CN116218129A

CN116218129A - Shell material and preparation method and application thereof

Info

Publication number: CN116218129A
Application number: CN202310275028.5A
Authority: CN
Inventors: 左常龙; 陈健; 张悦
Original assignee: Lenovo Beijing Ltd
Current assignee: Lenovo Beijing Ltd
Priority date: 2023-03-20
Filing date: 2023-03-20
Publication date: 2023-06-06

Abstract

The invention provides a shell material, a preparation method and application thereof. The shell material comprises the following raw materials in parts by weight: 35-100 parts of acrylonitrile/butadiene/styrene copolymer resin is recovered; 0-65 parts of acrylonitrile/butadiene/styrene copolymer resin; 2-5 parts of toughening agent; 0.2 to 1.0 part of antioxidant; 1 to 3.5 portions of lubricant; 0.3-1 part of weather-proof agent; 0.5 to 3 portions of coupling agent modified effect powder. According to the invention, the inorganic mineral effect powder modified by the coupling agent is combined with the recovered ABS to prepare the spraying-free recovered ABS material, plastic products with natural texture effects such as star-sky effect can be produced by injection molding, the influence of the recovered ABS performance on the mechanical performance of the material relative to the original material performance and the effect powder is solved, the low-defect spraying-free recovered ABS material with excellent mechanical performance is obtained, plastic products with natural texture effects such as star-sky effect can be produced by one-step injection molding, the surfaces of the products are free from defects, and the yield is high.

Description

Shell material and preparation method and application thereof

Technical Field

The invention relates to the technical field of materials, in particular to a shell material and a preparation method and application thereof.

Background

The plastic products are widely applied to daily necessities, household appliances, 3C digital products, automotive interiors, packages and the like. The spraying-free material is used as a scheme capable of replacing the spray paint, has the advantages of being environment-friendly, capable of being molded at one time, low in cost and capable of shortening the production period, can directly achieve the effects of high gloss, metal texture and the like through injection molding, and has emerged in the market along with the development of the spraying-free material. However, the existing spraying-free products are easy to have surface defects such as flow marks, welding lines, bright and dark lines and the like, and limit the application of the spraying-free technology.

On the other hand, in order to obtain better appearance effect, the spraying-free plastic usually introduces some inorganic material effect powder to achieve the appearance effect similar to starry sky, terrazzo and the like, and can directly obtain the material with special appearance requirement through injection molding, thereby avoiding the flow of spraying paint. However, the poor compatibility of the inorganic material and the plastic matrix can lead to further reduction of the mechanical properties of the material, and when the inorganic material is applied to a component, the structural reinforcement of the component is required to be carried out, so that the use can be satisfied, great limitation is brought, meanwhile, the risk cannot be completely eliminated, and the mechanical failure can still occur from time to time.

Meanwhile, as plastic products are widely used, the use amount of the global plastic products is increased year by year, plastic wastes cause irreversible damage and pollution to the earth environment, and in order to slow down the trend of resource reduction and environmental deterioration, the recycling of the consumed plastic products is more and more concerned, related specifications are formulated successively, and the addition of regenerated materials in virgin materials is encouraged, so that the cost of raw materials is reduced, and the environmental protection requirement is met. Plastics containing recycled components have lower mechanical properties due to the lower performance of recycled plastics than virgin materials. How to improve the mechanical properties of the recycled plastic is a main difficulty in recycling the plastic at present.

Disclosure of Invention

In view of the above, the technical problem to be solved by the invention is to provide a shell material, a preparation method and application thereof, wherein the prepared shell material is a spraying-free material and has the characteristics of low defects and excellent mechanical properties.

In order to achieve the above purpose, the invention provides a shell material, which comprises the following raw materials in parts by weight:

the recovered acrylonitrile/butadiene/styrene copolymer resin used in the present invention may be an acrylonitrile/butadiene/styrene copolymer resin that is generally recovered and reused, and is not particularly limited. Preferably, the proportion of the polybutadiene block is 15% to 25%, the proportion being a molar ratio.

