Matt PMMA (polymethyl methacrylate) resin composition as well as preparation method and application thereof

Abstract

The invention provides a matte PMMA (polymethyl methacrylate) resin composition as well as a preparation method and application thereof, the matte PMMA resin composition comprises specific parts of polymethyl methacrylate and polyvinylpyrrolidone, and the polymethyl methacrylate and the polyvinylpyrrolidone in specific parts by weight are selected for matching, so that the matte PMMA resin composition is prepared. According to the present invention, the PMMA resin composition has characteristics of low glossiness and matte effect on the premise of no addition of any matte agent, and does not affect the excellent physical property of the polymethyl methacrylate, such that the layering and other appearance problems of the product obtained after the injection molding of the obtained matte PMMA resin composition do not exist, and the toughness is significantly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a matte PMMA resin composition and a preparation method and application thereof. Background Art

[0002] Polymethyl methacrylate (PMMA) is an organic polymer material polymerized from methyl methacrylate monomer (MMA). It has excellent transparency and surface gloss, excellent weather resistance, high surface hardness and good high temperature performance, and is widely used in various fields. Since PMMA has excellent surface gloss, it is easy to produce total reflection, which can form a gorgeous appearance effect. However, in some applications, such as in cars or interior decoration products, the material surface is often required to have a low gloss effect, thereby achieving a matte effect.

[0003] At present, in order to obtain matte PMMA materials, the conventional practice is to reduce the surface roughness of the material by mold sun-texturing, and to reduce the gloss of the PMMA material by laser engraving or adding matte modifiers. Among them, the sun-texturing method is limited by the molding method and has a narrow application range. The laser engraving method is very complicated and inefficient, and is not suitable for mass production applications. The modifiers used in the method of adding matte modifiers are mostly some micron-level cross-linked microspheres, which are high in cost and added in high amounts, which have a greater impact on the physical properties of PMMA itself and will seriously affect the toughness of PMMA.

[0004] Therefore, in view of the above problems, it is urgent to develop a matte PMMA resin composition with low cost, low gloss and high toughness. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a matte PMMA resin composition, a preparation method and application thereof. By using specific weight portions of polymethyl methacrylate and polyvinyl pyrrolidone for combination, the obtained PMMA resin composition has a lower surface gloss and a matte effect, and at the same time has higher toughness, lower cost and good product appearance, which is very suitable for large-scale industrial production applications.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a matte PMMA resin composition, wherein the matte PMMA resin composition comprises the following components in parts by weight:

[0008] 90-98 parts by weight of polymethyl methacrylate;

[0009] Polyvinyl pyrrolidone 2-10 parts by weight.

[0010] The matte PMMA resin composition provided by the present invention comprises specific portions of polymethyl methacrylate (PMMA) and polyvinyl pyrrolidone (PVP). By adding a specific amount of PVP, not only the glossiness of the obtained PMMA resin composition is effectively reduced, and a matte effect is achieved, but also, since no matte agent is required to be added, the excellent physical properties of PMMA itself will not be affected, so that the obtained product after injection molding of the obtained matte PMMA resin composition will not have appearance problems such as delamination, and has high toughness. In addition, the matte PMMA resin composition also has the advantage of low cost, and is very suitable for large-scale industrial production applications.

[0011] Wherein, the content of polymethyl methacrylate in the matte PMMA resin composition can be 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight or 98 parts by weight.

[0012] The content of polyvinyl pyrrolidone in the matte PMMA resin composition can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.

[0013] The mass percentage of polymethyl methacrylate in the matte PMMA resin composition provided by the present invention should not be less than 90%.

[0014] Preferably, the melt index of the polymethyl methacrylate is ≤50g / 10min, for example, 50g / 10min, 40g / 10min, 30g / 10min, 20g / 10min, 15g / 10min, 10g / 10min, 8g / 10min, 7g / 10min, 6g / 10min, 5g / 10min, 4g / 10min, 3g / 10min, 2g / 10min or 1g / 10min, and more preferably ≤15g / 10min; the test temperature of the above melt index is 230°C and the load is 3.8kg. For specific testing, please refer to the ISO 1133-1-2022 standard.

[0015] Preferably, the K value of the polyvinyl pyrrolidone is 25 to 100, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95, etc., further preferably 55 to 95, and further preferably 80 to 92; by further limiting the K value of the polyvinyl pyrrolidone to the above-mentioned specific range, the obtained matte PMMA resin composition can achieve the best matte effect and the highest toughness.

