WO2022110662A1 - High-toughness and high-rigidity abs composite material dedicated to storage battery casings, preparation method therefor and application thereof - Google Patents

Abstract

A high-toughness and high-rigidity ABS composite material dedicated to storage battery casings, a preparation method therefor and an application thereof. The composite material comprises the following components in parts by weight: 10-20 parts of an ABS resin; 10-25 parts of an ABS high rubber powder; 40-55 parts of a styrene-acrylonitrile resin; 4-8 parts of wollastonite; 16-25 parts of a flame retardant; 0.3-1 part of an antioxidant; and the wollastonite is fibrous wollastonite. The composite material has both high rigidity and high toughness, the flexural modulus thereof is greater than 2300 MPa, and the toughness thereof is greater than 21 kJ/m²; in addition, the composite material can be applied in storage battery casings.

Description

A kind of high-toughness and high-rigidity ABS composite material for battery shell and its preparation method and application technical field

The invention relates to the field of engineering plastics, and more particularly, to a high-toughness and high-rigidity ABS composite material for battery shells and a preparation method and application thereof.

Background technique

Storage battery is a device that directly converts chemical energy into electrical energy, and is widely used. Batteries usually have fire protection requirements, so the current battery casings are usually made of flame-retardant plastics. During transportation, storage and use, batteries may encounter impacts, drops, etc., so there are high requirements on the toughness of battery shell materials, which generally need to pass the drop hammer impact test. Another problem in the use of the battery is that the battery shell is swelled and deformed due to the long time of electrification, the vulcanization of the electrode plate, the excessive viscosity of the electrolyte or the too little amount of the electrolyte, which affects the service life and safety of the battery. This puts forward high rigidity requirements for battery shell materials. For plastic materials, the toughness and rigidity of the material are often opposed and limit each other. Therefore, the current status of ABS materials used for preparing battery casings is that high toughness and high rigidity cannot be well satisfied at the same time.

Chinese patent (CN108752840A) discloses a special heat-resistant, high-impact and flame-retardant resin for battery shells, and specifically discloses 30-50 parts of ABS high rubber powder, 40-60 parts of styrene-acrylonitrile resin, and 10 parts of butadiene. ～30 parts, heat-resistant agent 20-35 parts, brominated flame retardant 10-18 parts, antimony flame retardant 3-8 parts, antioxidant 0.5-2 parts, anti-drip agent 0.1-1 part, although This product improves the toughness of ABS, but its rigidity is still not improved, which cannot fully meet the performance requirements of battery shell products.

Therefore, the ABS materials currently used for battery casings still have the above shortcomings, so it is very meaningful to invent a flame-retardant ABS material that takes into account both high toughness and high rigidity.

SUMMARY OF THE INVENTION

The present invention provides a high-toughness and high-rigidity ABS composite material specially used for the battery shell in order to overcome the defect that the battery shell of the prior art cannot take both high toughness and high rigidity into consideration.

Another object of the present invention is to provide a preparation method of the high-toughness and high-rigidity ABS composite material for the battery shell.

Another object of the present invention is to provide the application of the high-toughness and high-rigidity ABS composite material for the battery shell.

For achieving the above object, the technical scheme adopted in the present invention is:

A special high-toughness and high-rigidity ABS composite material for battery shells, comprising the following components calculated in parts by weight:

The wollastonite is fibrous wollastonite.

The invention utilizes the compounding of ABS high rubber powder, styrene-acrylonitrile resin and fibrous wollastonite to realize the high rigidity and high toughness of the ABS composite material. Among them, ABS high rubber powder and styrene-acrylonitrile resin can control the toughness of ABS composites; fibrous wollastonite has acicular crystal structure, which can enhance the rigidity of its ABS composites, and the addition of fibrous wollastonite does not affect the toughness of ABS composites. Will reduce the toughness of the composite material. For example, although conventional calcium carbonate and glass fiber can improve the rigidity, they have a great influence on the toughness of the composite material and cannot meet the high rigidity and high toughness of the composite material.

Fibrous wollastonite refers to wollastonite that is slender columnar, densely arranged in parallel, and has a certain length and width. Generally, the average length of fibrous wollastonite is 20-150 μm and the aspect ratio is 8-50. It is found that when the average length is 40-90 μm and the aspect ratio is 15-30, the effect of the composite material is more significant. More preferably, the average length of the fibrous wollastonite is 50-70 μm, the aspect ratio of the fibrous wollastonite is 20-25, and the effect of toughness and rigidity of the composite material is better.

