PS / MBS alloy material for co-extrusion as well as preparation method and application of PS / MBS alloy material

Abstract

The invention provides a PS / MBS alloy material for co-extrusion as well as a preparation method and application of the PS / MBS alloy material. The alloy material is prepared from the following raw materials in parts by mass: 50 to 90 parts of PS resin, 10 to 25 parts of MBS resin, 0 to 15 parts of compatilizer and 0.1 to 0.4 part of lubricant, the PS resin is selected from high impact polystyrene resin, the relative density is 1.0 g / cm < 3 >-1.05 g / cm < 3 >, and the thermal deformation temperature is 60-70 DEG C; the MBS resin is a core-shell type copolymer. The PS / MBS alloy material prepared by the preparation method provided by the invention can realize the technical effects of improving the surface glossiness of a PS plate co-extrusion layer and being environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a co-extrusion PS / MBS alloy material, its preparation method, and its application. Background Technology

[0002] With the increasing demand for diversified decoration, the surface gloss of PS foam board, a commonly used decorative material, has become an important factor for consumers. Currently, the co-extruded layer of PS foam board is mainly made using HIPS with color masterbatch, but the surface gloss of products produced by this method is relatively low, which cannot meet the market demand for high-gloss products.

[0003] However, there are currently two main methods commonly used in the market to solve the problem of low surface gloss of PS foam boards: one is to use HIPS with color masterbatch to make co-extruded layers, but the surface gloss of products made by this method is relatively low and cannot meet the needs of the high-end market; the other is to use a film-applying method, which can improve surface gloss, but requires the use of glue, which increases VOC emissions and may lead to environmental problems such as strong odor and formaldehyde release, which is not in line with the current trend of green and environmentally friendly development.

[0004] Therefore, there is an urgent need to develop a new type of modified material that can meet the requirements of PS sheet co-extrusion process, be formed in one step, significantly improve the surface gloss of the co-extruded layer, and avoid the environmental problems caused by the film lamination process, so as to meet the market demand for high-gloss, environmentally friendly PS foam boards. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a PS / MBS alloy material for co-extrusion, its preparation method and application, achieving the technical effect of improving the surface gloss of the co-extruded layer of PS sheet while being environmentally friendly.

[0006] According to a first aspect of the present invention, a co-extrusion alloy material is provided, comprising the following raw materials in parts by mass: 50-90 parts PS resin, 10-25 parts MBS resin, 0-15 parts compatibilizer, and 0.1-0.4 parts lubricant; The PS resin is selected from high-impact polystyrene resin with a relative density of 1.0 g / cm³. 3 ~1.05g / cm 3 The heat distortion temperature is 60~70℃; The MBS resin is a core-shell copolymer.

[0007] In some preferred embodiments, the MBS resin is selected from at least one of M-724, M-722 or M-732 from Kanebuchi Corporation of Japan.

[0008] In some preferred embodiments, the MBS resin is selected from Kanekachi Co., Ltd. of Japan, specifically M-724. M-724 and M-722 have higher gloss than M-732, with M-724 exhibiting superior impact strength compared to M-722.

[0009] In some embodiments, the mass ratio of the PS resin to the MBS resin is (5~9):1. Experiments show that the addition of MBS to the co-extruded alloy increases the surface gloss of the co-extruded layer, but excessive MBS will cause the material to soften and the gloss to decrease.

[0010] In some embodiments, the compatibilizer is at least one of maleic anhydride-grafted polyethylene (PE-g-mah), maleic anhydride-grafted polypropylene, or ethylene-methyl acrylate copolymer (EMA). The addition of the compatibilizer improves the compatibility between PS and MBS, further enhancing the gloss of the co-extruded material while maintaining good mechanical properties. Excessive compatibilizer can lead to insufficient stiffness in the co-extruded material and increased costs.

[0011] In some preferred embodiments, the compatibilizer is maleic anhydride-grafted polyethylene with a grafting rate of 3.5% to 4.5%.