[0016] It should be noted that the K value of polyvinyl pyrrolidone refers to a characteristic value related to the relative viscosity of polyvinyl pyrrolidone, and the relative viscosity of a polymer is a physical quantity related to the molecular weight of a polymer. Therefore, the K value of polyvinyl pyrrolidone can be used to characterize the average molecular weight of polyvinyl pyrrolidone. The larger the K value, the larger the molecular weight. In the present invention, the K value of the above-mentioned polyvinyl pyrrolidone can be tested with reference to "GB / T 33069-2016 Detection Method for Industrial Poly N-Vinyl Pyrrolidone".

[0017] Preferably, the PMMA resin composition comprises the following components in parts by weight:

[0018] 92-96 parts by weight of polymethyl methacrylate;

[0019] Polyvinyl pyrrolidone 4-8 parts by weight.

[0020] Preferably, the glossiness of the matte PMMA resin composition is less than 25%, for example, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16% or 15%, etc., and more preferably less than 20%.

[0021] The glossiness test method of the matte PMMA resin composition includes: adding the PMMA resin composition into an injection molding machine, setting the injection molding temperature to 230°C, using a high-gloss mold to injection mold a 2.0 mm thick high-gloss square plate, and then using a BYK 4561 gloss tester to test the glossiness of the high-gloss square plate at an angle of 80° according to GB / T8807-1988.

[0022] Preferably, the matte PMMA resin composition also includes an antioxidant.

[0023] Preferably, the content of the antioxidant in the matte PMMA resin composition is not higher than 1 part by weight, for example, 1 part by weight, 0.8 part by weight, 0.6 part by weight, 0.4 part by weight or 0.2 part by weight.

[0024] Preferably, the antioxidant includes any one of a hindered phenol antioxidant, a phosphite antioxidant or an organic sulfur antioxidant, or a combination of at least two thereof.

[0025] Among them, the hindered phenol antioxidants include but are not limited to antioxidant 1010, antioxidant 1076, and antioxidant 1098; the phosphite antioxidants include but are not limited to antioxidant 168; the organic sulfur antioxidants include but are not limited to dilauryl thiodipropionate, distearyl thiodipropionate, and dilauryl thiodipropionate.

[0026] Preferably, the matte PMMA resin composition also includes a lubricant.

[0027] Preferably, the content of the lubricant in the matte PMMA resin composition is not higher than 1 part by weight, for example, 1 part by weight, 0.8 part by weight, 0.6 part by weight, 0.4 part by weight or 0.2 part by weight.

[0028] Preferably, the lubricant includes any one of amide lubricants, polysiloxane lubricants, stearate lubricants, polyethylene wax or polypropylene wax, or a combination of at least two thereof.

[0029] Among them, the amide lubricant includes but is not limited to stearic acid amide; the polysiloxane lubricant includes but is not limited to polydiethylsiloxane; the stearate lubricant includes but is not limited to zinc stearate.

[0030] In a second aspect, the present invention provides a method for preparing the matte PMMA resin composition as described in the first aspect, the preparation method comprising: mixing polymethyl methacrylate, polyvinyl pyrrolidone, an optional antioxidant and an optional lubricant, and performing extrusion granulation in an extruder to obtain the matte PMMA resin composition.

[0031] Preferably, the mixing time is 1 to 3 min, for example, 1 min, 1.2 min, 1.4 min, 1.6 min, 1.8 min, 2 min, 2.2 min, 2.4 min, 2.6 min, 2.8 min or 3 min.

[0032] Preferably, the extruder is a twin-screw extruder.

[0033] Preferably, the temperatures of the working zones in the twin-screw extruder are: the temperatures of zone one and zone two are each independently 120-170°C (for example, 120°C, 130°C, 140°C, 150°C, 160°C or 170°C, etc.), the temperatures of zone three to zone five are each independently 190-210°C (for example, 190°C, 195°C, 200°C, 205°C or 210°C, etc.), and the temperatures of zone six to zone ten are each independently 170-190°C (for example, 170°C, 175°C, 180°C, 185°C or 190°C, etc.).