Different from one-dimensional fibrous wollastonite, the structure of sheet wollastonite is two-dimensional, and the addition of sheet wollastonite has a great influence on the toughness of the material, and the impact strength decreases rapidly. Therefore, one-dimensional fibrous wollastonite was selected.

Preferably, the rubber content of the ABS high rubber powder is 35-60% of the total weight of the ABS high rubber powder. If the high rubber powder is less than 35%, the toughening effect of the high rubber powder is not good; if the high rubber powder is higher than 60%, the material is soft and the rigidity is too poor.

Preferably, the content of acrylonitrile in the styrene-acrylonitrile resin is 20-40% of the total weight of the styrene-acrylonitrile resin, and the styrene-acrylonitrile resin within this range has a certain rigidity.

Preferably, the flame retardant includes 3-5 parts of chlorinated polyethylene; 10-15 parts of bromine-based flame retardant; and 3-5 parts of antimony-based flame retardant.

The brominated flame retardant is at least one of bromotriazine, tetrabromobisphenol A and brominated epoxy.

Preferably, the antimony-based flame retardant is antimony trioxide and/or antimony pentoxide.

The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

Preferably, the components of the composite material further include a lubricant.

The content of the lubricant is 0.3 to 1 part by weight.

The lubricant is at least one of amide, stearate or ester lubricants.

The present invention also includes the preparation method of the high-toughness and high-rigidity ABS composite material for the battery shell, comprising the following steps:

S1. Weigh ABS resin, ABS high rubber powder, styrene-acrylonitrile resin, wollastonite, chlorinated polyethylene, bromine-based flame retardant, antimony-based flame retardant, antioxidant and add it to the mixer to mix evenly, to obtain a premix;

S2. The premix prepared in S1 is sent to an extruder for kneading, extrusion and post-processing.

The post-processing includes drawing, cooling and dicing.

The application of the high-toughness and high-rigidity ABS composite material for the battery shell in the preparation of the battery shell.

Compared with the prior art, the beneficial effects of the present invention are:

The invention provides a high-toughness and high-rigidity ABS composite material for battery shells, which is compounded by ABS high rubber powder, styrene-acrylonitrile resin and wollastonite, and realizes that the ABS composite material has high rigidity and high toughness at the same time, bending The modulus is greater than 2300MPa and the toughness is greater than 21kJ/m ² , which can be applied to the preparation of battery shell products.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.

The reagents, methods and equipment used in the present invention, unless otherwise specified, are conventional reagents, methods and equipment in the technical field.

The raw materials used in the following examples and comparative examples are as follows:

ABS resin: AG10NP-AK, Taiwan Chemical Fiber Co., Ltd.;

ABS high rubber powder A: WD-132, rubber content 45%, Shandong Wanda Group Co., Ltd.;

ABS high rubber powder B: ABS 60P, rubber content 70%, Taiwan Guoqiao Petrochemical Co., Ltd.;

Styrene-acrylonitrile resin A: SAN NF2200 AK, acrylonitrile content 30%, Taiwan Chemical Fiber Co., Ltd.;

Styrene-acrylonitrile resin B: 50% acrylonitrile, SAN-2437, China Petroleum Jihua Group Corporation;

Fibrous wollastonite A: average length: 20μm, aspect ratio is 8, grade SYW-XA 180

Fibrous wollastonite B: average length: 50μm, aspect ratio of 20, grade SYW-XA 450

Fibrous wollastonite C: average length: 70μm, aspect ratio 25, grade SYW-XA 600

Fibrous wollastonite D: average length: 90μm, aspect ratio of 30, grade SYW-XA 800

Fibrous wollastonite E: average length: 40μm, aspect ratio is 15, grade SYW-XA 360

Fibrous wollastonite F: average length: 120μm, aspect ratio is 40, grade SYW-XA 1150

The above wollastonite is provided by Siyuan Mining Co., Ltd.