[0012] In some embodiments, the lubricant is at least one of stearamide, methyl bis-stearamide, or N,N'-ethylene bis-stearamide (EBS).

[0013] In some embodiments, the co-extrusion alloy material further includes the following additives in parts by weight: 0.1 to 1.0 parts antioxidant, 0.1 to 1.0 parts ultraviolet absorber, and 2 to 4 parts pigment.

[0014] In some embodiments, the antioxidant is a compound of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (antioxidant 1098) and tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), or a compound of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester (antioxidant 1076) and tris(2,4-di-tert-butylphenyl) phosphite.

[0015] In some preferred embodiments, the antioxidant is a compound of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and tris(2,4-di-tert-butylphenyl)phosphite in a mass ratio of 5:3.

[0016] In some embodiments, the ultraviolet absorber is at least one of benzophenone-based ultraviolet absorbers or benzotriazole-based ultraviolet absorbers.

[0017] In some preferred embodiments, the benzophenone-based ultraviolet absorber is 2-hydroxy-4-methoxybenzophenone (UV-9), and the benzotriazole-based ultraviolet absorber is 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV-P); the ultraviolet absorber is a compound of 2-hydroxy-4-methoxybenzophenone and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole in a mass ratio of 3:2.

[0018] In some embodiments, the pigment is selected from at least one of titanium dioxide, phthalocyanine blue, phthalocyanine green, titanium yellow, iron oxide red, pigment red 254, or carbon black. The pigment of the present invention can be an organic or inorganic pigment, and one or more mixed colors can be formulated as needed during production. The selection of pigment depends on the color requirements.

[0019] According to a second aspect of the present invention, a method for preparing a co-extrusion alloy as described in the first aspect is provided, comprising the following steps: S1: Mix MBS resin, lubricant, and optional antioxidants, UV absorbers and pigments to form a mixed powder; S2: Mix PS resin and compatibilizer to form mixed granules; S3: The mixed granules are added to the main hopper of the extruder, and the mixed powder is added to the feed port by side feeding. The mixture is melt-extruded and granulated after water treatment. After drying, PS / MBS alloy material for co-extrusion is obtained.

[0020] In some embodiments, the extruder is a parallel twin-screw extruder.

[0021] In some implementations, the mixing time in step S1 is 5 to 8 minutes.

[0022] In some implementations, the mixing time in step S2 is 3 to 5 minutes.

[0023] In some embodiments, in step S3, the temperature of the melt extrusion is 180~200℃, the screw speed is 150~250rpm, and the feeding speed is 10~15rpm.

[0024] Co-extrusion is a process that uses two independent extrusion systems to simultaneously extrude molten plastics of different materials or colors to form a two-layer structure sheet. The workflow generally includes: two extruders heating different materials to a molten state (such as PS foam base material and PS co-extruded material), the melt entering the die head through independent runners, the inner layer material passing through the die core first, and the outer layer material subsequently covering it. The pressure difference between the inner and outer layers must be controlled within a certain range (usually 5-10 MPa) to prevent delamination. The extruded wire is then cooled in a water bath. Therefore, the effectiveness of co-extrusion largely depends on the adhesion of the co-extruded materials.

[0025] According to a third aspect of the present invention, the application of the co-extrusion alloy material as described in the first aspect or the co-extrusion alloy material prepared by the preparation method described in the second aspect in the production of PS decorative panels is proposed. The PS / MBS alloy material prepared by the present invention is suitable for use as a co-extrusion layer of PS foamed board, and has good adhesion and high gloss surface effect.

[0026] According to one embodiment of the present invention, at least the following beneficial effects are achieved: 1. The present invention modifies the material by blending MBS resin with PS resin, which significantly improves the gloss compared to PS resin alone.

