High-rigidity and high-wear-resistance PMMA (polymethyl methacrylate) alloy material capable of being cured by visible light and preparation method of PMMA alloy material

Abstract

The invention relates to a visible-light-cured high-rigidity and high-wear-resistance PMMA alloy material and a preparation method thereof. The visible-light-cured high-rigidity and high-wear-resistance PMMA alloy material is specifically prepared from the following raw materials in parts by weight: 60-80 parts of polymethyl methacrylate (PMMA) resin, 10-20 parts of polycarbonate (PC) resin, 2-8 parts of vinyl ester resin, 3-10 parts of molybdenum disulfide powder, 1-3 parts of a photosensitive aid and 1-3 parts of styrene oxide. The preparation method has the beneficial effects that visible light (390-780 nm) is adopted to initiate free radical reaction of vinyl ester resin, and a three-dimensional net-shaped macromolecular chain structure obtained through crosslinking is introduced into a surface layer of the PMMA alloy material, so that the surface rigidity of the PMMA alloy material is improved, the effect of fixing an inorganic powder-molybdenum disulfide lamellar structure in the PMMA alloy material can be achieved, and the service life of the PMMA alloy material is prolonged. The prepared PMMA alloy material has the characteristics of reducing the wear volume and improving the wear resistance of a resin material, and the obtained PMMA alloy material has very excellent performance in various surface characteristic tests such as surface hardness, scratch resistance, friction coefficient, wear quality, wear resistance grade and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a visible light-cured high-rigidity and high-wear-resistant PMMA alloy material and a preparation method thereof. Background Art

[0002] The current trend toward higher performance and greater multifunctionality in polymer materials is becoming increasingly evident. Effective solutions generally fall into two categories: chemical modification and physical blending. Chemical modification typically involves the synthesis of novel polymers with novel structures and properties through polymerization reactions, while physical blending involves simply mixing and blending organic and inorganic materials with different properties. Both approaches have their own advantages and disadvantages in terms of difficulty, modification effectiveness, and cost.

[0003] Polymethyl methacrylate (PMMA), also known as acrylic, is an amorphous polymer material with a flexible molecular chain structure. While the flexible acrylate groups within its molecular chain impart low surface rigidity, the amorphous nature and low degree of crystallinity of its aggregated structure further exacerbate PMMA's surface defects, resulting in unfavorable surface properties such as a soft surface, poor wear resistance, susceptibility to scratching, and high abrasion during actual use. Existing technical solutions have mostly employed physical blending methods, achieving surface modification through the addition of organic / inorganic fillers such as molybdenum disulfide, fluororesins, and silicone resins. The inorganic modification scheme of fumed alumina / carbon black adopted in CN 112552629 A improves scratch resistance by simply increasing the surface rigidity of the PMMA material. However, excessive addition of inorganic powder can easily lead to a serious loss of PMMA's mechanical properties. In addition, this scheme fails to address other indicators such as friction coefficient, wear volume, and friction resistance grade. CN 109401161A and CN 111154210A both adopt organic modification schemes with different characteristics. The composite schemes of fluororesin / silicone powder and silicone rubber / silicone additives adopted in these schemes can actually only achieve a certain improvement in the scratch resistance of PMMA alloy materials. The addition of organic additives further reduces the surface hardness of the material, which is particularly unfavorable for testing other wear performance indicators. Ultimately, as a thermoplastic polymer, PMMA's flexible molecular chains are prone to sliding and lack effective fixation, which is the fundamental reason why its surface is easily worn. Therefore, a combination of chemical modification and physical modification must be adopted to introduce a certain degree of polymer three-dimensional cross-linked network structure into its surface structure in order to fundamentally improve and enhance the relevant surface properties of PMMA. Summary of the Invention

[0004] The purpose of the present invention is to overcome the weaknesses of the existing technology and provide a high-rigidity and high-wear-resistant PMMA alloy material that is cured by visible light. In view of the current situation that the existing technical solutions can only improve the scratch resistance of PMMA surface properties, but cannot fully take into account the requirements of more surface properties such as surface hardness, friction coefficient, friction resistance level, wear volume, etc., based on the efficient and easy-to-achieve visible light-induced cross-linking reaction of vinyl resin, a three-dimensional molecular chain structure is introduced into the surface layer of the PMMA alloy material, and the fixing effect of the molybdenum disulfide sheet structure is strengthened, so that the properties of the solid powder can be fully utilized, thereby achieving the modification goal of comprehensively improving the surface wear resistance of the PMMA alloy material.