The recovered acrylonitrile/butadiene/styrene copolymer resin preferably has a melt index of 15 to 35g/10min tested at 220 ℃ x 10 kg.

The weight content of the recovered acrylonitrile/butadiene/styrene copolymer resin is 35 to 100 parts by weight, preferably 65 to 100 parts by weight.

The invention takes the recovered acrylonitrile/butadiene/styrene copolymer resin (ABS) as the raw material, which reduces the cost of raw materials and meets the environmental protection requirement, but the recovered ABS has the defect of lower mechanical property, and the mechanical property of the material can be further reduced by introducing the effect powder.

In order not to influence the mechanical properties of the material, the effect powder is modified by a coupling agent, and optionally, the coupling agent is selected from silane coupling agents, more preferably 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane or 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane. The effect powder is preferably a sheet silicate mineral.

The coupling agent modified effect powder is prepared by mixing a coupling agent and effect powder and reacting; in the reaction process, the coupling agent and the effect powder are subjected to a coupling reaction through hydroxyl.

The invention pretreats the sheet silicate mineral by adopting the 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane or the 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, which is beneficial to the compatibility of the sheet silicate mineral, improves the dispersibility of the sheet silicate mineral in the recycled ABS material, further reduces the generation of material defects, and has lower appearance defects compared with metal effects. The test result shows that the special modified effect powder is added into the recycled ABS material, so that the mechanical properties, especially the impact resistance, of the material are well maintained. Meanwhile, the environment-friendly sheet silicate mineral and the recycled ABS are adopted as raw materials, so that the plastic pollution is reduced, the carbon emission is reduced, and the method has positive significance for environmental protection.

The addition amount of the coupling agent is preferably 1-10 wt% of the effect powder. The coupling agent modified effect powder prepared under the proportion condition can obtain the optimal mechanical property of the material.

The weight content of the coupling agent modified effect powder is 0.5-3 parts by weight.

At the same time, the present application also adjusts other components in the material.

The shell material provided by the invention can also comprise acrylonitrile/butadiene/styrene copolymer resin. The content of the acrylonitrile/butadiene/styrene copolymer resin is 0 to 65 parts by weight, preferably 0 to 35 parts by weight.

In the acrylonitrile/butadiene/styrene copolymer resin, the polybutadiene block ratio is preferably 15% to 25%, and the ratio is a molar ratio.

The acrylonitrile/butadiene/styrene copolymer resin preferably has a melt index of 10 to 30g/10min when tested at 220 ℃ x 10 kg.

The shell material provided by the invention also comprises a toughening agent. The toughening agent is preferably one or more of styrene-butadiene-styrene block copolymer grafted maleic anhydride (SBS-MAH) and hydrogenated styrene-butadiene-styrene block copolymer grafted maleic anhydride (SEBS-MAH); more preferred are styrene-butadiene-styrene block copolymers grafted with maleic anhydride, which preferably have a melt index of 10 to 40g/10min tested at 230 ℃ x 5 kg.

The invention adopts the styrene-butadiene-styrene block copolymer grafted maleic anhydride or the hydrogenated styrene-butadiene-styrene block copolymer grafted maleic anhydride as the toughening agent, which not only has the toughening effect, but also has the effect of a compatilizer, and the grafted maleic anhydride can react with the mineral of the sheet silicate pretreated by the coupling agent, thereby further improving the compatibility.

The toughening agent is 2-5 parts by weight, and the specific content comprises, but is not limited to, 2, 3,4 or 5 parts by weight.

The shell material provided by the invention also comprises an antioxidant. The antioxidant is preferably one or more of the antioxidant 1076 and the antioxidant 168, more preferably the antioxidant 1076 and the antioxidant 168. The weight content of the antioxidant 1076 is preferably 0.1 to 0.5 part by weight, and the weight content of the antioxidant 168 is preferably 0.1 to 0.5 part by weight. More preferably, the mass ratio of the antioxidant 1076 to the antioxidant 168 is 1:1.