[0034] In a third aspect, the present invention provides a use of the matte PMMA resin composition as described in the first aspect in preparing automotive interior or interior decoration products.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The matte PMMA resin composition provided by the present invention comprises specific parts of polymethyl methacrylate and polyvinyl pyrrolidone. By selecting specific weight parts of polymethyl methacrylate and polyvinyl pyrrolidone for combination, the obtained PMMA resin composition can have a lower gloss without adding any matte agent, thereby achieving a matte effect. At the same time, the excellent physical properties of polymethyl methacrylate itself will not be affected, so that the product obtained by injection molding of the obtained matte PMMA resin composition will not have appearance problems such as delamination, and even the toughness is significantly improved;

[0037] (2) The matte PMMA resin composition provided by the present invention has a gloss of only 8.0-19.2% after injection molding at an angle of 80°, and a toughness of up to 3.1-4.8 kJ / m 2 , and there is no delamination problem in the appearance, with low gloss, excellent toughness and good appearance. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0039] Some of the raw material information involved in the following examples and comparative examples are as follows:

[0040] (1) Polymethyl methacrylate (PMMA)

[0041] PMMA-1: melt index is 2g / 10min (230℃ / 3.8kg), purchased from Chimei Chemical, brand CM-205;

[0042] PMMA-2: melt index is 8 g / 10 min (230°C / 3.8 kg), purchased from Chi Mei Chemical, brand CM-207;

[0043] PMMA-3: melt index is 12 g / 10 min (230°C / 3.8 kg), purchased from Chi Mei Chemical, brand CM-211;

[0044] PMMA-4: melt index is 16 g / 10 min (230°C / 3.8 kg), purchased from Chi Mei Chemical, brand PMMASX303;

[0045] PMMA-5: melt index is 40 g / 10 min (230° C. / 3.8 kg), purchased from LG Chemical, brand BA410.

[0046] (2) Polyvinylpyrrolidone (PVP)

[0047] PVP-1: K value is 90, purchased from Shanghai Kema;

[0048] PVP-2: K value is 85, purchased from Shanghai Kema;

[0049] PVP-3: K value is 75, purchased from Shanghai Kema;

[0050] PVP-4: K value is 60, purchased from Shanghai Kema;

[0051] PVP-5: K value is 30, purchased from Shanghai Kema;

[0052] PVP-6: K value is 100, purchased from Shanghai Kema.

[0053] (3) Antioxidants

[0054] Antioxidant 1010: hindered phenol antioxidant, purchased from Tianjin Li'an Long New Materials Co., Ltd., brand RIANOX 1010;

[0055] Antioxidant 168: phosphite antioxidant, purchased from Tianjin Li'an Long New Materials Co., Ltd., brand name RIANOX 168.

[0056] (4) Lubricant: Vinyl bisstearamide, purchased from Tyco Brown Chemical (Zhangjiagang) Co., Ltd.

[0057] (5) Matting agent: styrene-acrylonitrile cross-linked microspheres, purchased from Shanghai Dingyuan Chemical Industry, brand name BTMA.

[0058] Examples 1 to 15 and Comparative Examples 1 to 3

[0059] Examples 1 to 15 and Comparative Examples 1 to 3 respectively provide a matte PMMA resin composition, and the components and amounts thereof are shown in Table 1 and Table 2;

[0060] In Table 1 and Table 2, the dosage units of each component are "parts by weight";

[0061] Table 1

[0062]

[0063] Table 2

[0064]

[0065]

[0066] The preparation method of the matte PMMA resin composition provided in Examples 1 to 15 and Comparative Examples 1 to 3 comprises: mixing PMMA, PVP (and / or matte agent), antioxidant and lubricant for 2 minutes, feeding into a twin-screw extruder for extrusion granulation, and obtaining the matte PMMA resin composition;

[0067] The twin-screw extruder is divided into ten zones, and the temperatures of the zones are: the temperatures of zones one and two are both 150°C, the temperatures of zones three to five are both 200°C, and the temperatures of zones six to ten are all 180°C.

[0068] Performance Test:

[0069] (1) Gloss: The PMMA resin composition was added into an injection molding machine, the injection molding temperature was set to 230°C, and a 2.0 mm thick high-gloss square plate was injection molded using a high-gloss mold. Then, the gloss of the high-gloss square plate at an angle of 80° was tested using a BYK 4561 gloss tester in accordance with GB / T 8807-1988.

[0070] (2) Toughness: In accordance with ISO 180-2000, injection molded A-type notched impact standard specimens are used to test the notched impact strength of the material.

[0071] (3) Delamination: The PMMA resin composition was added into an injection molding machine, the injection molding temperature was set to 230°C, and a 2.0 mm thick high-gloss square plate was injection molded using a high-gloss mold. Whether the high-gloss square plate was delaminated was visually observed.

