A styrene composition with fiber dot effect and preparation method thereof

Abstract

The present invention discloses a styrene composition with a fiber point effect and a preparation method thereof, which belongs to the field of engineering plastics. In the styrene composition product with a fiber point effect described in the present invention, a specific high-melting-point semi-aromatic high-temperature nylon is used as a fiber point. After being matched with a specific type of compatibilizer, the fiber point not only has a certain compatibility with the resin matrix, so that the product has a good shear resistance effect, but also has a good temperature resistance effect. When the product life cycle is complete and the recycling stage is carried out, it can also be effectively separated from the resin system to achieve a high recovery rate, which has a high commercial value. The present invention also discloses a preparation method of the product and its application in the preparation of electrical appliances and office appliances.

Description

Technical Field

[0001] The invention relates to the technical field of engineering plastics, and in particular to a styrene composition with a fiber point effect and a preparation method thereof. Background Art

[0002] Polystyrene (PS) resin is easy to process, has excellent dimensional stability, high impact strength and high rigidity, especially high-impact polystyrene (HIPS) resin, which can be injection molded, extruded, thermoformed, roto-molded, blow-molded, foam-molded, etc., and is widely used in household appliances, electronic appliances, office equipment and other product fields.

[0003] In order to enable various resin products, including PS resin, to obtain special design effects such as flocking and marble patterns, the existing technology introduces natural fibers or chemical fiber dots / fiber hairs into the system as fiber dots. For example, the technical solution disclosed in CN109486160A uses natural green tea powder treated with organosiloxane as fiber dots to achieve a flocking-like surface effect. However, green tea powder is very heat-sensitive, easily degrades, and has a short service life. The technical solution disclosed in CN112480544A uses cellulose as fiber dots to achieve a flocking-like effect on glass fiber-reinforced PP materials. However, cellulose is easily carbonized and discolored during processing, affecting the appearance and mechanical toughness properties.

[0004] At the same time, this fiber point component is actually an additional "impurity" component for the resin product system. When the product life cycle is complete, these fiber points also have a certain impact on the recycling of the product: the technical solution disclosed in CN114605744A uses PET fiber points grafted with maleic anhydride to obtain nano-filled polypropylene with a good touch, but the temperature and shear resistance of the PET fiber points are not high enough, and it cannot solve the problem that the fiber points of complex parts cannot be separated in subsequent recycling. Summary of the Invention

[0005] Based on the defects of the existing technology, the purpose of the present invention is to provide a styrene composition with a fiber point effect. The product uses a specific high-melting point semi-aromatic high-temperature nylon as a fiber point. After being matched with a specific type of compatibilizer, the fiber point not only has a certain compatibility with the resin matrix, so that the product has good shear resistance, but also has good temperature resistance. When the product life cycle is complete and the recycling stage is carried out, it can also be effectively separated from the resin system, achieving a high recovery rate, and has high commercial value.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A styrene composition with a fiber dot effect, comprising the following components in parts by weight:

[0008] 80-95 parts of polystyrene resin, 2-5 parts of compatibilizer, 3-7 parts of toughening agent, 0.3-1 part of weathering agent and 0.5-5 parts of fiber point;

[0009] The fiber point is semi-aromatic high-temperature nylon with a melting point of ≥300°C;

[0010] The compatibilizer is at least one of maleic anhydride grafted SEBS copolymer (maleic anhydride grafted hydrogenated polystyrene-polyethylene-polybutylene-polystyrene copolymer) and styrene-maleic anhydride copolymer.

[0011] In existing resin processing products, the fiber points that bring about the appearance design effect are actually "impurity" components for the base resin in the resin products. The introduction of this component will have a certain weakening effect on the toughness of the product, resulting in poor shear resistance of the product. At the same time, traditional fiber point components do not have temperature resistance, which causes the fiber points to melt during processing and use, and even completely merge with the resin matrix in a slow process, which not only affects the appearance design effect, but also when the product is in the recycling stage, the fiber points cannot be separated from the resin matrix, reducing the recyclability of the resin matrix and the fiber points themselves.

