A PMMA-ASA alloy material and its preparation method

Abstract

This application discloses a PMMA-ASA alloy material and its preparation method, relating to the field of polymer materials. By mass parts, the alloy material comprises: 45-60 parts of PMMA matrix material; 25-35 parts of ASA matrix material; 5-10 parts of a first functional polymer; and 5-10 parts of a second functional polymer; wherein the first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; and the second functional polymer is selected from a polyurethane elastomer with hydrogen bonding sites and hydrophobic side chains in its molecular backbone. This PMMA-ASA alloy material exhibits good hydrophobic / oleophobic antifouling and chemical corrosion resistance.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a PMMA-ASA alloy material and its preparation method. Background Technology

[0002] Thermally insulating PMMA-ASA alloy combines the high light transmittance (>92%) and high surface gloss (>90 GU) of PMMA (polymethyl methacrylate) with the excellent impact toughness and weather resistance of ASA (acrylonitrile-styrene-acrylate terpolymer). In existing technologies, by controlling the composition ratio of PMMA and ASA and adding a certain amount of colorant, light stabilizer, antioxidant, and other additives, the resulting alloy can achieve a high-gloss effect that can replace spray painting. Because the paint-free process reduces VOC emissions, lowers production energy consumption, and reduces scrap rates, high-gloss paint-free PMMA-ASA alloy is widely used in automotive interior and exterior trim parts, contributing to the lightweighting and environmental friendliness of automobiles.

[0003] However, due to the high surface energy of PMMA-ASA alloys containing a large number of polar groups such as ester and cyano groups, decorative parts made of PMMA-ASA are susceptible to water stains, oil stains, and corrosion from various chemicals during actual use, affecting their long-term use. Therefore, there is an urgent need for an alloy material that possesses the high toughness and high gloss of PMMA-ASA alloys (no need for painting), while also exhibiting hydrophobic / oleophobic anti-fouling properties and resistance to chemical corrosion. Summary of the Invention

[0004] In view of this, this application provides a PMMA-ASA alloy material and its preparation method, wherein the PMMA-ASA alloy material has good hydrophobic / oleophobic antifouling and chemical corrosion resistance.

[0005] The embodiments of this application are implemented as follows: Firstly, the embodiments of this application provide a PMMA-ASA alloy material, which, in parts by mass, comprises:

[0006] 45-60 parts of PMMA matrix material;

[0007] 25-35 parts of ASA matrix material;

[0008] 5-10 parts of the first functional polymer; and

[0009] 5-10 parts of the second functional polymer;

[0010] The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain.

[0011] Optionally, in some embodiments of this application,

[0012] The molecular structure of the first functional polymer is: Where x and y represent the molar contents of methyl methacrylate and hexafluoropropylene, respectively, x = 0.8–0.9 and y = 0.1–0.2; n represents the degree of polymerization of random copolymerization, an integer from 1000 to 1500; and / or

[0013] The molecular structure of the second functional polymer is as follows:

[0014] Where m represents the degree of polymerization of polyurethane elastomer, which is an integer from 30 to 80; and n represents the degree of polymerization of PDMS, which is an integer from 10 to 50.

[0015] Optionally, in some embodiments of this application, the alloy material further includes:

[0016] Light stabilizer 0.5–1.5 parts;

[0017] 0.5 to 1.5 parts of ultraviolet absorber;

[0018] 0.5–1.5 parts of the main antioxidant;

[0019] 0.3–0.8 parts of co-antioxidant; and

[0020] 0.5 to 1.5 parts of organic pigment.

[0021] Optionally, in some embodiments of this application, the light stabilizer is selected from one or more of light stabilizer UV120, light stabilizer 783, light stabilizer 791, and light stabilizer 4050; and / or

[0022] The ultraviolet absorber is selected from one or more of the following: ultraviolet absorber UV-234, ultraviolet absorber UV-1577, ultraviolet absorber UV-327, and ultraviolet absorber UV-571; and / or

[0023] The primary antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024; and / or

[0024] The auxiliary antioxidant is selected from one or more of antioxidant 168, antioxidant 626, antioxidant 2013, and antioxidant 360; and / or

[0025] The organic pigment is selected from aniline black.