[0027] 2. This invention, by controlling the processing technology, particularly by feeding granular and powdered materials separately, avoids uneven stratification caused by differences in material density. Simultaneously, the high-shear parallel twin-screw extruder mixing process allows the butadiene rubber phase in MBS to form a uniformly distributed nanoscale structure within the PS matrix, significantly affecting the surface gloss of the final product and ensuring a more ideal gloss level in the surface layer.

[0028] 3. The PS / MBS alloy material prepared by this invention is co-extruded onto the surface of PS foam board in one step, which not only solves the problem of low gloss of traditional HIPS materials, but also avoids environmental problems such as VOC emissions and formaldehyde release caused by adhesives in the film-applying process, thus meeting people's dual needs for diversified and environmentally friendly decoration materials. Attached Figure Description

[0029] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein: Figure 1 The photo shows the application of the co-extruded PS / MBS alloy prepared in Example 2 of this invention on a foamed board; Figure 2 The photo shows the application of the co-extruded PS / MBS alloy prepared in Example 3 of this invention on a foamed board; Figure 3 Photographs showing the application of the co-extruded PS / MBS alloy prepared in Comparative Example 1 of this invention on foamed boards; Figure 4 This is a photograph showing the application of the co-extruded PS / MBS alloy prepared in Comparative Example 2 of this invention on a foamed board. Detailed Implementation

[0030] The following will describe the concept and technical effects of the present invention clearly and completely with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention, but the present invention is not limited to the scope of the embodiments described.

[0031] Unless otherwise specified, the experimental methods in the following examples were performed according to conventional methods and conditions. Unless otherwise specified, the raw materials, reagents, or apparatus used in the following examples can be obtained from conventional commercial sources or by existing known methods. Unless otherwise specified, the experimental methods described are conventional methods. The PS resin used was high-impact polystyrene HIPS 425TVL manufactured by Kumho, South Korea, with a relative density of 1.04 g / cm³. 3 The heat distortion temperature is 76℃; the MBS resin is M724 from Kaneka Corporation of Japan.

[0032] Examples 1-5 and Comparative Examples 1-2 Comparative Example 1 uses existing technology, while Comparative Example 2 added excessive MBS resin, resulting in generally lower gloss and average adhesion after co-extrusion.

[0033] The embodiments of the present invention can be of any color, and even the addition of wood grain agents or pearlescent pigments can create a wood grain effect or a metallic effect. The co-extruded material has high gloss and good adhesion.

[0034] The raw material formulations for Examples 1-5 and Comparative Examples 1-2 are shown in Table 1: Table 1. Raw material formulations (parts by mass / kg) for the examples and comparative examples.

[0035] The preparation methods of Examples 1-5 and Comparative Example 2 include the following steps: 1. Mix the powdered materials MBS resin, antioxidant, UV absorber and pigment in a mixing hopper for 5 minutes to make powder packets; 2. Next, mix the granular PS resin and compatibilizer in the grinding bucket for 3 minutes until they are evenly mixed, forming granules for extrusion. 3. During extrusion, the majority of the granules are added to the main hopper, while the minority of the powder is added to the feed port via side feeding. The feed rates of the main feed and the side feed are controlled according to the formula ratio. Melt extrusion is carried out in a parallel twin-screw extruder. The melt extrusion temperature is shown in the table below, the screw speed is 200±10 rpm, and the feed speed is 50±5 rpm.

[0036]

[0037] 4. Cooling and granulation: The molten material is cooled by a water cooling device, with the cooling water temperature controlled at 20±5℃, and then granulated to obtain granular PS / MBS alloy material. 5. Drying treatment: The granulated PS / MBS alloy material is fed into a drying equipment and dried at 80℃ for 4 hours to reduce the moisture content to below 0.1%; 6. Packaging and storage: Pack the dried PS / MBS alloy material and store it in a dry, cool place, avoiding direct sunlight and humid environments.

[0038] Test case The products of the examples and comparative examples were injection molded into standard test strips according to standard dimensions. The physical performance test standards and test conditions are shown in Table 2, and the performance test results are shown in Table 3.

