CN114133676A

CN114133676A - Low-gloss, low-density and low-temperature-resistant ASA composite material and preparation method and application thereof

Info

Publication number: CN114133676A
Application number: CN202111152563.9A
Authority: CN
Inventors: 宋晓辉; 陈平绪; 叶南飚; 肖华明; 孙超正; 郝垠龙; 付锦锋; 杨霄云; 陶四平
Original assignee: Tianjin Kingfa Advanced Materials Co Ltd
Current assignee: Tianjin Kingfa Advanced Materials Co Ltd
Priority date: 2021-09-29
Filing date: 2021-09-29
Publication date: 2022-03-04
Anticipated expiration: 2041-09-29
Also published as: CN114133676B

Abstract

The invention discloses an ASA composite material with low gloss, low density and low temperature resistance, a preparation method and application thereof. The ASA composite material comprises the following components in parts by weight: 30-60 parts of AS resin, 15-40 parts of ASA rubber powder, 15-40 parts of PE resin, 5-10 parts of SEPS and 0.5-1.5 parts of processing aid; wherein the average particle size of the acrylic rubber in the ASA rubber powder is 500-1000 nm. The ASA composite material prepared by selecting the ASA rubber powder with large rubber particle size and performing synergistic action with SEPS, PE resin, AS resin and the like has low gloss, low density and low temperature resistance, and can be widely applied to preparing outdoor products, especially automobile tail decorative plate products.

Description

Low-gloss, low-density and low-temperature-resistant ASA composite material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of modified plastic processing, and particularly relates to a low-gloss, low-density and low-temperature resistant ASA composite material and a preparation method and application thereof.

Background

ASA (terpolymer of styrene, acrylonitrile and acrylic ester) material is a common polymer, and because acrylic ester does not contain double bonds, the material has good weather resistance, is a more preferable material variety for outdoor products, and is often applied to the fields of outdoor appliances, indicators, automobile exterior decorations and the like. In general, ASA materials are good in gloss, but some outdoor applications require low-gloss effects, such as automobile tail trim panels, and high gloss can cause light reflection at night, so that potential safety hazards exist. Meanwhile, outdoor products are also suitable for being used at lower temperature in winter, and have higher requirements on low-temperature toughness of materials. In addition, the reduction of the material density makes contribution to the weight reduction of the automobile, and meets the requirements of light weight, low emission and environmental protection. In summary, there is a need for an ASA material that can simultaneously meet the characteristics of low gloss, low density, and low temperature resistance.

Chinese patent CN101759984A discloses a low-gloss and ultraviolet-resistant PC/ASA composition, and the alloy material needs to be added with a series of copolymers for realizing low gloss, has a complex formula and has higher density of the PC-containing alloy material. Chinese patents CN107686624A and CN107652605A both disclose low-gloss ASA resin compositions, and a large amount of phenylmaleimide heat-resistant agent is added in order to reduce the gloss of the material, so that the impact toughness is greatly negatively affected, and the material becomes brittle.

Disclosure of Invention

Compared with the existing outdoor product material, the ASA composite material has the properties of low gloss, low density and low temperature resistance, and can effectively solve the problems that the potential product of the common ASA material of the automobile tail decorative plate product exposed outdoors is dazzlingly and heavily used, and the low temperature resistance effect is poor.

The invention also aims to provide a preparation method of the low-gloss, low-density and low-temperature resistant ASA composite material.

Another object of the present invention is to provide the use of the above low gloss, low density, low temperature resistant ASA composite in the preparation of outdoor products.

In order to achieve the purpose, the invention adopts the following technical scheme:

the ASA composite material with low gloss, low density and low temperature resistance is characterized by comprising the following components in parts by weight: 30-60 parts of AS resin, 15-40 parts of ASA rubber powder, 15-40 parts of PE resin, 5-10 parts of SEPS and 0.5-1.5 parts of processing aid;

wherein the average particle size of the acrylic rubber in the ASA rubber powder is 500-1000 nm.

Polyethylene (PE) material is a common crystalline material, exhibits low gloss, and still exhibits good performance at low temperatures. SEPS is a hydrogenated styrene-isoprene block copolymer, and is a product obtained by selectively hydrogenating a styrene-isoprene polymer; before the SEPS is processed, the polystyrene blocks are gathered into hard areas, and the polystyrene blocks begin to become soft and flowable under the action of heating and shearing force in the processing process; when cooled down, the polystyrene blocks rearrange and harden, locking up the rubber network, a physical phenomenon that gives SEPS high tensile strength and high elasticity; since SEPS has styrene and olefin segments, it has a certain compatibility with both ASA gum powder and PE resin.

In the invention, the ASA rubber powder with specific large rubber particle size is selected in an ASA composite material system and matched with SEPS, PE resin and AS resin to prepare the ASA composite material with low gloss, low density and low temperature resistance.

Preferably, the ASA composite comprises the following components in parts by weight: 45-55 parts of AS resin, 20-30 parts of ASA rubber powder, 20-30 parts of PE resin, 6-8 parts of SEPS and 0.6-1.0 part of processing aid.