[0026] Secondly, this application also provides a method for preparing the above-mentioned alloy material, comprising the following steps:

[0027] The composition, by weight parts, includes 45-60 parts of PMMA matrix material, 25-35 parts of ASA matrix material, 5-10 parts of the first functional polymer, and 5-10 parts of the second functional polymer; and

[0028] An alloy material is obtained by mixing PMMA matrix material, ASA matrix material, first functional polymer and second functional polymer under heating and melting conditions.

[0029] The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain.

[0030] Optionally, in some embodiments of this application, the method for preparing the first functional polymer includes:

[0031] Methyl methacrylate, an initiator, and a first solvent are mixed to obtain a first solution;

[0032] The first solution is contained in a sealed reaction vessel; and

[0033] Hexafluoropropylene was introduced into the reaction vessel, and the reaction yielded the first functional polymer.

[0034] Optionally, in some embodiments of this application, the molar ratio of methyl methacrylate to hexafluoroethylene is (0.8–0.9):(0.2–0.1); and / or

[0035] The reaction temperature for obtaining the first functional polymer is 70–90 °C; and / or

[0036] The reaction time to obtain the first functional polymer is 20–30 h; and / or

[0037] The reaction to obtain the first functional polymer is carried out under protective gas conditions; and / or

[0038] The initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, and diisopropyl peroxide; and / or

[0039] The first solvent is selected from one or more of acetonitrile, toluene, cyclohexanone, and n-butanol.

[0040] Optionally, in some embodiments of this application, the method for preparing the second functional polymer includes:

[0041] A second solution is obtained by mixing polycaprolactone, diphenylmethane diisocyanate, a first catalyst, and a second solvent.

[0042] The second solution was mixed with oxalohydrazide, and the reaction yielded the first intermediate.

[0043] A second functional polymer is obtained by mixing polydimethylsiloxane containing chlorine-terminated groups and a second catalyst with a first intermediate.

[0044] Optionally, in some embodiments of this application, the molar ratio of polycaprolactone, diphenylmethane diisocyanate, and oxalohydrazide is (0.95–1.05):(1.95–2.05):(0.95–1.05); and / or

[0045] The reaction temperature for obtaining the first intermediate is 50–80 °C; and / or

[0046] The reaction time to obtain the first intermediate is 2–8 h; and / or

[0047] The molar ratio of polydimethylsiloxane to diphenylmethane diisocyanate is 1:(18–25); and / or

[0048] The reaction temperature for obtaining the second functional polymer is -10 to 5 °C; and / or

[0049] The reaction time to obtain the second functional polymer is 2–6 h; and / or

[0050] The first catalyst is selected from one or more of dibutyltin dilaurate, N,N-dimethylcyclohexylamine, triethylamine, and bis(2-dimethylaminoethyl) ether;

[0051] The second catalyst is selected from one or more of potassium tert-butoxide, sodium methoxide, potassium ethoxide, and alkyllithium.

[0052] Optionally, in some embodiments of this application, when mixing PMMA matrix material, ASA matrix material, first functional polymer and second functional polymer under heating and melting conditions, 0.5 to 1.5 parts of light stabilizer, 0.5 to 1.5 parts of ultraviolet absorber, 0.5 to 1.5 parts of primary antioxidant, 0.3 to 0.8 parts of secondary antioxidant and 0.5 to 1.5 parts of organic pigment are added.

[0053] This invention incorporates a first functional polymer and a second functional polymer into a PMMA-ASA alloy. The first functional polymer, with its abundant fluorine atoms, increases the fluorine content of the alloy, reduces surface energy, and enhances its chemical corrosion resistance and hydrophobic / oleophobic antifouling properties. Simultaneously, the second functional polymer toughens the alloy. Utilizing polycaprolactone as a soft segment, the second functional polymer exhibits superior mechanical properties, while its high ester content ensures compatibility with the PMMA-ASA matrix. MDI serves as a capping agent, and its high benzene content ensures excellent compatibility with ASA. Oxalohydrazide acts as a chain extender, and multiple hydrogen bonds create tightly bound hard regions within the elastomer, ensuring excellent mechanical properties and chemical resistance. Furthermore, the multiple hydrogen bond sites on the elastomer's main chain can form strong hydrogen bond interactions with the PMMA and ASA matrices, further enhancing the overall mechanical properties and chemical resistance of the material. Side grafts of trace amounts of PDMS chains enrich the Si-O-Si segments on the surface, further reducing the surface energy and improving the material's hydrophobic / oleophobic antifouling properties and chemical resistance. Attached Figure Description

