A pmma composition, composite material and method of preparation and use

Abstract

This invention belongs to the field of polymer materials technology, specifically relating to a PMMA composition and a PMMA composite material, and further disclosing its preparation method and applications. The PMMA composite material of this invention utilizes the synergistic effect of PMMA resin matched with ACR resin, matting agent, scratching agent, processing aid, activator, and water. By adjusting the feeding sequence of each raw material during the melt mixing process, the orderly reactive extrusion of the entire material system is optimized, achieving performance optimization of the PMMA material. It can be widely used in industries such as decoration, advertising, furniture, and building materials.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a PMMA composition and a PMMA composite material, and further disclosing its preparation method and application. Background Technology

[0002] Polymethyl methacrylate (PMMA) is one of the most commonly used materials for decorative parts in the automotive, industrial electronics, and home appliance industries. Due to its unique molecular chain chemical structure, it possesses high hardness, high gloss, and excellent weather resistance. The macromolecular chains of PMMA contain flexible olefin groups and large side-chain ethyl acetate groups. Therefore, it not only has excellent flexibility and impact resistance but also boasts a high transparency unmatched by other polymer materials, even surpassing traditional inorganic glass materials, hence its alternative name, plexiglass.

[0003] However, PMMA's chemical structure also has its own unavoidable defects, namely, the material surface is relatively soft, easily scratched, not wear-resistant, and has poor chemical resistance due to the ester group's poor chemical resistance and easy chain degradation. This makes it unsuitable for use in scenarios requiring a matte appearance, such as decoration, advertising, furniture and building materials, and also limits its in-depth promotion and application in a wider range of fields.

[0004] Currently, the process typically involves pressing with frosted molds or frosted rollers. Directly applying the material through vacuum forming or heat sealing can reduce processing costs, but it is difficult to meet requirements for transparency, gloss, strength, and scratch resistance.

[0005] Currently, although various PMMA material modification processes have been developed in this field, there are still cases where the material's transparency, gloss, strength, or scratch resistance fails to meet requirements. Therefore, the field anticipates developing a PMMA composite material with excellent low-gloss, tensile and tear resistance, and scratch resistance, which would be of positive significance for its widespread application in industries such as decoration, advertising, furniture, and building materials. Summary of the Invention

[0006] Therefore, the technical problem to be solved by the present invention is to provide a PMMA composition, which, based on the matching of functional components, can be used to prepare PMMA composite materials with good transparency, low gloss, tensile strength, and scratch resistance.

[0007] The second technical problem to be solved by the present invention is to provide the use of the above-mentioned PMMA composition in the preparation of PMMA composite materials;

[0008] The third technical problem to be solved by the present invention is to provide a PMMA composite material and its preparation method. The PMMA composite material has good low gloss, tensile and tear resistance, and scratch resistance, and can be applied to industries such as decoration, advertising, furniture and building materials.

[0009] To solve the above-mentioned technical problems, the present invention provides a PMMA composition comprising the following components in parts by weight:

[0010] 60-95 parts by weight of PMMA resin;

[0011] 5-40 parts by weight of ACR resin;

[0012] Matting agent 1-5 parts by weight;

[0013] Scraping agent 0.1-5 parts by weight;

[0014] Processing aids: 0.01-5 parts by weight;

[0015] Activator 1-5 parts by weight;

[0016] Water 0.001-0.05 parts by weight.

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

[0018] 70-90 parts by weight of PMMA resin;

[0019] 10-30 parts by weight of ACR resin;

[0020] Matting agent 1-3 parts by weight;

[0021] Scraping agent 0.4-2 parts by weight;

[0022] Processing aids: 0.05-2 parts by weight;

[0023] Activator 2-4 parts by weight;

[0024] Water 0.003-0.03 parts by weight.

[0025] Specifically, the PMMA composition:

[0026] The PMMA resin has a molecular weight distribution of 1.6-2.5, preferably 1.8-2.2; and / or,

[0027] The PMMA resin has a viscosity-average molecular weight of 10,000-15,000 g / mol, preferably 12,000-14,000 g / mol; and / or,

[0028] The melt flow index (260°C, 10kg test) of the ACR resin is 3-15 g / 10min; preferably 5-10 g / 10min; and / or,

[0029] The matting agent comprises silica and / or cross-linked PMMA, preferably with a particle size of 1-30 μm; more preferably with a particle size of 3-10 μm; and / or,

[0030] The scraping agent comprises at least one of polyester silicone, erucamide, or phenyl silicone oil; preferably polyester silicone; and / or...

