementation mode
The present invention provides a kind of fire retardant PBT with no halogen/ASA alloys, include the component of following mass content：
Polybutylene terephthalate (PBT) 30~55%
Acrylonitrile-styrene-acrylic ester copolymer 10~20%
Halogen-free flame retardants 15~20%
Glass fibre 10~20%
Polymethyl methacrylate 3~8%
Antioxidant 0.3~1%
Processing aid 0.4~1%.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include the poly terephthalic acid fourth that mass content is 30~55%
Diol ester, preferably 35~50%, more preferably 40~45%.In the present invention, the polybutylene terephthalate (PBT)
(PBT) inherent viscosity is preferably 0.98~1.1, and more preferably 1.0~1.05.The present invention is to the source of the PBT without spy
Different restriction, using commercial product well known to those skilled in the art or the preparation method of PBT well known to those skilled in the art
It is prepared.In an embodiment of the present invention, the PBT can be specially the strange beautiful PW-978B in Zhenjiang.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include the acrylonitrile-styrene-that mass content is 10~20%
Acrylate copolymer, preferably 12~18%, more preferably 14~16%.In the present invention, the acrylonitrile-styrene-
The mass content of acrylonitrile is preferably 15~45% in acrylate copolymer (ASA), and more preferably 20~35%；The propylene
The mass content of styrene is preferably 40~60% in nitrile-copolymer in cinnamic acrylic ester ASA, and more preferably 45~55%；
The mass content of acrylate is preferably 5~30% in the acrylonitrile-styrene-acrylic ester copolymer ASA, more preferably
10~25%, most preferably 15~20%.
The present invention does not have the source of the ASA special restriction, using commercial product well known to those skilled in the art
Or it is prepared according to preparation method well known to those skilled in the art.In an embodiment of the present invention, the ASA can have
Body is the 1100-211M of Taiwan Changchun chemical production.
Fire retardant PBT with no halogen/ASA alloys that invention provides include the halogen-free flame retardants that mass content is 15~20%, preferably
It is 16~19%, more preferably 17~18%.In the present invention, the halogen-free flame retardants is preferably organic phosphorus flame retardant, more
It preferably includes one or more in triphenyl phosphate, butylbenzene system phosphate and phosphate toluene diphenyl ester.The present invention is to the nothing
The source of halogen fire retardant does not have special restriction, using commercial product well known to those skilled in the art.The present invention's
In embodiment, the halogen-free flame retardants can be specially Clariant OP-1240.In the present invention, the halogen-free flame retardants improves
The flame retardant property of alloy, and it is environmentally safe.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include the glass fibre that mass content is 10~20%, preferably
It is 12~18%, more preferably 14~16%.In the present invention, the glass fibre is preferably alkali-free glass fibre.In this hair
In bright, the glass fibre is preferably the continuous long fiber of 9~14 μm of diameter, more preferably the continuous long fiber of 10~12 μm of diameter.
The present invention does not have the source of the glass fibre special restriction, is using commercial product well known to those skilled in the art
It can.In an embodiment of the present invention, the glass fibre is preferably ERS200-T635C.In the present invention, the glass fibre
Tensile strength and bending strength can be improved, toughness of material is assigned while promoting the strength of materials so that alloy has excellent
Comprehensive performance.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include that mass content is 3~8% polymethyl methacrylates,
Preferably 4~7%, more preferably 5~6%.The present invention is to the molecular weight of the polymethyl methacrylate (PMMA) without spy
Different restriction, using the PMMA well known to those skilled in the art for being used to prepare polymer alloy.The present invention is to described
The source of PMMA does not have special restriction, using commercial product well known to those skilled in the art.In the implementation of the present invention
In example, the PMMA can be specially the CM-211 for very beautifying.In the present invention, the PMMA can improve as compatilizer
The compatibility of PBT, ASA and glass fibre improve boundary strength, to enable each component to play one's part to the full, improve alloy
Intensity and toughness.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include the antioxidant that mass content is 0.3~1%, preferably
0.4~0.9%, more preferably 0.6~0.8%.In the present invention, the antioxidant preferably includes four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2,4- di-tert-butylphenols) phosphite ester (antioxidant
168).In the present invention, described four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4- bis-
Tert-butyl phenol) mass ratio of phosphite ester is preferably 1:1.5~2.5, more preferably 1:1.8~2.