[0039] The products of the examples and comparative examples were injection molded into samples (mold temperature between 60℃ and 70℃, and temperature of each zone of the injection molding machine between 200℃ and 230℃) and their mirror gloss was tested, as shown in Table 3.

[0040] Table 2 Physical Performance Test Standards

[0041] Table 3 Performance test results of the examples and comparative examples

[0042] Efficacy verification shows that, compared with Comparative Examples 1-2, the Vicat softening point of the PS / MBS alloy produced by this invention decreases with the increase of MBS or compatibilizer in Examples 1-5, while the elongation at break increases with the increase of MBS or compatibilizer, and the tensile strength and flexural strength show the opposite trend. The melt index increases with the increase of compatibilizer. Furthermore, the alloy produced by this process exhibits better adhesion to other materials during co-extrusion, and the surface gloss and uniformity of the product are significantly improved.

[0043] A comparison of Examples 1-5 with Comparative Example 1 shows that adding an appropriate amount of MBS resin to HIPS 425TVL can significantly improve the gloss of the material while maintaining good mechanical properties, making it particularly suitable for co-extrusion applications. In Comparative Example 2, excessive addition of MBS not only increases cost but also reduces gloss compared to the examples. Examples 1, 2, and 3 demonstrate that a small amount of compatibilizer can significantly improve gloss, while further addition of compatibilizer has little effect on gloss improvement; simultaneously, interlayer peel strength increases with increasing compatibilizer dosage.

[0044] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. An alloy material for co-extrusion, characterized in that, The following raw materials are included in the preparation by weight: 50-90 parts PS resin, 10-25 parts MBS resin, 0-15 parts compatibilizer, and 0.1-0.4 parts lubricant; The PS resin is selected from high-impact polystyrene resin with a relative density of 1.0 g / cm³. 3 ~1.05g / cm 3 The heat distortion temperature is 60~70℃; The MBS resin is a core-shell copolymer.

2. The co-extrusion alloy material according to claim 1, characterized in that, The mass ratio of the PS resin to the MBS resin is (5~9):

1.

3. The co-extrusion alloy material according to claim 1, characterized in that, The compatibilizer is at least one of maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or ethylene-methyl acrylate copolymer.

4. The co-extrusion alloy material according to claim 1, characterized in that, The lubricant is at least one of stearamide, methyl bis-stearamide, or N,N'-ethylene bis-stearamide.

5. The co-extrusion alloy material according to claim 1, characterized in that, It also includes the following additives by weight: 0.1 to 1.0 parts antioxidant, 0.1 to 1.0 parts ultraviolet absorber, and 2 to 4 parts pigment.

6. The co-extrusion alloy material according to claim 5, characterized in that, The antioxidant is a compound of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and tris(2,4-di-tert-butylphenyl)phosphite, or a compound of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester and tris(2,4-di-tert-butylphenyl)phosphite.

7. The co-extrusion alloy material according to claim 5, characterized in that, The ultraviolet absorber is at least one of benzophenone-based ultraviolet absorbers or benzotriazole-based ultraviolet absorbers.

8. A method for preparing a co-extrusion alloy material as described in any one of claims 1-7, characterized in that, Includes the following steps: S1: Mix MBS resin, lubricant, and optional antioxidants, UV absorbers and pigments to form a mixed powder; S2: Mix PS resin and compatibilizer to form mixed granules; S3: The mixed granules are added to the main hopper of the extruder, and the mixed powder is added to the feed port by side feeding. The mixture is melt-extruded and granulated after water treatment. After drying, PS / MBS alloy material for co-extrusion is obtained.

9. The preparation method according to claim 8, characterized in that, In step S3, the temperature of the melt extrusion is 180~200℃, the screw speed is 150~250rpm, and the feeding speed is 10~15rpm.

10. The application of the co-extrusion alloy material according to any one of claims 1-7 or the co-extrusion alloy material prepared by the preparation method according to any one of claims 8-9 in the production of PS decorative panels.

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