[0031] The activator includes at least one of 2,2,4-trimethylhexamethylenediamine, tetramethylpropylenediamine, or hydroxyethylethylenediamine; and / or,

[0032] The processing aids include antioxidants, preferably at least one of hindered phenols, benzofurans, acryloyl-modified phenols, hydroxylamines, or phosphites; and / or,

[0033] The electrical conductivity of the water is 0.1-1.0 μS / cm.

[0034] The present invention also discloses the use of the PMMA composition in the preparation of PMMA composite materials.

[0035] The present invention also discloses a low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material, the raw materials of which include the PMMA composition.

[0036] The present invention also discloses a method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material, comprising the steps of taking a selected amount of PMMA resin and water for a first melt mixing step, continuing to add a selected amount of the ACR resin, activator, scratching agent and matting agent for a second melt mixing step, and continuing to add the processing aids for a third melt mixing step.

[0037] Specifically, the preparation method of the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material is as follows:

[0038] The processing temperature of the first melt-blending step is 180-190℃; and / or,

[0039] The processing temperature of the second melt-blending step is 210-240℃, and the vacuum degree is -0.04MPa to 0.2MPa; and / or,

[0040] The processing temperature of the third melt mixing step is 240-250℃.

[0041] Specifically, in the preparation method of the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material, the first melt blending, the second melt blending, and the third melt blending are carried out based on a screw extruder.

[0042] Preferably, the area where the screw is located is divided sequentially into an initial section, a middle section, and a tail section along the material transport direction of the extruder; wherein,

[0043] The PMMA resin and water are fed from the feed inlet of the primary section; the processing temperature of the primary section is controlled at 180-190℃;

[0044] The ACR resin, activator, scraping agent, and matting agent are fed from the feed inlet of the intermediate section; the processing temperature of the intermediate section is controlled at 210-240℃, and the vacuum degree is -0.04MPa to 0.2MPa;

[0045] The processing aid is fed from the feed inlet of the tail section; the processing temperature of the tail section is controlled at 240-250℃.

[0046] Specifically, in the preparation method of the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material, the initial section is located in the region of the screw extruder that is less than 20% of the total screw length, the middle section is located in the region of the screw extruder that is 20-60% of the total screw length, and the tail section is located in the region of the screw extruder that is greater than 60% of the total screw length.

[0047] Preferably, the screw extruder is divided into 10 zones according to the total length of its screw; wherein, the initial section is located in zone 1-2 of the total screw length, the middle section is located in zone 3-6 of the total screw length, and the tail section is located in zone 7-10 of the total screw length.

[0048] Specifically, the preparation method of the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material includes the steps of extruding, cooling, stretching, and pelletizing the melt-mixed material.

[0049] Preferably, the temperature of the cooling step is 40-50°C, and the cooling time is 5-15 seconds.

[0050] The present invention also discloses the application of the PMMA composition, the PMMA composite material, or the PMMA composite material prepared by the method in the fields of decoration, advertising, furniture and building materials.

[0051] The PMMA composite material of this invention utilizes the synergistic effect of PMMA resin, ACR resin, matting agent, scratching agent, processing aid, activator, and water. The PMMA composition exhibits good transparency, low gloss, tensile strength, and scratch resistance, and can be applied in industries such as decoration, advertising, furniture, and building materials.

[0052] The PMMA composite material of this invention optimizes the orderly reactive extrusion of the entire material system by adjusting the feeding sequence of each raw material during the melt mixing process. The PMMA resin and water are added first, causing ester bond hydrolysis. Subsequently added matting agents, with their surface hydroxyl and carboxyl groups reacting with the activator, undergo nucleophilic addition reactions, introducing amine groups as side chains. This allows the hydrolyzed PMMA segments to react with the compatibilized amine groups of the matting agent, resulting in a chemically bonded resin with a unique structure. This process also reduces silica agglomeration, improving the tensile strength of the material based on reactivity and compatibility, while simultaneously achieving excellent transparency, matte finish, and scratch resistance. The PMMA composite material of this invention optimizes the performance of PMMA materials through the optimization of the material feeding sequence, and can be widely used in industries such as decoration, advertising, furniture, and building materials. Detailed Implementation

[0053] To obtain a PMMA composite material with good transparency, low gloss, tensile strength, and scratch resistance, the present invention comprises the following components in parts by weight:

[0054] 60-95 parts by weight of PMMA resin;

[0055] 5-40 parts by weight of ACR resin;

[0056] Matting agent 1-5 parts by weight;

[0057] Scraping agent 0.1-5 parts by weight;

[0058] Processing aids: 0.01-5 parts by weight;

[0059] Activator 1-5 parts by weight;

[0060] Water 0.001-0.05 parts by weight.