[0012] Based on the above situation, the inventors introduced high-melting-point semi-aromatic high-temperature nylon as a fiber point into the polystyrene resin matrix. This component not only has good high-temperature resistance itself, but also has a large difference in melting point from the polystyrene resin, and will not slowly fuse. The overall product has the characteristic of being easy to recycle, and the components can be separated by simple melt extrusion and filtration.

[0013] In addition, the selection of compatibilizers is critical for the product. The main reason is that the use of compatibilizers can improve the compatibility between fiber points and components such as polystyrene resins, toughening agents, and weathering agents, so that the temperature resistance of the fiber points in the product is better. At the same time, the fiber points will not have too much negative impact on the toughness of the polystyrene resin. However, if the compatibility between the fiber points and the polystyrene resin is too good, then during the melt extrusion and filtration stage of product recycling, the fiber points and the matrix resin will be too evenly distributed and difficult to separate, and the recyclability will be significantly reduced. Therefore, after screening, the inventors found that using maleic anhydride grafted SEBS copolymers and styrene-maleic anhydride copolymers as compatibilizers in combination with fiber points can take into account the shear resistance and temperature resistance and recyclability of the product.

[0014] Preferably, the maleic anhydride content of the styrene-maleic anhydride copolymer is 20-25%, and the maleic anhydride grafting rate of the maleic anhydride-grafted SEBS copolymer is 1-2%.

[0015] Preferably, the semi-aromatic high-temperature nylon is at least one of polydecane terephthalamide (PA10T) and polyhexamethylene terephthalamide (PA6T).

[0016] For semi-aromatic high-temperature nylon used as fiber points, although its content is added in small amounts, its physical and chemical properties will still directly affect the performance and appearance of the product. After screening, PA10T and PA6T can make the product have better shear resistance and fiber point temperature resistance after the introduction of product components compared to other high-melting point nylons exceeding 300°C. In addition, PA10T also has bio-based properties, and the recycling and reuse of this component is more environmentally friendly. At the same time, when the semi-aromatic high-temperature nylon described in the present invention is used as a fiber point, the morphology, size and color of the fiber point can be adjusted according to the requirements of the product appearance effect. The effect presented by the prepared styrene composition product is a dot-shaped or sheet-shaped fiber point effect with sufficient fiber point length, which is different from the granular visual effect presented by existing products such as green tea powder.

[0017] Preferably, the average particle size of the fiber points is 0.3 to 1.0 mm.

[0018] Preferably, the polystyrene resin has a melt flow rate of 3 to 8 g / 10 min at 200° C. and a load of 5 kg according to ISO 1133-1-2011 Plastics—Thermoplastics—Determination of melt mass flow rate and melt volume flow rate.

[0019] More preferably, the polystyrene resin is high impact polystyrene.

[0020] More preferably, the high-impact polystyrene is a mixture of new high-impact polystyrene and recycled high-impact polystyrene, the melt flow rate of the new high-impact polystyrene at 200°C and 5kg load is 4 to 8g / 10min, and the melt flow rate of the recycled high-impact polystyrene at 200°C and 5kg load is 3 to 5g / 10min.

[0021] In the styrene composition product of the present invention, in order to ensure the toughness of the product, HIPS resin with low fluidity and high impact resistance is preferably used as the base resin. In order to increase the environmental friendliness and environmental friendliness of the product, new materials and recycled materials with similar melt flow rates can be selected and matched.

[0022] Preferably, the toughening agent is a styrene-butadiene-styrene block copolymer with a butadiene content of ≥60%; and the weathering agent is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.

[0023] Preferably, the fiber point effect styrene composition further comprises 0 to 4 parts of a processing aid.

[0024] More preferably, the processing aid is at least one of an antioxidant and a lubricant.

[0025] More preferably, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant, and the lubricant is at least one of an amide lubricant, a silicone lubricant, a stearic acid lubricant, and an organic wax lubricant.