[0005] The present invention is achieved through the following technical solutions:

[0006] A visible light-cured high-rigidity, high-wear-resistant PMMA alloy material and a preparation method thereof, comprising the following raw materials in parts by weight:

[0007]

[0008] The PMMA resin is low-melting, high-viscosity extrusion-grade polymethyl methacrylate, and its melt index MFR under the test conditions of 230° C. and 3.8 kg is ≤1.5 g / 10 min.

[0009] The PC resin is a copolymerized polycarbonate resin with high hardness and scratch resistance, and its ball pressure hardness is ≥125MPa and its abrasion loss is ≤15mg / 1000cy.

[0010] The vinyl resin is a bisphenol A type or phenolic type vinyl resin, has an acid value of 10±3.0 mgKOH / g, and a gel time (25° C.) of 15±5 min.

[0011] The molybdenum disulfide powder is a high-purity nano-scale inorganic molybdenum disulfide powder with a purity of ≥99.9% and an average particle size (D50) of 30-100 nm.

[0012] The photosensitizer is one or more of acetylacetone metal salt, acylphosphine oxide, polyetheramine and the like.

[0013] The styrene oxide is a colorless, low-viscosity liquid with a transparent appearance and a viscosity (20° C.) ≤ 0.8 Pa.s.

[0014] A second object of the present invention is to provide a visible light-cured PMMA alloy material with high rigidity and high wear resistance and a preparation method thereof, wherein the method comprises the following steps:

[0015] (1) Vinyl resin and styrene oxide are weighed in parts by weight, mixed evenly, and added to a glass container of a certain volume. The water bath temperature is adjusted to 55° C., and the mixture is dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder is weighed in parts by weight, added to the glass container, and stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the molybdenum disulfide with a lamellar structure.

[0016] (2) PMMA resin, PC resin and photosensitizer are weighed according to the weight parts, premixed in a high-pressure mixer for 5 minutes, and then the molybdenum disulfide inorganic powder coated with vinyl resin is added. After mixing evenly, the mixture is placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder through the feeding screw. The diameter of the twin-screw extruder used is 35 mm, and the aspect ratio L / D is 48. The temperature of each zone of the main barrel from the feed port to the head outlet is set to: 170°C, 190°C, 210°C, 220°C, 230°C, 220°C, 215°C, 210°C, 220°C, and the main barrel speed is 200 rpm. After the processes of melt extrusion, granulation, drying and the like, the high-rigidity and high-wear-resistant PMMA alloy material cured by visible light is obtained.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. Unlike traditional physical blending technology solutions, the present invention is based on a free radical cross-linking reaction cured by visible light (390-780nm), which constructs a three-dimensional cross-linked molecular chain structure in the surface layer of the PMMA alloy. This not only increases the surface hardness of the material, but also greatly reduces its friction coefficient and wear volume, especially the wear condition of metal materials.

[0019] 2. This easy-to-achieve cross-linking reaction also strengthens the modification effect of molybdenum disulfide as a high-efficiency solid phase powder to a certain extent. By combining it with the cross-linked polymer structure through pretreatment, it avoids the degree of wear in high-load and high-cycle wear tests, thereby giving the PMMA alloy material more lasting wear resistance.

[0020] 3. The PMMA alloy material obtained by the technical solution of the present invention, after being subjected to visible light enhanced irradiation under specific conditions (2kW metal halide lamp, illuminance 300mW / cm2, irradiation time 30min), the surface ball pressure hardness of the PMMA material increased from 140MPa to about 170MPa. After being stored for a certain period of time (30d, 60d) under natural light conditions, its ball pressure hardness index was further increased to a higher level of 180MPa-185MPa, indicating that the degree of cross-linking reaction inside the surface layer of the PMMA alloy material has increased; the test material From the key indicators of the material such as scratch resistance, friction coefficient, wear volume, and friction resistance level, it can be seen that not only the scratch resistance index (ΔL value) of the material has been reduced from the previous 2.2 to about 0.9, but the friction coefficient has also been greatly reduced to about 0.28. The wear quality of PMMA alloy material can reach as low as 76mg / 1000 circles. After undergoing high-load (10N) and long-cycle (10,000 times) wear resistance tests, the wear resistance level of PMMA alloy material has also been greatly improved from the poor level 1 (obviously visible surface wear) to level 4 (vaguely visible surface wear). DETAILED DESCRIPTION

[0021] The present invention will be further described below through specific embodiments, which are only used to illustrate the present invention rather than to limit the present invention.

