CN115536971B - Heat aging-resistant ASA/PBT composition and preparation method thereof - Google Patents
Heat aging-resistant ASA/PBT composition and preparation method thereof Download PDFInfo
- Publication number
- CN115536971B CN115536971B CN202110739171.6A CN202110739171A CN115536971B CN 115536971 B CN115536971 B CN 115536971B CN 202110739171 A CN202110739171 A CN 202110739171A CN 115536971 B CN115536971 B CN 115536971B
- Authority
- CN
- China
- Prior art keywords
- parts
- asa
- pbt
- heat aging
- carbon black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 230000032683 aging Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000006229 carbon black Substances 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 29
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- OYPRJOBELJOOCE-BKFZFHPZSA-N Calcium-45 Chemical group [45Ca] OYPRJOBELJOOCE-BKFZFHPZSA-N 0.000 claims description 3
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 25
- 239000002994 raw material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- -1 Polybutylene terephthalate Polymers 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a heat-aging-resistant ASA/PBT composition and a preparation method thereof, wherein the heat-aging-resistant ASA/PBT composition is prepared from 100 parts of ASA, 10-50 parts of PBT, 30-50 parts of glass fiber, 3-10 parts of styrene-acrylonitrile-GMA, 1-2 parts of lubricant, 4-6 parts of carbon black master batch and 0.1-0.2 part of antioxidant CA according to parts by weight. The heat-resistant aging ASA/PBT composition has excellent heat-resistant aging performance, high mechanical retention rate after a heat aging test, excellent mechanical evil energy and application prospect.
Description
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a heat aging-resistant ASA/PBT composition and a preparation method thereof.
Background
ASA is a terpolymer composed of acrylonitrile-Styrene-Acrylate, and belongs to an impact-modified resin. The structure is similar to that of ABS, both of which contain styrene and acrylonitrile. ASA retains the good mechanical and physical properties of ABS as engineering plastic, and has weather resistance much higher than that of ABS because of no double bond structure, and ASA resin has high impact resistance, high mechanical properties, good heat resistance, excellent colorability and the like.
Polybutylene terephthalate (Polybutylene terephthalate), also known as polytetramethylene terephthalate, PBT for short, is a polycondensate of terephthalic acid and 1, 4-butanediol. PBT is a milky semitransparent to opaque semi-crystalline thermoplastic polyester, has high heat resistance, can work for a long time at 140 ℃, has toughness, fatigue resistance, self-lubrication, low friction coefficient, is not resistant to strong acid and strong alkali, can resist organic solvents, is flammable, and is decomposed at high temperature. Because of these excellent properties, they are widely used in the fields of automobiles, mechanical equipment, precision instrument parts, electronic appliances, textiles, and the like.
In order to improve the performance of the polymer materials, the means adopted in the prior art is to compound more than two polymer materials, wherein the ASA/PBT alloy material has the advantages of ASA and PBT, but part of the ASA/PBT alloy material has poor mechanical properties, glass fiber is often used for cavity enhancement, but glass fiber reinforced ASA/PBT can accelerate plastic decomposition under continuous high temperature conditions, so that the material performance is reduced, the heat aging resistance is poor, and the application of the ASA/PBT composition in some high temperature environments is limited.
Disclosure of Invention
In view of the above, the invention is necessary to provide a heat-aging-resistant ASA/PBT composition, which has the advantages of remarkably improving the heat aging resistance of the ASA/PBT composition and having high retention rate of mechanical properties after aging by the compounding effect of carbon black master batch and antioxidant CA.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a heat aging resistant ASA/PBT composition, which is prepared from 100 parts of ASA, 10-50 parts of PBT, 30-50 parts of glass fiber, 3-10 parts of styrene-acrylonitrile-GMA, 1-2 parts of lubricant, 4-6 parts of carbon black master batch and 0.1-0.2 part of antioxidant CA according to parts by weight.
According to the invention, the carbon black master batch and the antioxidant CA are added into the ASA/PBT composition of the glass fiber system, and the heat aging resistance of the ASA/PBT composition of the glass fiber system is obviously improved by utilizing the compounding effect of the carbon black master batch and the antioxidant CA, so that the retention rate of mechanical properties after heat aging is high. In addition, since the carbon black master batch itself has conductivity, it also functions as an antistatic agent in the system. Furthermore, the styrene-acrylonitrile-GMA is mixed into the system, so that on one hand, the interfacial tension between ASA and PBT and the internal stress between two phases are reduced, the mechanical property of the composition is improved, and on the other hand, the addition of the styrene-acrylonitrile-GMA slightly improves the heat resistance of the ASA/PBT composition, so that the ASA/PBT composition has excellent comprehensive properties.