Brominated flame retardants: Brominated Epoxy (F-3014) is provided by Albemarle Company, USA; Bromotriazine (FR-245) and Tetrabromobisphenol A (FR-1524) are provided by Dead Sea Bromine Company, Israel;

Antimony flame retardants: antimony trioxide and antimony pentoxide, Huachang Antimony Industry Company;

Chlorinated polyethylene: CPE-132C, Keli Chemical Co., Ltd.;

Antioxidant: phosphite antioxidant tris(2,4-di-tert-butylphenyl) phosphite, hindered phenol antioxidant THANOX 1010, provided by Ciba CIBA Refining Company;

Lubricant: zinc stearate, magnesium stearate and ethylene bis-stearamide, Dongguan Nuojia Plastic & Chemical Co., Ltd.;

Calcium carbonate: CARBITAL S, Iridite Aluminate Co., Ltd.;

Fiberglass: ECS-13-4.5-526, China Jushi Co., Ltd.

Feldspar powder: water milled potassium feldspar powder, Guanhong New Materials Co., Ltd.

Flake wollastonite: XYNFW-B, Southern Wollastonite Co., Ltd.

The high-toughness and high-rigidity ABS composite materials for the battery shells of the embodiments and comparative examples of the present invention are prepared through the following process:

S1. Weigh ABS resin, ABS high rubber powder, styrene-acrylonitrile resin, wollastonite, chlorinated polyethylene, bromine-based flame retardant, antimony-based flame retardant, antioxidant and add it to the mixer to mix evenly, to obtain a premix;

S2. The premix prepared in S1 is sent to an extruder for kneading, extrusion and post-processing. The extrusion temperature is 180-190℃, the rotation speed is 300r/min, and the feeding is 50kg/h.

Examples 1 to 3

This example provides a series of high-toughness and high-rigidity ABS composite materials. The content of ABS high rubber powder selected in different embodiments is different. The specific formula is shown in Table 1 to explore the influence of different ABS high rubber powder contents on the performance of composite materials.

Table 1 Formulations (parts) of the composite materials of Examples 1 to 3

	Example 1	Example 2	Example 3
ABS resin	16	16	16
ABS high rubber powder A	10	15	25
Styrene-acrylonitrile resin A	40	40	40
Fibrous wollastonite B	6	6	6
Chlorinated polyethylene	3	3	3
Brominated flame retardant	14	14	14
Antimony flame retardant	3	3	3
Antioxidant	0.3	0.3	0.3

Examples 4 to 6

This example provides a series of high-toughness and high-rigidity ABS composite materials. The content of styrene-acrylonitrile resin selected in different embodiments is different. The specific formula is shown in Table 2 to explore the effect of different styrene-acrylonitrile resin content on the performance of composite materials. influences.

Table 2 The formula (parts) of the composite materials of Examples 4-6

	Example 4	Example 5	Example 6
ABS resin	16	16	16
ABS high rubber powder A	15	15	15
Styrene-acrylonitrile resin A	45	50	55
Fibrous wollastonite B	6	6	6
Chlorinated polyethylene	3	3	3
Brominated flame retardant	14	14	14
Antimony flame retardant	3	3	3
Antioxidant	0.3	0.3	0.3

Examples 7-9

This example provides a series of high-toughness and high-rigidity ABS composite materials. The content of wollastonite selected in different embodiments is different. The specific formula is shown in Table 3 to explore the effect of different wollastonite content on the performance of the composite material.

The formula (parts) of the composite material of the embodiment 7-9 of table 3

	Example 7	Example 8	Example 9
ABS resin	16	16	16

ABS high rubber powder A	15	15	15
Styrene-acrylonitrile resin A	40	40	40
Fibrous wollastonite B	4	7	8
Chlorinated polyethylene	3	3	3
Brominated flame retardant	14	14	14
Antimony flame retardant	3	3	3
Antioxidant	0.3	0.3	0.3

Examples 10 to 17

This embodiment provides a series of high-toughness and high-rigidity ABS composite materials, the formula of which is shown in Table 4

Formulations (parts) of Table 4 Examples 10-17

Comparative Examples 1 to 7

The comparative example provides a series of high-toughness and high-rigidity ABS composite materials, the formula of which is shown in Table 5

Table 5 Formulas (parts) of Comparative Examples 1 to 7

The prepared samples of the following examples and comparative examples were tested using ISO standards to test their relevant properties;

Flame retardant test standard: UL 94-2018, spline thickness 2.0mm;

Izod notched impact strength: ISO 180-2000;

Flexural modulus: ISO 178-2010;

Drop weight impact test: The weight of the drop weight is 1kg, the test height is 60cm, and the test sample is an injection-molded square plate of 2.0*100*100mm, with a total of 5 tests.