[0054] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0055] Figure 1 This is the infrared spectrum of the first functional polymer prepared in Example 1 of this application;

[0056] Figure 2 This is the infrared spectrum of the second functional polymer prepared in Example 1 of this application. Detailed Implementation

[0057] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0058] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0059] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0060] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0061] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0062] The structural formulas and molecular weights of some of the chemical reagents used in this application are described below:

[0063] Methyl methacrylate (MMA): Molecular weight = 100.12;

[0064] Hexafluoropropylene (HFP): Molecular weight = 150.02;

[0065] Polycaprolactone 2000 (PCL-2000): Molecular weight = 2000;

[0066] Single-terminated hydroxymethyl polydimethylsiloxane (PDMS-OH): Number average molecular weight = 2000, where n is an integer from 10 to 50;

[0067] Diphenylmethane diisocyanate (MDI): Molecular weight = 250.25;

[0068] Oxalic acid hydrazide: Molecular weight = 118.09;

[0069] thionyl chloride: Molecular weight = 118.97;

[0070] Triethylamine: Molecular weight = 101.19;

[0071] N,N'-Dicyclohexylcarbodiimide: Molecular weight = 206.33;

[0072] Potassium tert-butoxide: C4H9OK, molecular weight = 112.21;

[0073] The technical solution of this application is as follows:

[0074] In a first aspect, this application provides a PMMA-ASA alloy material, which, by mass parts, comprises:

[0075] 45-60 parts of PMMA matrix material;

[0076] 25-35 parts of ASA matrix material;

[0077] 5-10 parts of the first functional polymer; and

[0078] 5-10 parts of the second functional polymer;

[0079] The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain.

[0080] It should be noted that a hydrogen bond site refers to an atom that can form a hydrogen bond with a strongly polar hydrogen atom because it can provide a lone pair of electrons. For those skilled in the art, it is common knowledge to determine whether an atom can form a hydrogen bond with a hydrogen atom.

[0081] Specifically, in some embodiments, the molecular structure of the first functional polymer is as follows: Where x and y represent the molar contents of methyl methacrylate and hexafluoropropylene, respectively, x = 0.8–0.9 and y = 0.1–0.2; n represents the degree of polymerization of random copolymerization, an integer from 1000 to 1500. Blending the first functional polymer with PMMA and ASA can increase the fluorine content of the alloy material, reduce the surface energy, and improve the alloy material's resistance to chemical corrosion and its hydrophobic / oleophobic antifouling properties.

[0082] In some embodiments, the molecular structure of the second functional polymer is as follows:

[0083] Where m represents the degree of polymerization of the polyurethane elastomer, an integer from 30 to 80; and n represents the degree of polymerization of PDMS, an integer from 10 to 50. The second functional polymer utilizes polycaprolactone as the soft segment, exhibiting superior mechanical properties, while its high ester content ensures compatibility with the PMMA-ASA matrix. MDI serves as the end-capping agent, and its high benzene content ensures excellent compatibility with ASA. Oxalic acid hydrazide acts as a chain extender, and multiple hydrogen bonds enable the elastomer to form tightly bound hard regions, ensuring excellent mechanical properties and chemical resistance. Furthermore, the multiple hydrogen bond sites on the main chain of the second functional polymer elastomer can form strong hydrogen bond interactions with the PMMA and ASA matrices, enhancing the overall mechanical properties and chemical resistance of the material. Side grafts of trace amounts of PDMS chains enrich the Si-O-Si segments on the surface, further reducing the surface energy and improving the material's hydrophobic / oleophobic antifouling properties and chemical resistance.

[0084] It is understood that in the second functional polymer, the oxygen atom in the oxalohydrazide structure of the main chain serves as a hydrogen bond site. Specifically, NH provides a hydrogen nucleus, and the carbonyl oxygen provides a lone pair of electrons to form intermolecular hydrogen bonds. The hard segment structure of the extended oxalohydrazide contains multiple hydrogen and oxygen atoms capable of forming hydrogen bonds, thus enabling the formation of multiple hydrogen bonds. The -Si-O- in the side chain is a hydrophobic group. Furthermore, designing -Si-O- in the side chain of the second functional polymer ensures that its molecular chain segments can migrate to the material surface, enhancing the hydrophobic effect of the material. In some embodiments, the alloy material may further include:

[0085] Light stabilizer 0.5–1.5 parts;

[0086] 0.5 to 1.5 parts of ultraviolet absorber;

[0087] 0.5–1.5 parts of the main antioxidant;

[0088] 0.3–0.8 parts of co-antioxidant; and

[0089] 0.5 to 1.5 parts organic pigment. Adding light stabilizers and antioxidants can enhance the chemical weather resistance of alloy materials and extend their service life, while the addition of organic pigments can give the alloy materials a specific color and improve their appearance.