[0061] In some specific embodiments, the PMMA composition of the present invention uses 60-95 parts by weight of PMMA resin. For example, the amount added can be selected from 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 parts by weight, or within any range of the above values.

[0062] In some specific embodiments, the ACR resin in the PMMA composition of the present invention is used in an amount of 5-40 parts by weight. For example, the amount added can be selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 parts by weight, or within any range of the above values.

[0063] In some specific embodiments, the amount of matting agent in the PMMA composition of the present invention is 1-5 parts by weight. For example, the amount added can be selected from 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0 parts by weight, or within any range of the above values.

[0064] In some specific embodiments, the amount of the scraping agent in the PMMA composition of the present invention is 0.1-5 parts by weight. For example, the amount added can be selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0 parts by weight, or within any range of the above values.

[0065] In some specific embodiments, the processing aid in the PMMA composition of the present invention is used in an amount of 0.01-5 parts by weight. For example, the addition amount is selected from 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, etc. 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0 parts by weight, or within any range of the above values.

[0066] In some specific embodiments, the activator in the PMMA composition of the present invention is used in an amount of 1-5 parts by weight. For example, the amount added can be selected from 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0 parts by weight, or within any range of the above values.

[0067] In some specific embodiments, the amount of water used in the PMMA composition of the present invention is 0.001-0.05 parts by weight. For example, the amount added can be selected as 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, etc. 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50 parts by weight, or within any range of the above values.

[0068] In some specific embodiments, the PMMA resin has a molecular weight distribution of 1.6-2.5 and a viscosity-average molecular weight of 10,000-15,000 g / mol; preferably, it has a molecular weight distribution of 1.8-2.2 and a viscosity-average molecular weight of 12,000-14,000 g / mol. As an exemplary embodiment, the PMMA resin is selected from one or more of Wanhua HDS01, Wanhua HDS02, and Wanhua HDS03.

[0069] In some specific embodiments, the melt flow index (260°C, 10kg test) of the ACR resin is 3-15 g / 10min; preferably 5-10 g / 10min. As an exemplary embodiment, the ACR resin is selected from one or more of Rohm and Haas KM355P, Huaxing Additives ZB401, and ZB1.

[0070] In some specific embodiments, the matting agent includes silica and cross-linked PMMA, more preferably with a particle size of 1-30 μm; and more preferably with a particle size of 3-10 μm.

[0071] In some specific embodiments, the scraping agent includes at least one of polyester silicone, erucamide, or phenyl silicone oil; preferably polyester silicone.

[0072] In some specific embodiments, the activator includes at least one of 2,2,4-trimethylhexamethylenediamine, tetramethylpropylenediamine, or hydroxyethylethylenediamine.

[0073] In some embodiments, the processing aid includes an antioxidant. As an exemplary embodiment, the antioxidant includes at least one of hindered phenols, benzofurans, acryloyl-modified phenols, hydroxylamines, or phosphites.

[0074] In some specific embodiments, the electrical conductivity of the water is 0.1-1.0 μS / cm.

[0075] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0076] In the following embodiments of the present invention, the main raw materials used are exemplary as follows; unless otherwise specified, all other raw materials are common commercially available materials:

[0077] PMMA resin: HDS01, viscosity-average molecular weight 11000 g / mol, molecular weight distribution 1.9, Wanhua Chemical;

[0078] PMMA resin: HDS02, viscosity-average molecular weight 15000 g / mol, molecular weight distribution 1.6, Wanhua Chemical;

[0079] PMMA resin: HDS03, viscosity-average molecular weight 13000 g / mol, molecular weight distribution 2.5, Wanhua Chemical;

[0080] ACR resin: Rohm and Haas KM355P, melt index (tested at 260 degrees Celsius and 10 kg) is 2 g / 10 min;

[0081] ACR resin: Huaxing Additives Co., Ltd., ZB401, melt index (tested at 260 degrees Celsius and 10 kg) is 5 g / 10 min;