The total weight content of the antioxidant is preferably 0.2 to 1.0 part by weight.

The shell material provided by the invention also comprises a lubricant.

The lubricant is preferably one or more of stearate, vinyl bis-stearamide; more preferably magnesium stearate.

The weight content of the lubricant is preferably 1 to 3.5 parts by weight.

The shell material provided by the invention also comprises a weather-proof agent.

The weather-resistant agent is preferably one or more of hydroxyphenyl benzotriazoles and hindered amine light stabilizers; more preferably UV-P.

The weight content of the weather-resistant agent is preferably 0.3 to 1 part by weight.

When the material needs to have a certain color, toner can be added into the shell material.

The toner is not particularly limited, and can be adjusted according to the color requirements of the product, including but not limited to carbon powder and the like.

The addition amount of the toner can be adjusted according to the material and the color, and specifically can be 0.1-1.5 parts by weight.

The invention provides a preparation method of the shell material, which comprises the following steps:

a) Pretreating the effect powder by adopting a coupling agent to obtain coupling agent modified effect powder;

b) And mixing the recovered acrylonitrile/butadiene/styrene copolymer resin, the toughening agent, the antioxidant, the lubricant, the weather-resistant agent and the coupling agent modified effect powder, and performing melt extrusion granulation to obtain the shell material.

The step A) is preferably specifically:

and (3) placing the effect powder into a mechanical stirrer, dropwise adding the coupling agent while stirring, wherein the stirring speed of the mechanical stirrer is preferably 50-100 r/min, dropwise adding the coupling agent at a constant speed for 5-10 minutes, continuously stirring for 5-10 minutes after the dropwise adding is finished, and obtaining the coupling agent modified effect powder after the reaction is finished.

And then the acrylonitrile/butadiene/styrene copolymer resin, the toughening agent, the antioxidant, the lubricant, the weather-proof agent and the coupling agent modified effect powder are weighed according to the weight parts, are added into a stirrer for pre-dispersing, the stirring speed is preferably 30-80 r/min, and are added into a double-screw extruder for melt extrusion granulation after uniform mixing.

The parameter settings of the twin-screw extruder are preferably: the temperature of the extrusion one region to the five regions is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the rotating speed of the twin screw is 300-500r/min. The setting of the parameters can ensure that the material has higher yield.

The shell material can be obtained through injection molding, and is suitable for common plastic products such as household appliances, computers, decoration parts and the like, for example, table type and integrated machine decorative structural parts.

The invention also provides a plastic product shell which is prepared from the shell material.

Due to the addition of the effect powder, the plastic product shell can obtain the appearance similar to a starry sky or marble texture, and the product is more attractive.

Compared with the prior art, the invention provides a shell material. According to the invention, the inorganic mineral effect powder modified by the coupling agent is combined with the recovered ABS to prepare the spraying-free recovered ABS material, plastic products with natural texture effects such as starry sky feeling can be produced through injection molding, the influence of the recovered ABS performance on the mechanical properties of the material relative to the original material performance and the effect powder is solved through formula optimization, the low-defect spraying-free recovered ABS material with excellent mechanical properties is obtained, the plastic products with natural texture effects such as the simulated starry sky feeling can be produced through one-step injection molding, and the product surface is free of defects and high in yield.

Drawings

FIG. 1 is an appearance of the low defect spray-free recycled ABS material prepared in example 1;

FIG. 2 is an external view of an ABS material prepared in comparative example 1.

Detailed Description

In order to further illustrate the invention, the low defect spray-free recycled ABS material and the preparation method thereof provided by the invention are described in detail below with reference to examples.