[0026] Another object of the present invention is to provide a method for preparing the fiber point effect styrene composition, comprising the following steps:

[0027] After the components are uniformly mixed, they are placed in a twin-screw extruder for melt blending and extrusion, and subjected to vacuum extraction treatment, and then pelletized and dried to obtain the styrene composition with the fiber point effect.

[0028] Preferably, the fiber dots are prepared by melting semi-aromatic high-temperature nylon in a twin-screw extruder, coloring it with colorant, extruding it into pellets, and then grinding it into dot- or sheet-shaped fiber dots. The preparation method of the product of the present invention has simple steps, produces a high-quality and high-purity product, is easy to use and recycle, and can be produced on an industrial scale.

[0029] Preferably, the processing temperature of the twin-screw extruder in the melt blending extrusion stage is set to 120-230°C, wherein the processing temperature of zones 1 and 2 is set to 120-190°C, the processing temperature of zones 3 to 5 is set to 180-230°C, and the processing temperature of zones 6 to 10 is set to 190-230°C; the screw speed is set to 350-450rpm.

[0030] Another object of the present invention is to provide the use of the styrene composition with fiber point effect in the preparation of electrical appliances and office appliances.

[0031] Generally speaking, most plastic parts products involved in the electrical appliance field and the office equipment field have high requirements for appearance design, which is why plastic products containing fiber points are popular in these fields. The styrene composition with fiber point effect described in the present invention not only has a good appearance fiber point effect, but also has good shear resistance and temperature resistance, and the fiber points have high stability. When the product is fully operational, the resin matrix and the fiber points can be separated and recycled by simple recycling methods. Its practicality, economic benefits and environmental protection are far higher than existing similar products, and it has high commercial value.

[0032] The beneficial effect of the present invention is that the present invention provides a styrene composition with a fiber point effect, in which a specific high-melting point semi-aromatic high-temperature nylon is used as a fiber point. After being matched with a specific type of compatibilizer, the fiber point not only has a certain compatibility with the resin matrix, so that the product has good shear resistance, but also has good temperature resistance. When the product life cycle is complete and the recycling stage is carried out, it can also be effectively separated from the resin system, achieving a high recovery rate, and has high commercial value. DETAILED DESCRIPTION

[0033] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples. Its purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all conventional common reagents and instruments unless otherwise specified.

[0034] Examples 1 to 11

[0035] The embodiments of the fiber point effect styrene composition and the preparation method thereof of the present invention are shown in Table 1.

[0036] The preparation method of the styrene composition comprises the following steps:

[0037] After the components are evenly mixed, they are placed in a twin-screw extruder for melt blending and extrusion, and a double vacuum system is used for vacuum extraction to remove the generated small molecular gas. After underwater pelletizing and vacuum drying, the styrene composition with the fiber point effect is obtained.

[0038] The preparation method of the fiber dots is as follows: semi-aromatic high-temperature nylon is melted in a twin-screw extruder, coloring it with color powder, extruding it into granules, and then grinding it into dot-shaped or sheet-shaped fiber dots.

[0039] The processing temperature of the twin-screw extruder in the melt blending and extrusion stage is set to 120-230°C, wherein the processing temperature of zones 1 and 2 is set to 120-190°C, the processing temperature of zones 3 to 5 is set to 180-230°C, and the processing temperature of zones 6 to 10 is set to 190-230°C; the screw speed is set to 350-450rpm.

[0040] Comparative Examples 1 to 6

[0041] The difference between the comparative examples and the examples is only in the types and proportions of the components, as shown in Table 2.