[0082] ACR resin: Huaxing Additives Co., Ltd., ZB1, melt index (tested at 260 degrees Celsius and 10 kg) is 10 g / 10 min;

[0083] Matting agent: Degussa silica, TS100, particle size 10μm;

[0084] Matting agent: Degussa silica, OK412, particle size 6μm;

[0085] Matting agent: Degussa silica, OK412LC, particle size 3μm;

[0086] Matting agent: Jingtong Technology crosslinked PMMA, HMT, particle size 8μm;

[0087] Scratcher: Dow Corning MB50-008;

[0088] Scratcher: Dow Corning MB40-006;

[0089] Scratcher: Dow Corning MB50-007;

[0090] Activator: 2,2,4-trimethylhexamethylenediamine, tetramethylpropylenediamine, or hydroxyethylethylenediamine;

[0091] Water: conductivity 0.1-1.0 μS / cm.

[0092] Example 1

[0093] The PMMA composite material described in this embodiment includes the following raw material components:

[0094] PMMA resin HDS01, 60kg;

[0095] ACR resin KM355P, 40kg;

[0096] Matting agent TS100, 1 kg;

[0097] Scratching agent MB50-008, 5kg;

[0098] Activator 2,2,4-trimethylhexamethylenediamine, 1 kg;

[0099] Antioxidant 168, 0.2 kg;

[0100] Water, 0.001kg.

[0101] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 180°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 210°C and a vacuum of -0.1 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 240°C.

[0102] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0103] Example 2

[0104] The PMMA composite material described in this embodiment includes the following raw material components:

[0105] PMMA resin HDS02, 70kg;

[0106] ACR resin ZB12, 20kg;

[0107] Matting agent OK412, 2kg;

[0108] Scratching agent MB40-006, 0.4kg;

[0109] Activator tetramethylpropanediamine, 3 kg;

[0110] Antioxidant 168, 0.2 kg;

[0111] Water, 0.002kg.

[0112] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 190°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 210°C and a vacuum of -0.2 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 250°C.

[0113] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0114] Example 3

[0115] The PMMA composite material described in this embodiment includes the following raw material components:

[0116] PMMA resin HDS02, 90kg;

[0117] ACR resin ZB401, 10kg;

[0118] Matting agent OK412LC, 5kg;

[0119] Scratching agent MB50-007, 1kg;

[0120] Activator: hydroxyethyl ethylenediamine, 4 kg;

[0121] Antioxidant 168, 0.2 kg;

[0122] Water, 0.05 kg.

[0123] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 185°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 240°C and a vacuum of -0.04 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 245°C.

[0124] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0125] Example 4

[0126] The PMMA composite material described in this embodiment includes the following raw material components:

[0127] PMMA resin HDS03, 80kg;

[0128] ACR resin ZB12, 5kg;

[0129] Matting agent OK412, 3kg;

[0130] Scratching agent MB40-006, 2kg;

[0131] Activator: Tetramethylpropanediamine, 2 kg;

[0132] Antioxidant 168, 0.2 kg;

[0133] Water, 0.03kg.

[0134] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 185°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 225°C and a vacuum of -0.1 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 240°C.

[0135] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0136] Example 5

[0137] The PMMA composite material described in this embodiment includes the following raw material components:

[0138] PMMA resin HDS01, 95kg;

[0139] ACR resin ZB12, 20kg;

[0140] Matting agent OK412, 3kg;

[0141] Scratching agent MB50-007, 0.1kg;

[0142] Activator 2,2,4-trimethylhexamethylenediamine, 5 kg;

[0143] Antioxidant 168, 0.2 kg;

[0144] Water, 0.02 kg.

[0145] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 180°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 225°C and a vacuum of -0.1 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 250°C.

[0146] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0147] Example 6

[0148] The PMMA composite material described in this embodiment includes the following raw material components:

[0149] PMMA resin HDS03, 60kg;

[0150] ACR resin ZB401, 30kg;

[0151] Matting agent TS100, 2kg;

[0152] Scratching agent MB50-007, 2kg;

[0153] Activator: Tetramethylpropanediamine, 1 kg;

[0154] Antioxidant 168, 0.2 kg;

[0155] Water, 0.02 kg.

[0156] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 190°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 210°C and a vacuum of -0.1 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 250°C.