Further, ASA and PBT used in the present invention are not particularly limited, and ASA and PBT conventional in the art may have a melt index of 5 to 30g/10min at 240℃under 5kg test conditions in one or more embodiments of the present invention.
The melt index of the PBT under the test condition of 2.16kg at 235 ℃ is 5-30g/10min.
The glass fiber in the present invention may be any kind or specification of glass fiber in the art, and is not particularly limited, and in one or more embodiments of the present invention, the glass fiber is an alkali-free glass fiber, and has a metric number of 1000-2500tex and a diameter of 8-15 μm.
Further, in the styrene-acrylonitrile-GMA, the mass fraction of the GMA is 10+/-0.5%.
In one or more embodiments of the present invention, the lubricant is selected from calcium stearate, it being understood that any lubricant known in the art to be useful in ASA, PBT can be used in the present invention.
Further, the carbon black master batch is prepared by mixing 20-40 parts of ASA, 5-15 parts of calcium stearate and 45-75 parts of carbon black according to parts by weight, wherein a mode of extruding to obtain the carbon black master batch after uniformly mixing the components in the prior art can be adopted, the specific process is not particularly limited, and in one or more embodiments of the invention, the components are added into a high-speed mixer to be mixed to obtain a uniform mixed material; adding the mixture into a double-screw extruder, and granulating after melt extrusion of the extruder to obtain carbon black master batch, wherein the temperature of each heating zone of the extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and 230 ℃ of a die head.
The invention also provides a preparation method of the heat aging resistant ASA/PBT composition, which comprises the following steps:
100 parts of ASA, 10-50 parts of PBT, 3-10 parts of styrene-acrylonitrile-GMA, 1-2 parts of lubricant, 4-6 parts of carbon black master batch and 0.1-0.2 part of antioxidant CA are fully mixed according to the weight proportion to obtain a uniform mixed material, and the mixing mode, time and the like are not particularly limited, so long as the uniform mixing of all raw material components can be ensured;
and adding the mixed material into a double-screw extruder, adding 30-50 parts of glass fibers into the double-screw extruder through a fiber feeding port, and carrying out melting, extrusion and granulation to obtain the heat aging-resistant ASA/PBT composition.
Further, the heating temperature range of the double-screw extruder is 180-240 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the ASA/PBT composition has excellent comprehensive performance, obviously improved heat aging resistance and high retention rate of mechanical properties after heat aging. The ASA/PBT composition has high tensile strength and notch impact strength and excellent mechanical properties.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Specific information of the raw material components in the following examples and comparative examples is as follows:
ASA: sand based (raw GE) GELOY XTPM302, melt index 10g/10min (240 ℃,5 kg);
PBT: mitsubishi 5010R5, japan, melt index 20g/10min (235 ℃,2.16 kg);
glass fiber: boulder ER14-1000-988A;
styrene-acrylonitrile-GMA: the manufacturer is Guangdong Airst New Material Co., ltd, and the mass fraction of GMA is 10+/-0.5 percent:
calcium stearate: jiangxi Hongyuan chemical industry;
carbon black master batch: adding 30 parts by weight of ASA, 10 parts by weight of calcium stearate and 60 parts by weight of carbon black into a high-speed mixer for mixing to obtain a uniform mixed material; adding the mixture into a double-screw extruder, and granulating after melt extrusion of the extruder to obtain carbon black master batch, wherein the temperature of each heating zone of the extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and 230 ℃ of a die head.
Antioxidant CA: wuhan Lanabi pharmaceutical chemical Co., ltd.
It is understood that the specific parameters of the above raw material components are only examples for making the technical solution of the present invention clearer, and do not represent that the technical solution of the present invention can only adopt the above raw material components, and the specific protection scope is subject to the claims. In the following examples and comparative examples, "parts" and the like are parts by weight unless otherwise specified.
Example 1
Adding 100 parts of ASA, 10 parts of PBT, 3 parts of styrene-acrylonitrile-GMA, 1 part of lubricant, 4 parts of carbon black master batch and 0.1 part of antioxidant CA into a high-speed mixer to mix so as to obtain a uniform mixed material;
adding the mixed material into a double-screw extruder, adding 30 parts of glass fibers into the extruder through a fiber feeding port, and granulating after melt extrusion through the extruder to obtain an ASA/PBT composition; wherein the temperature of each heating zone of the extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and the die head is 240 ℃.