[0022] Raw materials used in the embodiments of the present invention:

[0023] PMMA: polymethyl methacrylate PMMA SR6500, with a melt index (MFR) of 0.7 g / 10 min at 230°C and 3.8 kg, manufactured by Asahi Kasei Corporation of Japan.

[0024] PC resin: polycarbonate Lexan DMX2415P, ball pressure hardness 129MPa, abrasion loss 10mg / 1000cy, SABIC Innovative Plastics.

[0025] Vinyl resin-1: bisphenol A type vinyl resin R-802, acid value of 8-10 mgKOH / g, gel time (25° C.) of 12-15 min, Showa Highpolymer Co., Ltd. of Japan.

[0026] Vinyl resin-2: phenolic vinyl resin Atlac 590, acid value of 10-13 mgKOH / g, gel time (25° C.) of 16-20 min, Royal DSM of the Netherlands.

[0027] Molybdenum disulfide powder: Nano-scale molybdenum disulfide flaky inorganic powder with a gray-black appearance, a purity of ≥99.9%, and an average particle size (D50) of 50nm.

[0028] Photosensitizer-1: manganese acetylacetonate MnAA, black or brown-black crystalline powder, purity ≥99%, effective manganese content 15-15.6%, Hubei Xinghengye Technology Co., Ltd.

[0029] Photosensitizer-2: 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), white powder, obtained from Changzhou Huadong Chemical Research Institute.

[0030] Photosensitizer-3: Fast-curing polyetheramine Jeffamine XTJ-590, colorless or light yellow liquid, Huntsman, USA.

[0031] Styrene oxide: also known as phenyl ethylene oxide, colorless or light yellow liquid, purity ≥99%, Shanghai Kaisai Chemical Co., Ltd.

[0032] Product performance test:

[0033] Ball indentation hardness: Tested according to the standard method outlined in ISO 2039-1, using standard test discs (Ø80 × 6 mm) injection molded in a DRK-QY plastic ball indentation hardness tester. A 5 mm diameter steel ball was used, with a pressure of 358 N and a loading time of 30 seconds. Surface hardness of the discs was compared at room temperature (23°C) before and after exposure to visible light (2kW metal halide lamp, 300 mW / cm², 30 minutes). After exposure to visible light, the discs were exposed to natural sunlight for 30 and 60 days before testing their surface hardness.

[0034] Scratch resistance test: Injection molded standard panels measuring 160×120×3.2mm were exposed to standard visible light (2kW metal halide lamp, 300mW / cm² illuminance, 30 minutes) using the standard method outlined in PV3974. The test load was 3N and the frequency was 1000mm / min. The change in surface brightness (ΔL) was compared three days before and after the scratch test.

[0035] Friction coefficient test: Injection molded standard test pieces of 160×120×3.2mm were subjected to visible light irradiation under standard conditions (2kW metal halide lamp, illuminance 300mW / cm2, irradiation time 30min), and then tested according to the standard method shown in ISO8295. The friction material was Q235 ordinary carbon structural steel.

[0036] Wear volume testing: Standard Φ50×10 wafers were injection molded and exposed to standard visible light irradiation (2kW metal halide lamp, 300mW / cm² illumination, 30 minutes of irradiation). The wear volume was then measured on a Taber abrasion machine according to the standard method outlined in ISO 3537, with the turntable rotating at a constant speed of 60 rpm. The wear volume of the wafers was measured after 1000 rotations.

[0037] Wear resistance grade: Injection molding of a standard sample plate measuring 160×120×3.2mm, conducted on a reciprocating wear resistance testing machine LTAO-643, with a test load of 5N, a stroke of 100mm, a friction frequency of 30 times / min, and a friction count of 10,000 times.