[0157] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0158] Example 7

[0159] The PMMA composite material described in this embodiment includes the following raw material components:

[0160] PMMA resin HDS01, 60kg;

[0161] ACR resin KM355P, 40kg;

[0162] Matting agent HMT, 1 kg;

[0163] Scratching agent MB50-008, 5kg;

[0164] Activator 2,2,4-trimethylhexamethylenediamine, 1 kg;

[0165] Antioxidant 168, 0.2 kg;

[0166] Water, 0.001kg.

[0167] The PMMA composite material preparation method described in this embodiment uses an extruder with 10 screw length partitions to melt-blend the raw materials. Parts 1-2 are the initial stage, parts 3-6 are the middle stage, and parts 7-10 are the final stage. In part 1, PMMA resin and water are added, and the temperature in part 1-2 is set at 180°C. In part 4, ACR resin, matting agent, scraping agent, and activator components are added, and the temperature in part 3-6 is set at 210°C and a vacuum of -0.1 MPa. In part 7, an antioxidant is added, and the temperature in part 7-10 is set at 240°C.

[0168] After the above materials are melt-blended, the extruded strips are passed through 50°C water, cooled for 10 seconds, drawn into strips, and then pelletized to obtain the desired PMMA composite material.

[0169] Comparative Example 1

[0170] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that all raw materials are added in Zone 1 during the preparation of the PMMA composite material.

[0171] Comparative Example 2

[0172] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that the specific feeding process in the preparation of the PMMA composite material is as follows: the raw materials are melt-mixed using an extruder with 10 zones along the screw length. In zone 1, activator, ACR resin, matting agent, and scraping agent are added, and the temperature of zones 1-2 is set at 180°C; in zone 4, PMMA resin and water are added, and the temperature of zones 3-6 is set at 210°C and a vacuum of -0.1 MPa; in zone 7, antioxidant is added, and the temperature of zones 7-10 is set at 240°C.

[0173] Comparative Example 3

[0174] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that the specific feeding process in the preparation of the PMMA composite material is as follows: the raw materials are melt-mixed using an extruder with 10 zones of screw length. PMMA resin is added in zone 1, and the temperature of zones 1-2 is set at 180°C; ACR resin and matting agent are added in zone 4, and the temperature of zones 3-6 is set at 210°C and vacuum at -0.1MPa; antioxidant is added in zone 7, and the temperature of zones 7-10 is set at 240°C.

[0175] Comparative Example 4

[0176] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that POE elastomer is used instead of ACR resin.

[0177] Comparative Example 5

[0178] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that all raw materials are added in zone 4 during the preparation of the PMMA composite material.

[0179] Comparative Example 6

[0180] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that all raw materials are added in zone 7 during the preparation of the PMMA composite material.

[0181] Comparative Example 7

[0182] The PMMA composite material system described in this comparative example is the same as that in Example 1, except that the matting agent is replaced with talc during the preparation of the PMMA composite material.

[0183] Experimental Example

[0184] The PMMA composite materials prepared by the above embodiments and comparative schemes were subjected to the following performance tests, and the main test methods are as follows:

[0185] Cross-scratch color difference test: using PV3952, the downward pressure is 10N;

[0186] Gloss test: GB / T 9754, measured at a 60° angle;

[0187] Tensile strength test: The test shall be conducted in accordance with GB / T 1040, and the test speed shall be 50 mm / min;

[0188] Transmittance test: ASTM D1003 was used, and the test thickness was 2mm.

[0189] Agglomeration point quantity test: Injection molded 2mm color sample, record the number of aggregation points per 1m. 2 The number of points with an aggregation point diameter ≥ 0.2 mm in the area.

[0190] The performance test results of the PMMA composite material in this experimental example are shown in Table 2 below.

[0191] Table 2 Performance Test Results

[0192]

[0193] Through the above Examples 1-7 and Comparative Examples 1, 2, 3, 5, and 6, it can be seen that changing the order of material addition affects the gloss, tensile properties, and other properties of PMMA materials. As can be seen from Comparative Examples 2 and 3 and Comparative Examples 1, 5, and 6, the method of adding materials in sections helps to improve the gloss of the product and reduce the tensile strength. Furthermore, the schemes in Examples 1-7 of this application, by reasonably setting the method of material addition, have obtained PMMA materials with superior properties, including scratch resistance, low gloss, high tensile strength, and lower agglomeration point.

[0194] Through the above comparative example 4 and examples 1-7, it can be found that the POE raw material has poor compatibility with PMMA, which leads to adverse effects such as poor scratch resistance, increased gloss, and reduced tensile strength of PMMA material.