Example 2
Adding 100 parts of ASA, 20 parts of PBT, 5 parts of styrene-acrylonitrile-GMA, 2 parts of lubricant, 5 parts of carbon black master batch and 0.2 part of antioxidant CA into a high-speed mixer to mix so as to obtain a uniform mixed material;
adding the mixed material into a double-screw extruder, adding 40 parts of glass fibers into the extruder through a fiber feeding port, and granulating after melt extrusion through the extruder to obtain an ASA/PBT composition; wherein the temperature of each heating zone of the extruder is 180 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃ and 230 ℃ of the die head.
Example 3
Adding 100 parts of ASA, 30 parts of PBT, 8 parts of styrene-acrylonitrile-GMA, 2 parts of lubricant, 6 parts of carbon black master batch and 0.2 part of antioxidant CA into a high-speed mixer to mix so as to obtain a uniform mixed material;
adding the mixed material into a double-screw extruder, adding 50 parts of glass fibers into the extruder through a fiber feed port, and granulating after melt extrusion through the extruder to obtain an ASA/PBT composition; wherein the temperature of each heating zone of the extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃ and 235 ℃ of the die head.
Example 4
Adding 100 parts of ASA, 40 parts of PBT, 10 parts of styrene-acrylonitrile-GMA, 2 parts of lubricant, 6 parts of carbon black master batch and 0.2 part of antioxidant CA into a high-speed mixer to mix so as to obtain a uniform mixed material;
adding the mixed material into a double-screw extruder, adding 50 parts of glass fibers into the extruder through a fiber feed port, and granulating after melt extrusion through the extruder to obtain an ASA/PBT composition; wherein the temperature of each heating zone of the extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and 230 ℃ of the die head.
Example 5
Adding 100 parts of ASA, 50 parts of PBT, 10 parts of styrene-acrylonitrile-GMA, 2 parts of lubricant, 5 parts of carbon black master batch and 0.2 part of antioxidant CA into a high-speed mixer to mix so as to obtain a uniform mixed material;
adding the mixed material into a double-screw extruder, adding 30 parts of glass fibers into the extruder through a fiber feeding port, and granulating after melt extrusion through the extruder to obtain an ASA/PBT composition; the temperature of each heating zone of the extruder was 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, and 235 ℃ of the die head.
Example 6
This example uses the same implementation as example 5, except that: the carbon black master batch in this example was made by mixing 20 parts ASA, 5 parts calcium stearate and 45 parts carbon black.
Example 7
This example uses the same implementation as example 5, except that: the carbon black master batch in this example was prepared by mixing 40 parts ASA, 15 parts calcium stearate and 75 parts carbon black.
Comparative example 1
The present comparative example uses the same embodiment as example 5, except that: the "5 parts of carbon black master batch and 0.2 part of antioxidant CA" in example 5 were replaced with "5.2 parts of carbon black master batch", and the other raw material components were added and prepared in the same manner as in example 5.
Comparative example 2
The present comparative example uses the same embodiment as example 5, except that: the "5 parts of carbon black master batch and 0.2 part of antioxidant CA" in example 5 were replaced with "5.2 parts of antioxidant CA", and the other raw material components were added and prepared in the same manner as in example 5.
Comparative example 3
The present comparative example uses the same embodiment as example 5, except that: the same procedure as in example 5 was repeated except that "0.2 part of antioxidant CA" in example 5 was replaced with "0.2 part of antioxidant 1098" and the other raw material components were added.
Comparative example 4
The present comparative example uses the same embodiment as example 5, except that: the same procedure as in example 5 was repeated except that "0.2 part of antioxidant CA" in example 5 was replaced with "0.2 part of antioxidant 300" and that the other raw material components were added.
Comparative example 5
The present comparative example uses the same embodiment as example 5, except that: the same procedure as in example 5 was repeated except that "0.2 part of antioxidant CA" in example 5 was replaced with "0.2 part of antioxidant 168" and the other raw material components were added.
Comparative example 6
The present comparative example uses the same embodiment as example 5, except that: the "5 parts of carbon black master batch and 0.2 part of antioxidant CA" in example 5 were replaced with "2.6 parts of antioxidant 1098 and 2.6 parts of antioxidant 168", and the other raw material components were added and prepared in the same manner as in example 5.
Comparative example 7
The present comparative example uses the same embodiment as example 5, except that: 100 parts of ASA and 10 parts of styrene-acrylonitrile-GMA in example 5 were replaced with "110 parts of ASA", and the other raw material components were added and prepared in the same manner as in example 5.