[0042] Among the components described in each embodiment and comparative example,

[0043] New HIPS resin: PS350K produced by Guoqiao Petrochemical, with a melt flow rate of 5g / 10min at 200℃ and 5kg load;

[0044] HIPS recycled resin: LRHPS-BCWA1134 (KS) produced by Guangdong Kingfa Technology, with a melt flow rate of 4g / 10min at 200℃ and 5kg load;

[0045] Toughener: GLOBALPRENE 3566, produced by Li Changrong Chemical, a styrene-butadiene-styrene block copolymer with a butadiene content of approximately 60%;

[0046] Compatibilizer 1: SZ23110 produced by Polyscope, styrene-maleic anhydride copolymer, maleic anhydride content is 23%;

[0047] Compatibilizer 2: Globalprene 9901 produced by Li Changrong Chemical, maleic anhydride grafted SEBS copolymer, maleic anhydride grafting rate of 1.6%;

[0048] Compatibilizer 3: SEBS 7551 produced by Li Changrong Chemical, a styrene-ethylene-butylene-styrene block copolymer;

[0049] Compatibilizer 4: SBG-001 produced by Jiayirong, a toughening compatibilizer with a butadiene-GMA core-shell structure;

[0050] Fiber point 1: Vicnyl 600P, PA10T resin produced by Zhuhai Wantong Special Engineering Plastics Co., Ltd., with a melting point of 316°C;

[0051] Fiber point 2: Vicnyl 400P produced by Zhuhai Wantong Special Engineering Plastics Co., Ltd., PA6T resin, melting point 308°C;

[0052] Fiber point 3: Genestar N1001A produced by Kuraray, PA9T resin, melting point 300℃;

[0053] Fiber point 4: XTR31S produced by DSM, PA4T resin, melting point is 320℃;

[0054] Fiber point 5: SB500 produced by Yizheng Chemical, PET modified resin, melting point is 260℃;

[0055] Weathering agent: a mixture of commercially available hindered amine light stabilizer and benzotriazole ultraviolet light absorber in a mass ratio of 1:1;

[0056] Antioxidant: a mixture of commercially available hindered phenol antioxidant and phosphite antioxidant in a mass ratio of 1:1;

[0057] Lubricant: Commercially available vinyl bisstearamide;

[0058] Unless otherwise specified, the components and raw materials used in the Examples and Comparative Examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all the same. The fiber dots used in the Examples and Comparative Examples of the present invention are specifically prepared by melting, coloring, extruding and granulating the corresponding resins through the above-mentioned fiber dot preparation steps before preparing the styrene composition product, and finally grinding them into dots or flakes with an average particle size of 0.5 mm.

[0059] Table 1

[0060]

[0061] Table 2

[0062]

[0063]

[0064] Effect Example 1

[0065] In order to verify the performance of the styrene composition with fiber point effect of the present invention, the products of each embodiment and comparative example were subjected to the following performance tests, and the specific steps are as follows:

[0066] (1) Notched impact strength test: Each product is subjected to an Izod notched impact strength test according to ISO 180-2000, with the test notch being an A-type notch;

[0067] (2) Fiber point temperature resistance test: Each product was injection molded into a color plate at a molding temperature of 240-250°C at a rate of 50 mm / s and 300 mm / s, respectively. The average length of the fiber points on the color plate surface was tested using a fiber length distribution tester. The average length retention rate (%) was calculated as follows: (average length at 300 mm / s / average length at 50 mm / s) × 100%.

[0068] (3) Fiber point separation rate test during recycling: The injection molded parts of each product (including but not limited to strips, color plates, and parts of other shapes) are crushed into flakes by a crusher, and then melt-extruded and filtered by a single-screw. The melting temperature is set to 200-230°C, and filtered through a 100-200 mesh filter. The weight of the product before and after filtration is weighed to obtain the fiber point separation rate. The separation rate (%) is calculated as follows: (product weight before filtration - product weight after filtration) / product weight before filtration ÷ the proportion of fiber points in the product formula × 100%.

[0069] The test results are shown in Tables 3 and 4.