[0072] The PMMA resin compositions provided in Examples 1 to 15 and Comparative Examples 1 to 3 were tested according to the above test method. The test results are shown in Table 3:

[0073] Table 3

[0074]

[0075]

[0076] According to the data in Table 3, we can see that:

[0077] (1) The PMMA resin compositions provided in Examples 1 to 15 have a glossiness of 8.0 to 19.2% and a toughness of 3.1 to 4.8 kJ / m 2 , and the injection molded products have no delamination problems, and have low gloss, excellent toughness and good appearance;

[0078] Among them, the PMMA resin compositions provided in Examples 1 to 3, Examples 6 to 7 and Examples 10 to 12 have a glossiness as low as 8.0 to 9.8%, and a toughness as high as 3.6 to 4.8 kJ / m 2 , with the highest toughness and lowest gloss, and the best matte effect.

[0079] (2) By comparing the data of Example 1 and Comparative Examples 1-2, it can be seen that the relative amounts of PMMA and PVP will affect the matte effect and toughness of the PMMA resin composition obtained; if the relative amount of PMMA is too low (Comparative Example 1), it is easy to cause the toughness of the PMMA resin composition obtained to be significantly reduced, and the glossiness is improved, the matte effect is deteriorated, and the appearance of the injection molded product also shows stratification; and if the relative amount of PVP is too low (Comparative Example 2), it is easy to cause the glossiness of the PMMA resin composition obtained to be significantly increased, the matte effect is significantly reduced, and the toughness is also reduced.

[0080] (3) By comparing the data of Example 1 and Comparative Example 3, it can be seen that the glossiness of the PMMA resin composition obtained by adding a conventional matte agent is significantly higher than that of the PMMA resin composition obtained by adding PVP, and the toughness decreases significantly. This shows that the present invention, by adding a specific amount of PVP, not only effectively reduces the glossiness of the PMMA resin composition obtained and achieves a matte effect, but also does not affect the physical properties of the PMMA resin composition itself.

[0081] The applicant declares that the present invention illustrates a matte PMMA resin composition and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A matte PMMA resin composition, characterized in that: The matte PMMA resin composition comprises the following components in parts by weight: 90-98 parts by weight of polymethyl methacrylate; Polyvinyl pyrrolidone 2-10 parts by weight.

2. The matte PMMA resin composition according to claim 1, characterized in that: The melt index of the polymethyl methacrylate is ≤50 g / 10 min, preferably ≤15 g / 10 min.

3. The matte PMMA resin composition according to claim 1 or 2, characterized in that: The K value of the polyvinyl pyrrolidone is 25-100, preferably 55-95, and more preferably 80-92.

4. The matte PMMA resin composition according to claim 1, characterized in that: The PMMA resin composition comprises the following components in parts by weight: 92-96 parts by weight of polymethyl methacrylate; Polyvinyl pyrrolidone 4-8 parts by weight.

5. The matte PMMA resin composition according to claim 1 or 4, characterized in that: The glossiness of the matte PMMA resin composition is less than 25%, preferably less than 20%; Preferably, the matte PMMA resin composition further comprises an antioxidant; Preferably, the content of antioxidant in the matte PMMA resin composition is not higher than 1 part by weight; Preferably, the antioxidant includes any one of a hindered phenol antioxidant, a phosphite antioxidant or an organic sulfur antioxidant, or a combination of at least two thereof.

6. The matte PMMA resin composition according to claim 1 or 4, characterized in that: The matte PMMA resin composition also includes a lubricant; Preferably, the content of lubricant in the matte PMMA resin composition is not higher than 1 part by weight; Preferably, the lubricant includes any one of amide lubricants, polysiloxane lubricants, stearate lubricants, polyethylene wax or polypropylene wax, or a combination of at least two thereof.

7. A method for preparing the matte PMMA resin composition according to any one of claims 1 to 6, characterized in that: The preparation method comprises: mixing polymethyl methacrylate, polyvinyl pyrrolidone, an optional antioxidant and an optional lubricant, and performing extrusion granulation in an extruder to obtain the matte PMMA resin composition.

8. The preparation method according to claim 7, characterized in that: The mixing time is 1 to 3 minutes.

9. The preparation method according to claim 7 or 8, characterized in that: The extruder is a twin-screw extruder; Preferably, the temperatures of the working zones in the twin-screw extruder are: the temperatures of zone 1 and zone 2 are independently 120-170°C, the temperatures of zone 3-5 are independently 190-210°C, and the temperatures of zone 6-10 are independently 170-190°C.

10. Use of the matte PMMA resin composition according to any one of claims 1 to 6 in preparing automobile interior decoration or interior decoration products.

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