The present invention does not have the source of the antioxidant special restriction, using commercially available production well known to those skilled in the art
Product.In an embodiment of the present invention, the antioxidant 1010 can be specially the Irganox1010 of Ciba companies；It is described anti-
Oxygen agent 168 can be specially the Irgafos168 of Ciba companies.
Fire retardant PBT with no halogen provided by the invention/ASA alloys include the processing aid that mass content is 0.4~1%, preferably
It is 0.5~0.8%, more preferably 0.6~0.7%.In the present invention, the processing aid preferably includes annular terephthalic acid (TPA)
Butanediol ester (CBT).The present invention does not have the source of the CBT special restriction, using city well known to those skilled in the art
Sell product.In an embodiment of the present invention, the CBT can be specially the CBT functional resins of Cyclics companies of the U.S..
In the present invention, the CBT can improve the bond state of glass fibre and alloy substrate, improve mobility.
The present invention also provides the preparation method of fire retardant PBT with no halogen described in above-mentioned technical proposal/ASA alloys, including it is following
Step：
(1) by polybutylene terephthalate (PBT), acrylonitrile-styrene-acrylic ester copolymer, poly-methyl methacrylate
Ester, antioxidant and processing aid mixing, obtain matrix material；
(2) it is squeezed out after mixing the matrix material that the step (1) obtains with halogen-free flame retardants and glass fibre, obtains Halogen
Flame-retardant PBT/ASA alloys.
The present invention is by polybutylene terephthalate (PBT), acrylonitrile-styrene-acrylic ester copolymer, polymethyl
Sour methyl esters, antioxidant and processing aid mixing, obtain matrix material.In the present invention, the temperature of the mixing is preferably room temperature.
In the present invention, the mixing preferably carries out under agitation；The rate of the stirring is preferably 500~1000r/min, more excellent
It is selected as 700~800r/min；The time of the stirring is preferably 10~20min, more preferably 12~16min.The present invention is to institute
The device for stating mixing does not have special restriction, using the device well known to those skilled in the art for preparing mixed material.
In the present invention, the mixing carries out preferably in high-speed mixer.
The present invention is preferably before mixing dried raw material.In the present invention, the drying temperature of the PBT and ASA is excellent
It is selected as 90~130 DEG C, more preferably 100~120 DEG C；The drying time of the PBT and ASA is preferably 3~5h.In the present invention
In, the halogen-free flame retardants, PMMA, glass fibre, antioxidant and processing aid drying temperature be preferably 65~75 DEG C, it is more excellent
It is selected as 68~72 DEG C；Halogen-free flame retardants, PMMA, glass fibre, antioxidant and processing aid drying time be preferably 11~
13h。
After obtaining matrix material, the present invention squeezes out after mixing described matrix material with halogen-free flame retardants and glass fibre, obtains
Fire retardant PBT with no halogen/ASA alloys.In the present invention, the temperature of the extrusion is preferably 190~240 DEG C, more preferably 200~
230 DEG C, most preferably 210~220 DEG C.
The present invention does not have special restriction to the mixing of described matrix material and glass fibre and the device of extrusion, using ability
The device of fiber-reinforced polymer is prepared known to field technique personnel.In the present invention, described matrix material and glass fibre
Mixing and squeeze out carried out preferably in double screw extruder.Preferably described matrix material is added by main feeding funnel by the present invention
In double screw extruder, mouth is added from glass in glass fibre and is added, then halogen-free flame retardants is added from lateral feeder
It squeezes out.In the present invention, the stage casing that mouth is preferably placed at twin-screw is added in the glass.In the present invention, the side spout is excellent
Bit selecting is in the stage casing of twin-screw.
In the present invention, the screw speed of the double screw extruder is preferably 250~400rpm, more preferably 300~
350rpm.In the present invention, the diameter of the screw rod of the double screw extruder is preferably 35~75mm, more preferably 50~
60mm.In the present invention, the temperature of each section of the double screw extruder is preferably：One area：190~200 DEG C；2nd area：200~
210℃；3rd area：200~210 DEG C；4th area：210~220 DEG C；5th area：220~230 DEG C；6th area：220~230 DEG C；7th area：
220~230 DEG C；8th area：230~240 DEG C；Head temperature：230~240 DEG C.