Example 1

(1) Pretreatment of the effect powder is carried out by adopting a coupling agent:

and (3) placing the spotted effect powder into a mechanical stirrer, wherein the adding amount of the coupling agent is 1wt% of the effect powder, dropwise adding the coupling agent while stirring, stirring at a speed of 80r/min by the mechanical stirrer, dropwise adding the coupling agent at a constant speed, continuously stirring for 10 minutes after the dropwise adding is completed, and standing by after the completion of the dropwise adding.

(2) Preparing a low-defect spraying-free recovered ABS material, and weighing the low-defect spraying-free recovered ABS material according to parts by weight:

and (3) taking back the acrylonitrile/butadiene/styrene copolymer resin, the toughening agent, the antioxidant 1#, the antioxidant 2#, the lubricant, the weather resistant agent, the toner and the coupling agent modified effect powder according to the mass parts, adding the mixture into a stirrer for pre-dispersing, stirring at 50r/min, adding the mixture into a double-screw extruder after uniformly mixing, extruding the mixture into a double-screw extruder with the temperature of 190 ℃ in sequence from one region to five regions, 200 ℃, 210 ℃ and 220 ℃ and the double-screw rotational speed of 400r/min, and carrying out melt extrusion granulation to obtain the low-defect spraying-free recovered ABS material.

The recovered acrylonitrile/butadiene/styrene copolymer resin described above had a polybutadiene block content of 15% and a melt index of 15g/10min tested at 220℃under 10 kg.

The coupling agent is 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane;

the toughening agent is styrene-butadiene-styrene block copolymer grafted maleic anhydride (SBS-MAH), and the melt index of the toughening agent is 10g/10min under the condition of 230 ℃ and 5 kg;

the antioxidant 1# is an antioxidant 1076, and the antioxidant 2# is an antioxidant 168;

the lubricant is magnesium stearate;

the weather-proof agent is UV-P;

the toner is carbon black;

the effect powder is sheet silicate.

The appearance diagram of the prepared low-defect spray-free recovered ABS material is shown in figure 1.

Example 2

Example 2 differs from example 1 in that 65 parts of the acrylonitrile/butadiene/styrene copolymer resin and 35 parts of the acrylonitrile/butadiene/styrene copolymer resin are recovered.

The acrylonitrile/butadiene/styrene copolymer resin has a polybutadiene block content of 15% and a melt index of 10g/10min tested at 220 ℃ under 10 kg.

Example 3

Example 3 is different from example 1 in that the recovered acrylonitrile/butadiene/styrene copolymer resin is 35 parts and the acrylonitrile/butadiene/styrene copolymer resin is 65 parts.

The acrylonitrile/butadiene/styrene copolymer resin has a polybutadiene content of 15% and a melt index of 10g/10min tested at 220 ℃ under 10 kg.

Example 4

Example 4 differs from example 1 in that the coupling agent is added in an amount of 10wt% of the effect powder.

Example 5

Example 5 differs from example 1 in that the toughening agent is 5 parts.

Example 6

Example 6 differs from example 1 in that the polybutadiene block content of the acrylonitrile/butadiene/styrene copolymer was recovered at 25%.

Example 7

Example 7 differs from example 1 in that the recovered acrylonitrile/butadiene/styrene copolymer has a test melt index of 35g/10min at 220 ℃ x 10 kg.

Example 8

Example 8 differs from example 1 in that the toughener has a test melt index of 40g/10min at 230 ℃ x 5 kg.

Example 9

Example 9 differs from example 1 in that the coupling agent is 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.

Example 10

Example 10 differs from example 1 in that the toughening agent is hydrogenated styrene-butadiene-styrene block copolymer grafted maleic anhydride (SEBS-MAH).

Example 11

Example 11 differs from example 1 in that antioxidant 1#0.5 parts, antioxidant 2#0.5 parts.

Example 12

Example 12 differs from example 1 in 3.5 parts of lubricant.

Example 13

Example 13 differs from example 1 in that the weathering agent is 1 part.

Example 14

Example 14 differs from example 1 in that the coupling agent modifies effect powder 3 parts.