Preferably, the acrylonitrile content in the AS resin is 25 wt.% to 35 wt.%.

Preferably, the SEPS is a star-shaped multi-arm polymer; the styrene content in the SEPS ranges from 5 wt% to 30 wt%.

Preferably, the average particle size of the acrylic rubber in the ASA rubber powder is 600-800 nm.

Preferably, the PE resin is linear low density polyethylene.

Preferably, the at least one processing aid antioxidant or lubricant.

More preferably, the antioxidant is at least one of hindered phenols or phosphites, specifically at least one of 1010, 1076, 3114, 168 or PEP-36.

More preferably, the lubricant is at least one of stearic acids, polyethylenes, esters, paraffins or amides, and specifically at least one of BS-3818, 617A and EBS B50.

The invention also provides a preparation method of the ASA composite material, which comprises the following steps:

and uniformly mixing the AS resin, the ASA rubber powder, the PE resin, the SEPS and the processing aid, performing melt blending, extruding and granulating to obtain the low-gloss, low-density and low-temperature resistant ASA composite material.

Preferably, the melt blending temperature is 190-210 ℃, and the rotation speed of an extrusion screw is 250-450 rpm.

The use of the above-described ASA composite in the preparation of outdoor products is also within the scope of the present invention.

Preferably, the ASA composite is used for preparing the automobile tail decorative plate.

Compared with the prior art, the invention has the following beneficial effects:

(1) the ASA rubber powder with larger rubber particle size is selected to be used in synergy with SEPS, PE resin, AS resin and the like, so that the prepared ASA composite material has low gloss, low density and low temperature resistance, can be widely applied to preparing outdoor products, and is especially used for preparing automobile tail decorative plates.

(2) The preparation method of the low-gloss, low-density and low-temperature resistant ASA composite material provided by the invention has a simple production process and is suitable for mass production.

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.

Some of the reagents selected in the examples and comparative examples of the present invention are described below:

AS resin:

1. the model is as follows: SAN NF2200 (acrylonitrile content 25 wt.%): ningbo Tai Co;

2. the model is as follows: SAN 350 (acrylonitrile content 30 wt.%): korea Jinhu petrochemical company;

3. the model is as follows: SAN 310TR (acrylonitrile content 19 wt.%): korea Jinhu petrochemical company;

ASA rubber powder:

1. the model is as follows: q350 (average particle diameter of acrylic rubber 800nm) manufacturer: east China sea plastics corporation;

2. the model is as follows: DH10 (average particle size of acrylic rubber 600 nm): east China sea plastics corporation;

3. the model is as follows: XC510A (average particle diameter of acrylic rubber: 100nm) manufacturer: korea Jinhu petrochemical company;

SEPS：

1. star multi-arm SEPS model: SEPS YH-4030 (styrene content 5 wt.%): the ba ling petrochemical company;

2. linear non-multi-arm SEPS model: SEPS YH-4020 (styrene content 27 wt.%): the ba ling petrochemical company;

3. linear non-multi-arm SEPS model: SEPS YH-4010 (styrene content 37 wt.%): the ba ling petrochemical company;

PE resin:

1. linear low density polyethylene type: LLDPE 7042 manufacturer: jilin petrochemical company;

2. linear low density polyethylene type: LLDPE M2320 manufacturer: guangzhou, China petrochemical company;

3. high density polyethylene type: HDPE 5000S manufacturer: yangzi petrochemical company;

processing aid:

antioxidant:

1. hindered phenol type: 1010 manufacturer: a new material of the Lianlong;

2. phosphite type: 168 manufacturer: a new material of the Lianlong;

lubricant:

1. stearic acid type: manufacturer BS-3818: chemical industry of Huaming Tai;

2. polyethylene wax type: 617A manufacturer: HONEYWELL;

the ASA composite materials of the examples and the comparative examples of the invention are prepared by the following processes:

according to the proportion, placing AS resin, ASA rubber powder, PE resin, SEPS and processing aids into a mixer to be uniformly mixed, wherein the rotating speed of the mixer is 250rpm, and the mixing time is 5 min; after mixing, melting and mixing the raw materials by a double-screw extruder, and extruding and granulating the mixture to obtain the ASA composite material;

wherein the first zone temperature of the double-screw extruder is 190 ℃, the second zone temperature is 190 ℃, the third zone temperature is 200 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 200 ℃, the sixth zone temperature is 200 ℃, the seventh zone temperature is 200 ℃, the eighth zone temperature is 205 ℃, and the ninth zone temperature is 210 ℃; the screw speed of the twin-screw extruder was 300 rpm.

The performance test methods and standards of the ASA composite materials of the examples and the comparative examples of the invention are as follows:

(1) density: according to ISO 1183-1-2012;

(2) tensile strength: testing according to ISO 527-2-2016, wherein the tensile speed is 50 mm/min;

(3) flexural modulus: the sample is injected and molded into a mechanical sample strip, and the test is carried out according to ISO 178-2010 with the bending speed of 2 mm/min;

(4) notched izod impact strength: the test was performed according to ISO 180-: TypeA, test temperature-20 ℃;

(5) gloss: the gloss 60 ℃ was tested according to ISO-2813-2014.

Examples 1 to 12

This example provides a series of ASA composites having the formulations shown in Table 1.

TABLE 1 examples 1 to 12 formulations (parts)

	1	2	3	4	5	6	7	8	9	10	11	12
													AS resin 1	50	/	/	50	50	50	50	50	45	55	60	30
AS resin 2	/	50	/	/	/	/	/	/	/	/	/	/
													AS resin 3	/	/	50	/	/	/	/	/	/	/	/	/
ASA rubber powder 1	25	25	25	/	25	25	25	25	20	40	30	15
													ASA rubber powder 2	/	/	/	25	/	/	/	/	/	/	/	/
SEPS 1	7	7	7	7	/	/	7	7	5	10	8	5
													SEPS 2	/	/	/	/	7	/	/	/	/	/	/	/
SEPS 3	/	/	/	/	/	7	/	/	/	/	/	/
													PE resin 1	25	25	25	25	25	25	/	/	20	30	40	15
PE resin 2	/	/	/	/	/	/	25	/	/	/	/	/
													PE resin 3	/	/	/	/	/	/	/	25	/	/	/	/
Antioxidant 1	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.1	0.1	0.4	0.1
													Antioxidant 2	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.1	0.1	0.4	0.1
Lubricant 1	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.2	0.15	0.35	0.15
													Lubricant 2	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.2	0.15	0.35	0.15

Comparative examples 1 to 3

This comparative example provides a series of ASA composites having the formulations shown in Table 2.

TABLE 2 formulation of comparative examples 1 to 3 (parts)

Comparative example	1	2	3
				AS resin 1	50	50	50
ASA rubber powder 1	/	25	25
				ASA powder 3	25	/	/
SEPS 1	7	/	7
				PE resin 1	25	25	/
Antioxidant 1	0.2	0.2	0.2
				Antioxidant 2	0.2	0.2	0.2
Lubricant 1	0.25	0.25	0.25
				Lubricant 2	0.25	0.25	0.25

The results of the performance test of the ASA composites of each example and comparative example according to the above-mentioned method are shown in table 3.

TABLE 3 results of Performance test of each example and comparative example

As can be seen from Table 3, the ASA composite materials prepared in the embodiments 1-12 of the invention all have low gloss, low density and low temperature resistance; the impact strength of the alloy is more than or equal to 12kJ/m at the temperature of minus 20 DEG C²The glossiness is less than or equal to 55. In examples 3, 6 and 8, the AS resin, the SEPS resin or the PE resin are respectively selected to be out of the preferable range, and the comprehensive performance of the composite material is slightly reduced.

Compared with the comparative example 1, the ASA rubber powder with large particle size is added in the example, so that the low-gloss effect is better, and the low-temperature impact strength is higher and the low-temperature resistance is better; the large-size rubber can generate more silver lines when the material is impacted, absorb more energy and be beneficial to improving the impact strength.

Compared with comparative examples 2-3, the low-gloss effect and the low-temperature resistance of the material in example 1 are better, and the strength and the modulus of the material are better; the star-shaped multi-arm polymer and the linear low-density polyethylene have rich structural networks, more absorbed energy and better toughening effect; and meanwhile, the molecular chains of the polymer are larger, and the glossiness is lower.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. The ASA composite material with low gloss, low density and low temperature resistance is characterized by comprising the following components in parts by weight: 30-60 parts of AS resin, 15-40 parts of ASA rubber powder, 15-40 parts of PE resin, 5-10 parts of SEPS and 0.5-1.5 parts of processing aid;

2. The ASA composite according to claim 1, wherein the ASA composite comprises the following components in parts by weight: 45-55 parts of AS resin, 20-30 parts of ASA rubber powder, 20-30 parts of PE resin, 6-8 parts of SEPS and 0.6-1.0 part of processing aid.

3. The ASA composite AS claimed in claim 1, wherein the acrylonitrile content of the AS resin is 25 wt.% to 35 wt.%.

4. The ASA composite of claim 1, wherein the SEPS is a star-shaped multi-arm polymer; the styrene content in the SEPS ranges from 5 wt% to 30 wt%.

5. The ASA composite as claimed in claim 1, wherein the acrylic rubber in the ASA rubber powder has an average particle size of 600-800 nm.

6. The ASA composite of claim 1, wherein the PE resin is linear low density polyethylene.

7. The ASA composite of claim 1, wherein the processing aid is at least one of an antioxidant or a lubricant.

8. The ASA composite of claim 7, wherein the antioxidant is at least one of a hindered phenol or a phosphite; the lubricant is at least one of stearic acids, polyethylenes, esters, paraffins or amides.

9. The method for preparing the ASA composite material according to any one of claims 1 to 8, comprising the steps of:

10. Use of an ASA composite as claimed in any one of claims 1 to 8 in the manufacture of an outdoor product.