[0195] By comparing the schemes in Example 7 with those in Examples 1-7, it can be found that although other types of matting agents such as talc have better overall properties, they cannot achieve the low-gloss performance requirement when other types of matting agents are used. The overall performance of the PMMA material system in this application is better.

[0196] In summary, the PMMA composite material described in this invention has good transparency, low gloss, tensile strength, and scratch resistance, and can be applied in industries such as decoration, advertising, furniture, and building materials.

[0197] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A PMMA composition, characterized in that, The components include the following parts by weight: 60-95 parts by weight of PMMA resin; 5-40 parts by weight of ACR resin; Matting agent 1-5 parts by weight; Scraping agent 0.1-5 parts by weight; Processing aids: 0.01-5 parts by weight; Activator 1-5 parts by weight; Water 0.001-0.05 parts by weight.

2. The PMMA composition according to claim 1, characterized in that: The PMMA resin has a molecular weight distribution of 1.6-2.5; and / or, The PMMA resin has a viscosity-average molecular weight of 10,000-15,000 g / mol; and / or, The melt flow index of the ACR resin is 3-15 g / 10 min; and / or, The matting agent comprises silica and / or cross-linked PMMA, preferably with a particle size of 1-30 μm; and / or, The scraping agent comprises at least one of polyester silicone, erucamide, or phenyl silicone oil; and / or, The activator includes at least one of 2,2,4-trimethylhexamethylenediamine, tetramethylpropylenediamine, or hydroxyethylethylenediamine; and / or, The processing aids include antioxidants, preferably at least one of hindered phenols, benzofurans, acryloyl-modified phenols, hydroxylamines, or phosphites; and / or, The electrical conductivity of the water is 0.1-1.0 μS / cm.

3. Use of the PMMA composition of claim 1 or 2 for the preparation of PMMA composite materials.

4. A low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material, characterized in that, Its processing raw materials include the PMMA composition described in claim 1 or 2.

5. A method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material as described in claim 4, characterized in that, The process includes a first melt-blending step of taking a selected amount of PMMA resin and water, a second melt-blending step of continuing to add a selected amount of the ACR resin, activator, scraping agent and matting agent, and a third melt-blending step of continuing to add the processing aids.

6. The method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material according to claim 5, characterized in that: The processing temperature of the first melt-blending step is 180-190℃; and / or, The processing temperature of the second melt-blending step is 210-240℃, and the vacuum degree is -0.04MPa to 0.2MPa; and / or, The processing temperature of the third melt mixing step is 240-250℃.

7. The method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material according to claim 5 or 6, characterized in that, The first melt blending, the second melt blending, and the third melt blending are carried out based on a screw extruder; Preferably, the area where the screw is located is divided sequentially into an initial section, a middle section, and a tail section along the material transport direction of the extruder; wherein, The PMMA resin and water are fed from the feed inlet of the primary section; the processing temperature of the primary section is controlled at 180-190℃; The ACR resin, activator, scraping agent, and matting agent are fed from the feed inlet of the intermediate section; the processing temperature of the intermediate section is controlled at 210-240℃, and the vacuum degree is -0.04MPa to 0.2MPa; The processing aid is fed from the feed inlet of the tail section; the processing temperature of the tail section is controlled at 240-250℃.

8. The method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material according to claim 7, characterized in that, The initial section is located in the region of the screw extruder that is less than 20% of the total screw length; the middle section is located in the region of the screw extruder that is 20-60% of the total screw length; and the tail section is located in the region of the screw extruder that is greater than 60% of the total screw length. Preferably, the screw extruder is divided into 10 zones according to the total length of its screw; wherein, the initial section is located in zone 1-2 of the total screw length, the middle section is located in zone 3-6 of the total screw length, and the tail section is located in zone 7-10 of the total screw length.

9. The method for preparing the low-gloss, tensile-tear-resistant, and scratch-resistant PMMA composite material according to any one of claims 5-8, characterized in that, The method also includes the steps of extruding, cooling, stretching, and pelletizing the melt-blended material; Preferably, the temperature of the cooling step is 40-50°C, and the cooling time is 5-15 seconds.

10. The application of the PMMA composition of claim 1 or 2, the PMMA composite material of claim 4, or the PMMA composite material prepared by the method of any one of claims 5-9 in the fields of decoration, advertising, furniture and building materials.

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