Table 6 Performance test results of each embodiment and comparative example

From Examples 1 to 3, as the content of high rubber powder increases, the toughness (impact strength) of the composite material increases continuously, and the rigidity (flexural modulus) decreases gradually. High rubber powder has a significant toughening effect, but using too much will affect the rigidity.

From Examples 2 and 4 to 6, when the amount of styrene-acrylonitrile resin is increased, the rigidity of the composite material increases and the toughness decreases accordingly. Styrene-acrylonitrile resin has a certain effect of stiffening, and at the same time will affect the toughness of the material.

It can be seen from Examples 2 and 7 to 9 that the rigidity of the composite material is continuously improved and the toughness of the composite material is slightly decreased by increasing the addition amount of wollastonite B. This shows that the toughening effect of wollastonite B is remarkable without reducing the toughness of the material.

Example 10 added lubricant without affecting the high toughness and high rigidity of the ABS composite.

From Examples 2 and 11 to 15, as the average length of the fibrous wollastonite used increases from 20 μm to 120 μm, the aspect ratio increases from 8 to 40. The results show that the average length used is 50 to 70 μm, and the long diameter When the ratio is 20 to 25, the fibrous wollastonite has a good balance of rigidity and toughness.

From Examples 16 to 17, the rigidity of ABS high rubber powder with a rubber content of 70% will decrease; when the styrene-acrylonitrile resin with acrylonitrile content of 50% is used, its toughness will also decrease.

From the comparative examples 1 to 3, without adding high rubber powder, the toughness of the material is very poor; without adding styrene-acrylonitrile resin and wollastonite, the rigidity of the material is low, which cannot meet the requirements of the battery shell.

From the comparative examples 4 to 7, the rigidity of the material is not improved by adding granular powdered calcium carbonate, which cannot meet the requirements of the battery shell. affects the toughness of the material.

In addition, it can be seen that Examples 1 to 15 can pass the drop weight impact test for evaluating battery materials, and have both rigidity and toughness balance; while Comparative Examples 1 and 5 to 7 have poor toughness and cannot pass the drop weight impact test. The flexural modulus of Comparative Examples 2 to 3 is low and the rigidity is insufficient.

Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. A special high-toughness and high-rigidity ABS composite material for battery shell, characterized in that it comprises the following components calculated by weight:

   

   The wollastonite is fibrous wollastonite.
2. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the average length of the fibrous wollastonite is 40-90 μm, and the aspect ratio of the fibrous wollastonite is 15-15 μm 30.
3. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the average length of the fibrous wollastonite is 50-70 μm, and the aspect ratio of the fibrous wollastonite is 20-20 μm 25.
4. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the rubber content of the ABS high rubber powder is 35-60% of the total weight of the ABS high rubber powder.
5. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the content of acrylonitrile in the styrene-acrylonitrile resin is 20-40% of the total weight of the styrene-acrylonitrile resin.
6. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the flame retardant comprises 3-5 parts of chlorinated polyethylene; 10-15 parts of bromine-based flame retardant; antimony-based flame retardant 3 to 5 doses.
7. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 5, wherein the antimony-based flame retardant is antimony trioxide and/or antimony pentoxide.
8. The high-toughness and high-rigidity ABS composite material for battery shells according to claim 1, wherein the composite material further comprises a lubricant.
9. The preparation method of the high-toughness and high-rigidity ABS composite material specially used for battery shells according to any one of claims 1 to 8, characterized in that, comprising the following steps:

   S1. Weigh ABS resin, ABS high rubber powder, styrene-acrylonitrile resin, wollastonite, chlorinated polyethylene, bromine-based flame retardant, antimony-based flame retardant, antioxidant and add it to the mixer to mix evenly, to obtain a premix;

   S2. The premix prepared in S1 is sent to an extruder for kneading, extrusion and post-processing.
10. Application of the high-toughness and high-rigidity ABS composite material for battery shells according to any one of claims 1 to 8 in the preparation of battery shells.