[0070] Table 3

[0071]

[0072] Table 4

[0073] Test items Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 <![CDATA[Notched impact strength (KJ / m 2 )]]> 13.7 6.8 8.2 12.3 8 9.3 Average fiber length retention rate (%) -- 88.1 92.5 95.8 63.9 95.5 Fiber point separation rate% -- 96.1 95.2 73.5 25.1 68.8

[0074] It can be seen from Tables 3 and 4 that the products obtained in each embodiment have good comprehensive properties: the notched impact strength can reach 10KJ / m 2 As shown above, the average length retention rate of the fiber points can reach more than 90%, and the fiber point separation rate during recycling can reach more than 90%. According to Examples 4 and 9 to 11, it can be seen that the scheme of the present invention uses high-melting-point semi-aromatic high-temperature nylon as fiber points to achieve the expected product effect, and PA10T and PA6T have the best effect. It can be seen from Example 2, Comparative Example 1 and Comparative Example 2 that, at an appropriate content, the introduction of fiber dots has no significant effect on the toughness of the resulting styrene composition, but if the content is too high, the toughness of the product will decrease and it will be less resistant to shearing. It can be seen from Comparative Examples 3 and 4 that when semi-aromatic high-temperature nylon is selected as the fiber dot component, the compatibilizer used with it is very important, and the compatibility between the product components and the recovery efficiency of the fiber dots and resin in the product need to be taken into account. If the selection is inappropriate, the toughness of the product may be significantly reduced, or the fiber dot separation efficiency may deteriorate when the product is recycled. It can be seen from Comparative Example 6 that even if the appropriate type of compatibilizer is selected, if its content is added too much, it is likely to cause the degree of bonding between the fiber dots and the matrix resin to be too high, affecting the subsequent process separation and recovery effect. It can be seen from Comparative Example 5 that the existing commonly used PET fiber dots cannot meet good temperature resistance and recycling performance, and at the same time, this component has a greater impact on the toughness of the matrix resin in the product. The semi-aromatic high-temperature nylon fiber dots described in the present invention can achieve a perfect replacement.

[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A styrene composition with a fiber point effect, characterized in that: The composition comprises the following components in parts by weight: 80-95 parts of polystyrene resin, 2-5 parts of compatibilizer, 3-7 parts of toughening agent, 0.3-1 part of weathering agent and 0.5-5 parts of fiber point; The fiber point is semi-aromatic high-temperature nylon with a melting point of ≥300°C; The polystyrene resin has a melt flow rate of 3 to 8 g / 10 min at 200° C. and a load of 5 kg; The compatibilizer is at least one of a maleic anhydride grafted SEBS copolymer and a styrene-maleic anhydride copolymer.

2. The fiber point effect styrene composition according to claim 1, characterized in that: The semi-aromatic high-temperature nylon is at least one of polydecane terephthalamide and polyhexamethylene terephthalamide.

3. The fiber point effect styrene composition according to claim 1, characterized in that: The polystyrene resin is high-impact polystyrene, which is a mixture of new high-impact polystyrene and recycled high-impact polystyrene. The melt flow rate of the new high-impact polystyrene at 200°C and a load of 5kg is 4 to 8g / 10min, and the melt flow rate of the recycled high-impact polystyrene at 200°C and a load of 5kg is 3 to 5g / 10min.

4. The fiber point effect styrene composition according to claim 1, characterized in that: The toughening agent is a styrene-butadiene-styrene block copolymer with a butadiene content of ≥60%; the weathering agent is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.

5. The fiber point effect styrene composition according to claim 1, characterized in that: The components of the fiber point effect styrene composition also include 0 to 4 parts of a processing aid; the processing aid is at least one of an antioxidant and a lubricant.

6. The method for preparing the fiber point effect styrene composition according to any one of claims 1 to 5, characterized in that: The following steps are involved: After the components are evenly mixed, they are placed in a twin-screw extruder for melt blending and extrusion, and subjected to vacuum extraction treatment, and then pelletized and dried to obtain the styrene composition with the fiber point effect.

7. The method for preparing a styrene composition with fiber point effect according to claim 6, characterized in that: The processing temperature of the twin-screw extruder in the melt blending and extrusion stage is set to 120-230°C, wherein the processing temperature of zones 1 and 2 is set to 120-190°C, the processing temperature of zones 3 to 5 is set to 180-230°C, and the processing temperature of zones 6 to 10 is set to 190-230°C; the screw speed is set to 350-450rpm.

8. Use of the fiber dot effect styrene composition according to any one of claims 1 to 5 in the preparation of electrical appliances and office appliances.

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