After the completion of extrusion, the present invention is dried after being preferably granulated the product of the extrusion, obtain fire retardant PBT with no halogen/
ASA alloys.The not special restriction of operation of the present invention to the granulation, using the skill of granulation well known to those skilled in the art
Art scheme.In the present invention, the grain size of the granulation is preferably 3~5mm.In the present invention, the temperature of the drying is excellent
It is selected as 95~105 DEG C, more preferably 98~102 DEG C；The time of the drying is preferably 1.5~2h.
In order to further illustrate the present invention, with reference to embodiment to fire retardant PBT with no halogen provided by the invention/ASA alloys
And preparation method thereof be described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
30.1%, ASA 20%, compatilizer PMMA 8%, antioxidant 1010 0.3%, 168 0.6%, processing aid 1%；Then exist
Mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to the material of double screw extruder
In bucket, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；Six
Area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124020%, glass 20%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 2:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
34.2%, ASA 20%, compatilizer PMMA 7%, antioxidant 1010 0.1%, 168 0.2%, processing aid 0.5%；Then
The mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to double screw extruder
In hopper, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；
6th area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124018%, glass 20%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 3:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
39.2%, ASA 20%, compatilizer PMMA 5%, antioxidant 1010 0.1%, 168 0.2%, processing aid 0.5%；Then
The mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to double screw extruder
In hopper, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；
6th area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124020%, glass 15%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 4:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
44.2%, ASA 15%, compatilizer PMMA 7%, antioxidant 1010 0.1%, 168 0.2%, processing aid 0.5%；Then
The mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to double screw extruder
In hopper, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；
6th area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124018%, glass 15%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 5:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
49.1%, ASA 15%, compatilizer PMMA 3%, antioxidant 1010 0.1%, 168 0.2%, processing aid 0.6%；Then
The mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to double screw extruder
In hopper, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；
6th area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124015%, glass 17%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 6:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
48.9%, ASA 20%, compatilizer PMMA 5%, antioxidant 1010 0.2%, 1680.4%, processing aid 0.5%；Then exist
Mixed at room temperature 10min in high-speed mixer, stir speed (S.S.) 700r/min；Uniformly mixed material is added to the material of double screw extruder
In bucket, control temperature of each section exists：One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；Six
Area：225℃；7th area：225℃；8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-
124015%, glass 10%, lateral spout and glass are added mouth and are added, through double screw extruder melt blending extrusion, water cooling,
It air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 7:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；PB50% is weighed,
ASA 10%, compatilizer PMMA 4%, antioxidant 1010 0.1%, 1680.2%, processing aid 0.7%；Then mixed in high speed
10min is mixed in conjunction machine；Uniformly mixed material is added in the hopper of double screw extruder, and control temperature of each section exists：One area：
190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；6th area：225℃；7th area：225℃；8th area：
230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-124015%, glass 20%, lateral spout and glass
Fibre is added mouth and is added, and through double screw extruder melt blending extrusion, water cooling, air-dries, pelletizing, obtains fire retardant PBT with no halogen/ASA and closes
Gold.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
Embodiment 8:
ASA and PBT is 6 hours dry at 110 DEG C, remaining auxiliary agent is 12 hours dry at 70 DEG C；Weigh PBT
55%, ASA 10%, compatilizer PMMA 6%, antioxidant 1010 0.2%, 168 0.3%, processing aid 0.5%；Then exist
10min is mixed in high-speed mixer；Uniformly mixed material is added in the hopper of double screw extruder, and control temperature of each section exists：
One area：190℃；2nd area：200℃；3rd area：210℃；4th area：210℃；5th area：220℃；6th area：225℃；7th area：225℃；
8th area：230℃；Head temperature：230℃；Screw speed 350rpm, fire retardant OP-124018%, glass 10%, lateral feeding
Mouthful and glass mouth is added and is added, through double screw extruder melt blending extrusions, water cooling, air-dried, pelletizing, obtain fire retardant PBT with no halogen/
ASA alloys.
The fire retardant PBT with no halogen that the present embodiment is prepared/ASA alloy properties are as shown in table 1.