Test case
1. ASA/PBT compositions prepared in examples 1-5 and comparative examples 1-7 were injection molded using ASTM standards, and the spline dimensions (length. Times. Width. Times. Thickness) were:
(1) Tensile bars (dumbbell) 170mm x 13mm x 3.2mm;
(2) Notch impact spline, 127mm x 13mm x 3.2mm, v-notch with notch depth 1/5;
tensile strength was measured according to ASTM D638, at a tensile speed of 5mm/min; notched impact strength was measured according to ASTM D6110; surface resistivity was measured according to ASTM D257. The results are shown in Table 1.
TABLE 1 results of Performance test of ASA/PBT compositions
| Tensile Strength/Mpa | Notched impact strength/KJ/square meter | Surface resistivity | |
| Example 1 | 108 | 13.2 | 6.3*10 9 |
| Example 2 | 125 | 11.5 | 1.8*10 9 |
| Example 3 | 131 | 10.8 | 1.1*10 9 |
| Example 4 | 127 | 11.6 | 1.6*10 9 |
| Example 5 | 94 | 14.0 | 7.5*10 9 |
| Comparative example 1 | 82 | 10.9 | 6.2*10 8 |
| Comparative example 2 | 90 | 13.6 | 3.4*10 12 |
| Comparative example 3 | 89 | 13.5 | 7.6*10 9 |
| Comparative example 4 | 88 | 12.8 | 7.9*10 9 |
| Comparative example 5 | 85 | 11.7 | 7.5*10 9 |
| Comparative example 6 | 91 | 13.3 | 4.2*10 12 |
| Comparative example 7 | 68 | 5.6 | 7.1*10 9 |
2. The heat aging test was performed on the injection molded bars in test 1, and the tensile strength and notched impact strength after the heat aging test were tested, and the results are shown in table 2, and the heat aging test is specifically: and using a blast constant temperature drying oven, wherein the fluctuation degree and uniformity degree of the temperature are +/-1 ℃, the ageing temperature of the material is 160 ℃, and the heat ageing time is 2000 hours.
TABLE 2 Heat aging test results for ASA/PBT compositions
Note that: table 2 retention of tensile strength after heat aging%o=tensile strength after heat aging/tensile strength before heat aging x 100%;
notched impact strength retention after heat aging%notched impact strength after heat aging/notched impact strength before heat aging x 100%.
As can be seen from the test results in tables 1 and 2, after the carbon black master batch and the antioxidant CA are added together, compared with the traditional antioxidant system or single carbon black master batch and antioxidant CA, the heat aging resistance of the ASA/PBT composition can be obviously improved, and the retention rate of mechanical properties after heat aging is obviously superior to that of other antioxidant systems or single carbon black master batch and antioxidant CA.
Furthermore, as can be seen by comparing example 5 with comparative example 7, the addition of styrene-acrylonitrile-GMA improves the mechanical properties of the composition, mainly because it reduces the interfacial tension between ASA and PBT and the internal stress between the two phases; meanwhile, the addition of the styrene-acrylonitrile-GMA slightly improves the heat resistance of the composition.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The heat aging resistant ASA/PBT composition is characterized by being prepared from 100 parts of ASA, 10-50 parts of PBT, 30-50 parts of glass fiber, 3-10 parts of styrene-acrylonitrile-GMA, 1-2 parts of lubricant, 4-6 parts of carbon black master batch and 0.1-0.2 part of antioxidant CA according to parts by weight; in the styrene-acrylonitrile-GMA, the mass fraction of the GMA is 10+/-0.5%; the carbon black master batch is prepared by mixing 20-40 parts of ASA, 5-15 parts of calcium stearate and 45-75 parts of carbon black according to parts by weight; the ASA is a terpolymer composed of acrylonitrile-styrene-acrylate.
2. The heat aging resistant ASA/PBT composition of claim 1, wherein the ASA has a melt index of 5 to 30g/10min at 240 ℃ under 5kg test conditions.
3. The heat aging resistant ASA/PBT composition of claim 1, wherein the PBT has a melt index of 5 to 30g/10min at 235 ℃ under 2.16kg test conditions.
4. The heat aging resistant ASA/PBT composition of claim 1, wherein the glass fibers are alkali free glass fibers having a metric number of 1000 to 2500tex and a diameter of 8 to 15 μm.
5. The heat aging resistant ASA/PBT composition of claim 1, wherein the lubricant is selected from the group consisting of calcium stearate.
6. A process for the preparation of a heat aging resistant ASA/PBT composition according to any one of claims 1 to 5, comprising the steps of:
100 parts of ASA, 10-50 parts of PBT, 3-10 parts of styrene-acrylonitrile-GMA, 1-2 parts of lubricant, 4-6 parts of carbon black master batch and 0.1-0.2 part of antioxidant CA are fully mixed according to the weight ratio to obtain a uniform mixed material;
and adding the mixed material into a double-screw extruder, adding 30-50 parts of glass fibers into the double-screw extruder through a fiber feeding port, and carrying out melting, extrusion and granulation to obtain the heat aging-resistant ASA/PBT composition.