[0038] Example 1

[0039] According to the data of Example 1 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and the mixture was dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The mixture was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0040] According to the data of Example 1 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed respectively and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added, mixed uniformly, and placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder. The powder was then fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0041] Example 2

[0042] According to the data of Example 2 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and magnetic stirring was performed at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The powder was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0043] According to the data of Example 2 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed respectively and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added, mixed uniformly, and placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder. The powder was then fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0044] Table 1 Formulation of visible light-cured high-rigidity, high-wear-resistant PMMA alloy materials (unit: g)

[0045] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 PMMA 73 67 68 67 67 67 77 PC 20 10 15 15 15 15 15 Vinyl Resin-1 2 6 6 6 Vinyl Resin-2 8 6 Molybdenum disulfide powder 3 10 6 8 8 8 8 Photosensitizer-1 1 1 1 Photosensitizer-2 2 1.5 1 Photosensitizer-3 3 1.5 1.5 Styrene oxide 1 3 2 1.5 1.5 1.5

[0046] Example 3

[0047] According to the data of Example 3 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and the mixture was dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The mixture was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0048] According to the data of Example 3 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed respectively and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added, mixed uniformly, and placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder. The powder was then fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0049] Example 4

[0050] According to the data of Example 4 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and the mixture was dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The mixture was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0051] According to the data of Example 4 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed respectively and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added and mixed uniformly. The mixture was placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0052] Example 5

[0053] According to the data of Example 5 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and the mixture was dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The mixture was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0054] According to the data of Example 5 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed respectively and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added and mixed uniformly. The mixture was placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0055] Example 6

[0056] According to the data of Example 6 shown in Table 1, vinyl resin and styrene oxide were weighed respectively, mixed uniformly, and added to a glass container of a certain volume. The water bath temperature was adjusted to 55° C., and the mixture was dispersed by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, molybdenum disulfide powder was weighed according to the stated weight parts and added to the glass container. The mixture was stirred at a high speed of 300 rpm for 30 minutes to obtain a vinyl resin coating layer of a certain thickness and uniform distribution on the surface of the lamellar structure of molybdenum disulfide.

[0057] According to the data of Example 6 shown in Table 1, PMMA resin, PC resin, and photosensitizer were weighed separately and premixed in a high-pressure mixer for 5 minutes. Then, molybdenum disulfide inorganic powder coated with vinyl resin was added and mixed uniformly. The mixture was placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder via the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the main barrel sections from the feed port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the visible light-cured, high-rigidity, high-wear-resistant PMMA alloy material was obtained.

[0058] Comparative Example 1

[0059] According to the data of Comparative Example 1 shown in Table 1, PMMA resin, PC resin, and molybdenum disulfide powder were weighed and mixed uniformly to obtain a mixed raw material:

[0060] The dried mixed raw materials were placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder through the feeding screw. The twin-screw extruder used had a diameter of 35 mm and an aspect ratio (L / D) of 48. The temperatures of the zones of the main barrel from the feeding port to the die outlet were set to 170° C., 190° C., 210° C., 220° C., 230° C., 220° C., 215° C., 210° C., and 220° C. The main barrel speed was 200 rpm. After melt extrusion, granulation, drying, and other processes, the PMMA alloy material was obtained.

[0061] Comparative Example 2

[0062] Modified PMMA / PC alloy—HCM5370, Shanghai Kumho Sunny Co., Ltd., commercially available.

[0063] Table 2 Test results of visible light cured high rigidity and high wear resistance PMMA alloy materials

[0064]

[0065] Combining the components and test data of the Examples and Comparative Examples in Tables 1 and 2, it can be seen that PMMA / PC alloys, as highly compatible polyester alloys, have low surface hardness (approximately 140 MPa), high coefficient of friction (0.8-0.9), and severe wear and abrasion due to the limited properties of their component materials. This hinders their application as novel decorative materials. While the addition of molybdenum disulfide can improve the alloy's wear resistance to some extent (Comparative Example 1), the improvement is low and relatively narrow. However, the introduction of a visible light-induced curing crosslinking system into the PMMA alloys significantly improves the material's surface properties. After irradiation crosslinking under standard conditions (2 kW metal halide lamp, 300 mW / cm² illumination, 30 min irradiation), the ball pressure hardness of the PMMA alloys generally increases to 160-170 MPa. After 30 and 60 days of storage under natural light, the ball pressure hardness can be further increased to 175-180 MPa (Examples 5 and 6). Further testing shows that the surface cross-linked structure of the PMMA alloy material can also directly promote the overall improvement of wear resistance. The friction coefficient of the material is reduced by 50-70% year-on-year, reaching a minimum of 0.28, and the corresponding wear mass is also greatly reduced from the previous 241 mg and 406 mg (Comparative Examples 1 and 2) to 97 mg and 76 mg (Examples 5 and 6). Comparison of the improvement effects of each embodiment shows that the compounded photosensitizer system has better use effect than a single additive. Among them, when the ratio of manganese acetylacetonate MnAA / polyetheramine Jeffamine XTJ-590 is 1:1.5 (Example 6), the obtained PMMA alloy material has the best modification effect. Not only is the friction coefficient and wear mass of the material the lowest, but the scratch resistance index (ΔL) test is also reduced from 2.2 before modification to 0.9, and the wear resistance grade test also reaches the highest level 4 (barely visible) in the test.

