CN115536971B

CN115536971B - Heat aging-resistant ASA/PBT composition and preparation method thereof

Info

Publication number: CN115536971B
Application number: CN202110739171.6A
Authority: CN
Inventors: 杨刚; 方永炜; 姚晨光; 朱敏; 邹冲
Original assignee: Hefei Genius New Materials Co Ltd
Current assignee: Hefei Genius New Materials Co Ltd
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2024-03-29
Anticipated expiration: 2041-06-30
Also published as: CN115536971A

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

Heat aging-resistant ASA/PBT composition and preparation method thereof

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

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;

7. The process according to claim 6, wherein the twin-screw extruder is heated at a temperature in the range of 180 to 240 ℃.