7. The process according to claim 6, wherein the twin-screw extruder is heated at a temperature in the range of 180 to 240 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110739171.6A CN115536971B (en) | 2021-06-30 | 2021-06-30 | Heat aging-resistant ASA/PBT composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110739171.6A CN115536971B (en) | 2021-06-30 | 2021-06-30 | Heat aging-resistant ASA/PBT composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536971A CN115536971A (en) | 2022-12-30 |
| CN115536971B true CN115536971B (en) | 2024-03-29 |
Family
ID=84717571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110739171.6A Active CN115536971B (en) | 2021-06-30 | 2021-06-30 | Heat aging-resistant ASA/PBT composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536971B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080049345A (en) * | 2006-11-30 | 2008-06-04 | 주식회사 삼양사 | Thermoplastic resin composition and molded product using the same |
| CN104629249A (en) * | 2013-11-14 | 2015-05-20 | 上海杰事杰新材料(集团)股份有限公司 | Weather-resistant glass-fiber-reinforced ABS/PBT (acrylonitrile-butadiene-styrene/polybutylene terephthalate) alloy material and preparation method thereof |
| CN105754179A (en) * | 2016-03-07 | 2016-07-13 | 苏州莱特复合材料有限公司 | Flame retardant HDPE cable 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 |
| CN107778853A (en) * | 2016-08-29 | 2018-03-09 | 合肥杰事杰新材料股份有限公司 | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof |
-
2021
- 2021-06-30 CN CN202110739171.6A patent/CN115536971B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080049345A (en) * | 2006-11-30 | 2008-06-04 | 주식회사 삼양사 | Thermoplastic resin composition and molded product using the same |
| CN104629249A (en) * | 2013-11-14 | 2015-05-20 | 上海杰事杰新材料(集团)股份有限公司 | Weather-resistant glass-fiber-reinforced ABS/PBT (acrylonitrile-butadiene-styrene/polybutylene terephthalate) alloy material and preparation method thereof |
| CN105754179A (en) * | 2016-03-07 | 2016-07-13 | 苏州莱特复合材料有限公司 | Flame retardant HDPE cable 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 |
| CN107778853A (en) * | 2016-08-29 | 2018-03-09 | 合肥杰事杰新材料股份有限公司 | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536971A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109401302A (en) | Good surface high impact nylon/POK alloy and preparation method thereof | |
| CN102108181A (en) | Thermoplastic alloy and preparation method thereof | |
| CN109486013B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN111944240A (en) | Polypropylene composite material and preparation method thereof | |
| CN102942736B (en) | High-glass fiber content reinforced polypropylene material and preparation method thereof | |
| CN108912600A (en) | A kind of fiber reinforcement PEEK/PPA alloy material and preparation method thereof | |
| CN109370210B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof | |
| CN109504078B (en) | Efficient enhanced halogen-free flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of nylon resin and preparation method thereof | |
| CN109535701B (en) | Efficient enhanced flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof | |
| CN108047705B (en) | Flame-retardant polyamide composition and preparation method thereof | |
| CN113429781A (en) | Long glass fiber reinforced bio-based polyamide 56, alloy and preparation method thereof | |
| CN115536971B (en) | Heat aging-resistant ASA/PBT composition and preparation method thereof | |
| CN112266613A (en) | Polyphenylene sulfide composite material, preparation method thereof and injection molding part | |
| CN106939112B (en) | High-gloss HIPS/recycled PET bottle flake composite material and preparation method thereof | |
| CN107974079B (en) | Nylon ABS alloy composite material and preparation method thereof | |
| CN113956653A (en) | Aramid fiber reinforced polyamide composite material and preparation method thereof | |
| CN109486154B (en) | Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof | |
| CN110760177B (en) | Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN106810856A (en) | Bellows material and preparation method thereof | |
| CN105462225A (en) | Anti-static PC-PBT alloy material and preparation method thereof and safe toe cap | |
| CN111944308A (en) | Nylon 6 composite material with low linear expansion coefficient and preparation method thereof | |
| CN114292510B (en) | PC-ABS alloy material and preparation method thereof | |
| CN111484721A (en) | Low-temperature impact resistant PC/ABS composite material and preparation method thereof | |
| CN111978719A (en) | Polyamide 66 composite material and preparation method thereof | |
| CN114479463B (en) | Extrusion-grade PPS composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |