CN112759908B - Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof - Google Patents

Abstract

The invention relates to a scratch-repairable highlight ABS composition and a preparation method thereof. According to the invention, the scratch repairing agent is added, the ester exchange inhibitor is adopted to regulate and control the enrichment of the scratch repairing agent on the surface, and the scratch repairing agent is melted and regenerated at a lower temperature, so that the material has the scratch repairable characteristic.

Description

Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof

Technical Field

The invention belongs to the field of modified plastics, and particularly relates to a scratch-repairable highlight ABS composition and a preparation method thereof.

Background

Acrylonitrile-butadiene-styrene copolymer (ABS) is one of five common plastics, and has the advantages of balanced rigidity and toughness, high gloss, easy forming and the like, so that the ABS and alloy materials thereof are widely applied to products such as household appliances, automobiles and the like. However, the general ABS and its alloy are often used for preparing high-gloss products, and are often scratched during transportation and use, even the high-hardness ABS/PMMA alloy is difficult to avoid scratches, and the scratches are often not repairable after being generated.

Chinese patent CN109553964A discloses a nylon composite material with scratch self-repairing function, and the repair of scratches is realized by utilizing self-repairing microcapsules to release epoxy resin which is subjected to reaction crosslinking after the material is scratched. However, the self-repairing microcapsules are easy to break and lose effectiveness in the process of processing the twin-screw, are not friendly to modification of modified plastics, and limit the application of the modified plastics.

Chinese patent CN106832372A discloses a method for repairing cracks of a high polymer material by a solvent fumigation method, compared with a method for self-repairing microcapsules, the method does not need to embed a repairing agent for encapsulation or hollow fibrosis in advance; more high polymer materials can be suitable for selection of fumigation solvent. However, the method needs a closed solvent fumigation environment, and is difficult to operate for repairing some products in use or large products.

In addition, the intrinsic repair method utilizes reversible chemical reactions for self-repair, which generally include Diels-Alder reactions, dynamic valence supply chemistry, disulfide bond reactions, hydrogen bond-containing supramolecular structures, pi-pi stacking, particle polymers and the like, and these systems are not suitable for conventional modified polymer materials.

Therefore, a new scratch-repairable ABS composite is desired.

Disclosure of Invention

The invention aims to solve the technical problem of providing a scratch-repairable highlight ABS composition and a preparation method thereof, wherein after a product injection-molded by the composition is scratched, the scratch can be desalted and repaired through hot air treatment at 60-80 ℃.

The invention provides a scratch-repairable highlight ABS composition, which comprises the following raw material components in percentage by mass:

the ABS resin contains 12-35 wt% of acrylonitrile, 8-35 wt% of butadiene and 30-80 wt% of styrene.

The ABS resin can be produced by a one-step polymerization process with a core-shell structure, or by a two-step process of blending butadiene graft SAN copolymer subjected to emulsion graft polymerization with acrylonitrile-styrene copolymer (AS resin, SAN); the commercially available ABS resin may be selected as the matrix resin, or a blend of butadiene-grafted SAN copolymer and SAN in certain amounts and proportions may be selected as the matrix resin.

The melt flow rate of the PBT resin is 10-25g/10min under the conditions of 250 ℃ and 1.5kg load.

The scratch repairing agent is Polycaprolactone (PCL), the viscosity average molecular weight of the PCL is 50000-120000, and the melting point of the PCL is 58-63 ℃.

The compatilizer is at least one of styrene-maleic anhydride copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-N-phenylmaleimide-maleic anhydride copolymer.

The ester exchange inhibitor is at least one of phosphate, pyrophosphate, phosphite and alkyl phosphate.

The nucleating agent is at least one of nano montmorillonite and nano talcum powder.

The other auxiliary agent is at least one of an antioxidant, a lubricant and a weather-resistant agent.

The antioxidant is antioxidant 1010 or antioxidant 168.

The lubricant is EBS.

The weather resisting agent is at least one of benzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent and hindered amine light stabilizer.

The invention also provides a preparation method of the scratch-repairable highlight ABS composition, which comprises the following steps:

mixing the raw materials in a mixer, adding the raw materials from a main feeding port of a double-screw extruder, controlling the temperature of each section of the double-screw extruder to be 180-240 ℃, controlling the rotating speed of screws to be 200-600 r/min, and water-cooling, bracing and granulating to obtain the product.

The invention also provides application of the scratch-repairable highlight ABS composition in household appliances or automobiles.

Advantageous effects

(1) According to the invention, through the addition of the scratch repair agent, the ester exchange inhibitor is adopted to regulate and control the enrichment of the scratch repair agent on the surface, and the material has the characteristic of being capable of repairing scratches by utilizing the melting regeneration of the scratch repair agent at a lower temperature, and after an injection molded product is scratched, the scratches can be desalted and repaired through hot air treatment at 60-80 ℃.

(2) The compatibility between the scratch repair agent and the ABS resin is improved through the bridging effect of the PBT resin, and the impact property of the material is improved.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The raw material sources are as follows:

ABS resin: 121H, LG chemistry;

AS resin: 310TR, brocade lake petrifaction;

ABS graft rubber powder: MAG-50, benzene-collar;

PBT resin: 1100A, southeast stars;

polycaprolactone: 800C, viscosity average molecular weight 80000;1200C, viscosity average molecular weight 120000; the photo-wonderful industry;

a compatilizer: SZ 23110, polyscope;

ester exchange inhibitor: alkyl phosphate, ai Dike; sodium dihydrogen pyrophosphate, kesu columbic;

nucleating agent: nano talcum powder, HTPUltra5L, liaoning Ai Haiyi rice mining;

antioxidant: 1010 or 168, basf;

lubricant: EBS, changzhou matcha;

weather resisting agent: 234 or 770, basf.

The preparation method comprises the following steps:

the raw materials were mixed in a mixer at 1000 rpm for 5min. And then carrying out melt blending by a co-rotating double-screw extruder, setting the temperature of each section of the double-screw extruder to be 180-240 ℃ according to the conventional technology in the field, setting the rotating speed of a screw to be 200 r/min, and carrying out water cooling, bracing and granulating.

And (3) performance testing:

(1) Testing the notch impact strength of the cantilever beam according to a standard ISO 180 method; the heat distortion temperature was measured according to the method of ISO Standard 75-2/A.

(2) Scratch repairable test method:

the scratch was subjected to a reciprocating heat treatment with a 65 ℃ hot air gun, and after cooling, the repair of the scratch was visually observed and recorded.

TABLE 1 example proportions (in% by mass)

TABLE 2 comparative example ratio (mass percent)

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Comparative example 6

ABS resin

85％

70％

60.3％

58.8％

PC resin

60％

PBT resin

10％

10％

10％

10％

70％

800C

25％

25％

25％

25％

25％

Compatilizer

3％

3％

3％

3％

3％

3％

Alkyl phosphate ester

0.3％

0.3％

1.5％

0.3％

0.3％

Nucleating agent

0.5％

0.5％

0.5％

0.5％

0.5％

0.5％

Antioxidant agent

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

Lubricant agent

0.5％

0.5％

0.5％

0.5％

0.5％

0.5％

Weather-resistant agent

0.5％

0.5％

0.5％

0.5％

0.5％

0.5％

TABLE 3 effects of the examples

TABLE 4 comparative example effects

Detecting items

Unit of

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Comparative example 6

Notched Izod impact Strength

kJ/m 2

17.5

12.7

23.3

14.3

35.1

5.2

Repair of scratches

/

Is very poor

In general

In general

In general

Is very poor

Is very poor

The scratch-repairable high-gloss ABS compositions obtained in examples 1 to 10 exhibit good notched Izod impact strength through bridge compatibilization of PBT resin and control of transesterification reaction by a transesterification inhibitor, and simultaneously can realize scratch repair through hot air treatment. Examples 4-7 show that with increasing amounts of transesterification inhibitors, the degree of transesterification reaction is reduced and the material exhibits better scratch repair; however, since the transesterification reaction is limited, the impact strength of the material is slightly reduced. Compared with example 5, the polycaprolactone is lacked, and the scratch on the surface of the comparative example 1 cannot be repaired. Compared with the example 5, the PBT resin is lack of bridging, the impact strength of the material is greatly reduced, and the scratch repair effect is general. Comparative examples 3 to 4 removed the ester interchange inhibitor and increased the amount of the ester interchange inhibitor, the scratch repair effect was general, and comparative example 4 also decreased the impact strength, as compared to example 5. In comparison with example 5, in the case where the base resin is a PC resin or a PBT resin as it is, the scratch repair effect is not achieved by the formulation used in the present invention, and thus the present invention is particularly suitable for ABS resins.

Claims (10)

1. A scratch-repairable high-gloss ABS composition, which is characterized in that: the raw material components by mass percent are as follows:

wherein the scratch repairing agent is polycaprolactone PCL, and the viscosity average molecular weight is 50000-120000.

2. The composition of claim 1, wherein: the ABS resin contains 12-35 wt% of acrylonitrile, 8-35 wt% of butadiene and 30-80 wt% of styrene.

3. The composition of claim 1, wherein: the melt flow rate of the PBT resin is 10-25g/10min under the conditions of 250 ℃ and 1.5kg load.

4. The composition of claim 1, wherein: the melting point of the polycaprolactone PCL is 58-63 ℃.

5. The composition of claim 1, wherein: the compatilizer is at least one of styrene-maleic anhydride copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-N-phenylmaleimide-maleic anhydride copolymer.

6. The composition of claim 1, wherein: the ester exchange inhibitor is at least one of phosphate, pyrophosphate, phosphite and alkyl phosphate.

7. The composition of claim 1, wherein: the nucleating agent is at least one of nano montmorillonite and nano talcum powder.

8. The composition of claim 1, wherein: the other auxiliary agent is at least one of an antioxidant, a lubricant and a weather-resistant agent.

9. A method for preparing the scratch-repairable high-gloss ABS composition of claim 1, comprising the steps of:

mixing the raw materials in a mixer, adding the raw materials from a main feeding port of a double-screw extruder, controlling the temperature of each section of the double-screw extruder to be 180-240 ℃, controlling the rotation speed of a screw to be 200-600 r/min, and water-cooling, bracing and granulating to obtain the product.

10. Use of the scratch-repairable high-gloss ABS composition according to claim 1 in household appliances or automobiles.