Comparative example 1

(1) The effect powder is not pretreated;

(2) Preparing a spraying-free recovered ABS material, and weighing the material according to parts by weight:

and (3) weighing the acrylonitrile/butadiene/styrene copolymer resin, the toughening agent, the antioxidant No. 1, the antioxidant No. 2, the lubricant, the weather-resistant agent, the toner and the pretreatment effect powder according to the mass parts, adding the mixture into a stirrer for pre-dispersing, stirring at the speed of 50r/min, uniformly mixing, adding the mixture into a double-screw extruder, extruding the mixture into a region-to-region temperature of 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the double-screw rotating speed of 400r/min, and carrying out melt extrusion granulation to obtain the spraying-free recovered ABS material.

the lubricant is magnesium stearate;

the weather-proof agent is UV-P;

the toner is carbon black;

the effect powder is sheet silicate minerals.

The appearance diagram of the prepared ABS material is shown in FIG. 2. As shown in fig. 2, the effect powder was not modified, resulting in a significant flow mark of the prepared material upon injection molding.

Comparative example 2

Comparative example 2 differs from comparative example 1 in that the acrylonitrile/butadiene/styrene copolymer resin was replaced with a recycled acrylonitrile/butadiene/styrene copolymer resin having a test melt index of 15g/10min at 220 ℃ x 10 kg.

Performance testing

The products prepared in examples 1-14 and comparative examples 1-2 were subjected to mechanical properties testing.

The test methods are shown in table 1.

TABLE 1 test conditions and test criteria

Physical Properties	Test conditions	Test standard
			Melt flow Rate	220℃*10kg	ASTM D1238
Density of	23℃	ASTM D792
			Tensile Strength	50mm/min	ASTM D638
Flexural Strength	3mm/min	ASTM D790
			Flexural modulus	3mm/min	ASTM D790
IZOD notched impact Strength 1/8'	5.5J,23℃	ASTM D256
			Heat distortion temperature	1.82MPa,100mm span	ASTM D648

The test results are shown in Table 2.

TABLE 2 results of Performance test for examples 1-14 and comparative examples 1-2

The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims

1. The shell material comprises the following raw materials in parts by weight:

2. the shell material according to claim 1, wherein in the coupling agent modified effect powder, the coupling agent is selected from silane coupling agents, and the effect powder is selected from sheet silicate minerals.

3. The shell material according to claim 1, wherein the coupling agent modified effect powder is prepared by mixing a coupling agent and effect powder for reaction;

the addition amount of the coupling agent is 1-10wt% of the effect powder.

4. The shell material according to claim 1, wherein the ratio of polybutadiene segments in the recovered acrylonitrile/butadiene/styrene copolymer resin is 15% to 25%;

the melt index of the recovered acrylonitrile/butadiene/styrene copolymer resin is 15-35 g/10min under the condition of 220 ℃ and 10 kg.

5. The shell material according to claim 1, wherein the ratio of polybutadiene segments in the acrylonitrile/butadiene/styrene copolymer resin is 15% to 25%;

the acrylonitrile/butadiene/styrene copolymer resin has a melt index of 10-30 g/10min under the condition of 220 ℃ and 10 kg.

6. The shell material of claim 1, wherein the toughening agent is selected from one or more of styrene-butadiene-styrene block copolymer grafted maleic anhydride, hydrogenated styrene-butadiene-styrene block copolymer grafted maleic anhydride.

7. The housing material of claim 1, wherein the antioxidant is selected from one or more of antioxidant 1076 and antioxidant 168.

8. The shell material according to claim 1, wherein the lubricant is selected from one or more of stearates, vinyl bis-stearamides;

the weather-proof agent is selected from one or more of hydroxyphenyl benzotriazoles and hindered amine light stabilizers.

9. A method of producing the shell material of any one of claims 1 to 8, comprising the steps of:

10. A plastic product housing prepared from the shell material of any one of claims 1 to 8.