[0066] The present invention describes a high-rigidity, high-wear-resistant PMMA alloy material and its preparation method, combining the advantages of current chemical modification methods (visible light-induced curing and cross-linking reaction) and physical blending modification (molybdenum disulfide filling modification). Compared with physical blending modification alone, this method offers more comprehensive and significant improvements. Furthermore, by using visible light, which is more readily available and more stable, as the irradiation light source, the material post-processing cost is low, and the environmental and equipment requirements are also lower. This is an ideal solution for the emerging development trends of PMMA alloy materials, such as multifunctionalization and environmental friendliness.

Claims

1. A visible light-cured PMMA alloy material with high rigidity and high wear resistance, characterized by: The invention comprises the following raw materials in parts by weight:

2. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The PMMA resin is low-melting, high-viscosity extrusion-grade polymethyl methacrylate, and its melt index MFR under the test conditions of 230° C. and 3.8 kg is ≤1.5 g / 10 min.

3. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The PC resin is a copolymerized polycarbonate resin with high hardness and scratch resistance, and its ball pressure hardness is ≥125MPa and its abrasion loss is ≤15mg / 1000cy.

4. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The vinyl resin is a bisphenol A type or phenolic type vinyl resin, the acid value of which is 10±3.0 mgKOH / g and the gel time (25° C.) is 15±5 min.

5. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The molybdenum disulfide powder is a high-purity nano-scale molybdenum disulfide inorganic powder with a purity of ≥99.9% and an average particle size (D50) of 30-100 nm.

6. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The photosensitizer is one or more of acetylacetone metal salt, acylphosphine oxide, polyetheramine and the like.

7. The visible light-cured high-rigidity, high-wear-resistant PMMA alloy material according to claim 1, characterized in that: The styrene oxide is a colorless, low-viscosity liquid with a transparent appearance and a viscosity (20° C.) ≤ 0.8 Pa.s.

8. The method for preparing a high-rigidity and high-wear-resistant PMMA alloy material cured by visible light according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Weighing vinyl resin and styrene oxide according to the weight parts, mixing them evenly, and adding them to a glass container of a certain volume. Adjusting the water bath temperature to 55° C., and dispersing them by magnetic stirring at a low speed of 150 rpm for 10 minutes. Then, weighing molybdenum disulfide powder according to the weight parts, adding them to the glass container, and stirring them at a high speed of 300 rpm for 30 minutes, so that a vinyl resin coating layer of a certain thickness and uniform distribution is obtained on the surface of the lamellar structure of molybdenum disulfide. (2) PMMA resin, PC resin and photosensitizer are weighed according to the weight parts, premixed in a high-pressure mixer for 5 minutes, and then the molybdenum disulfide inorganic powder coated with vinyl resin is added. After mixing evenly, the mixture is placed in the main feeding bin of a tightly meshed co-rotating twin-screw extruder and fed into the barrel of the extruder through the feeding screw. The diameter of the twin-screw extruder used is 35 mm, and the aspect ratio L / D is 48. The temperature of each zone of the main barrel from the feed port to the head outlet is set to: 170°C, 190°C, 210°C, 220°C, 230°C, 220°C, 215°C, 210°C, 220°C, and the main barrel speed is 200 rpm. After the processes of melt extrusion, granulation, drying and the like, the high-rigidity and high-wear-resistant PMMA alloy material cured by visible light is obtained.

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