The performance test results of fire retardant PBT with no halogen/ASA alloys in 1 Examples 1 to 8 of table
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Density g/m3 | 1.57 | 1.55 | 1.53 | 1.53 | 1.55 | 1.51 | 1.55 | 1.52 |
| Tensile strength/MPa | 103.3 | 107.3 | 102.5 | 105.3 | 104.8 | 95.5 | 104.2 | 98.5 |
| Bending strength/MPa | 155.8 | 150.3 | 135.6 | 133.8 | 142.5 | 128.6 | 146.9 | 135.6 |
| Notch impact strength/Kj.m-2 | 5.3 | 5.8 | 6.3 | 6.9 | 4.9 | 6.8 | 5.5 | 6.4 |
| UL94(1.6mm) | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
As can be seen from the above embodiments, fire retardant PBT with no halogen provided by the invention/ASA alloys have good intensity, tough
Property and flame retardant property, and it is environment friendly and pollution-free.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
Several improvements and modifications can also be made, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of fire retardant PBT with no halogen/ASA alloys, includes the component of following mass content：
Polybutylene terephthalate (PBT) 30~55%
Acrylonitrile-styrene-acrylic ester copolymer 10~20%
Halogen-free flame retardants 15~20%
Glass fibre 10~20%
Polymethyl methacrylate 3~8%
Antioxidant 0.3~1%
Processing aid 0.4~1%.
2. fire retardant PBT with no halogen according to claim 1/ASA alloys, which is characterized in that include the group of following mass content
Point：
Polybutylene terephthalate (PBT) 35~50%
Acrylonitrile-styrene-acrylic ester copolymer 12~18%
Halogen-free flame retardants 16~19%
Glass fibre 12~18%
Polymethyl methacrylate 4~7%
Antioxidant 0.4~0.9%
Processing aid 0.5~0.8%.
3. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the poly terephthalic acid fourth
The inherent viscosity of diol ester is 0.98~1.1.
4. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the acrylonitrile-styrene-
The mass content of acrylonitrile is 15~45% in acrylate copolymer, and the mass content of styrene is 40~60%, acrylic acid
The mass content of ester is 5~30%.
5. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the halogen-free flame retardants is secondary
Phosphoric acid salt fire retardant.
6. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the glass fibre is alkali-free
Glass fibre.
7. fire retardant PBT with no halogen according to claim 6/ASA alloys, which is characterized in that the glass fibre is a diameter of 9
~14 μm of continuous long fiber.
8. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the antioxidant includes four
[β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester and three (2,4- di-tert-butylphenols) phosphite esters.
9. fire retardant PBT with no halogen according to claim 1 or 2/ASA alloys, which is characterized in that the processing aid includes ring
Shape mutual-phenenyl two acid bromide two alcohol ester.
10. a kind of preparation method of any one of claim 1~9 fire retardant PBT with no halogen/ASA alloys, including following step
Suddenly：
(1) by polybutylene terephthalate (PBT), acrylonitrile-styrene-acrylic ester copolymer, polymethyl methacrylate,
Antioxidant and processing aid mixing, obtain matrix material；
(2) it is squeezed out after mixing the matrix material that the step (1) obtains with halogen-free flame retardants and glass fibre, obtains halogen-free flameproof
PBT/ASA alloys.
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| CN110746898A (en) * | 2019-10-25 | 2020-02-04 | 深圳市象形科技有限公司 | High strength protection film that shocks resistance |
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| KR20170039015A (en) * | 2015-09-30 | 2017-04-10 | 코오롱플라스틱 주식회사 | Polyester resin composition and molded artice manufactured therefrom |
| CN106589844A (en) * | 2016-12-01 | 2017-04-26 | 广州科苑新型材料有限公司 | PBT/ASA alloy material and preparing method thereof |
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| CN103788588A (en) * | 2012-10-30 | 2014-05-14 | 上海长伟锦磁工程塑料有限公司 | Low-warping high-rigidity conductive PBT composite material and preparation method |
| KR20170039015A (en) * | 2015-09-30 | 2017-04-10 | 코오롱플라스틱 주식회사 | Polyester resin composition and molded artice manufactured therefrom |
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| CN110746898A (en) * | 2019-10-25 | 2020-02-04 | 深圳市象形科技有限公司 | High strength protection film that shocks resistance |
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