[0090] In some embodiments, the light stabilizer may be selected from one or more of the light stabilizer UV120, light stabilizer 783, light stabilizer 791 and light stabilizer 4050; preferably, the light stabilizer may be light stabilizer UV120.

[0091] In some embodiments, the ultraviolet absorber may be selected from one or more of ultraviolet absorbers UV-234, UV-1577, UV-327, and UV-571; preferably, the ultraviolet absorber may be selected from ultraviolet absorber UV-234.

[0092] In some embodiments, the primary antioxidant may be selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098 and antioxidant 1024; preferably, the primary antioxidant may be antioxidant 1076.

[0093] In some embodiments, the co-antioxidant is selected from one or more of antioxidant 168, antioxidant 626, antioxidant 2013 and antioxidant 360; preferably, the co-antioxidant may be antioxidant 168.

[0094] In some embodiments, the organic pigment may be selected from aniline black.

[0095] Secondly, this application also provides a method for preparing the above-mentioned alloy material, comprising the following steps:

[0096] S01: By weight parts, it provides 45-60 parts of PMMA matrix material, 25-35 parts of ASA matrix material, 5-10 parts of the first functional polymer, and 5-10 parts of the second functional polymer; and

[0097] S02: Under heating and melting conditions, PMMA matrix material, ASA matrix material, first functional polymer and second functional polymer are mixed to obtain alloy material.

[0098] The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain.

[0099] In some embodiments, the method for preparing the first functional polymer includes:

[0100] S11: Mix methyl methacrylate, initiator and first solvent to obtain first solution;

[0101] S12: Contain the first solution in a sealed reaction vessel; and

[0102] S13: Hexafluoropropylene is introduced into the reaction vessel, and the reaction yields the first functional polymer.

[0103] It should be noted that the term "closed reaction vessel" here does not refer to a completely sealed container, but rather to a state of relative isolation from the atmospheric environment. For example, in some embodiments, the closed reaction vessel may be a sealed reaction vessel that can be connected to the outside world through pipes, but it can still be considered a closed reaction vessel.

[0104] Specifically, in some embodiments, the reaction equation for obtaining the first functional polymer is as follows:

[0105]

[0106] Where 0.9 and 0.1 represent the molar content of methyl methacrylate and hexafluoropropylene, respectively; n represents the degree of polymerization of random copolymerization, which is an integer from 1000 to 1500.

[0107] In some embodiments, the molar ratio of methyl methacrylate to hexafluoroethylene can be (0.8-0.9):(0.2-0.1), for example, 0.8:0.2, 0.85:0.15, 0.9:0.1, etc. When the molar ratio of methyl methacrylate to hexafluoroethylene is within the above range, the fluorine atom content in the first functional polymer can be controlled within a reasonable range.

[0108] In some embodiments, the reaction temperature for obtaining the first functional polymer can be 70 to 90°C, for example, 70°C, 75°C, 80°C, 85°C, 90°C or any two of the above values. When the reaction temperature is within the aforementioned range, the reaction can be guaranteed to proceed smoothly.

[0109] In some embodiments, the reaction time to obtain the first functional polymer can be 20 to 30 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours or any two of the above values. When the reaction time is within the aforementioned range, it can be ensured that the reaction reaches the target degree of polymerization.

[0110] In some embodiments, the reaction to obtain the first functional polymer can be carried out under a protective gas condition; for example, it can be carried out under a protective gas condition such as nitrogen, helium, neon, or argon.

[0111] In some embodiments, the initiator may be selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, and diisopropyl peroxide. The initiator can initiate a free radical polymerization reaction, allowing the reaction to proceed.

[0112] In some embodiments, the first solvent may be selected from one or more of acetonitrile, toluene, cyclohexanone, and n-butanol.

[0113] In some embodiments, the method for preparing the second functional polymer includes:

[0114] S21: Polycaprolactone, diphenylmethane diisocyanate, the first catalyst and the second solvent are mixed to obtain a second solution;

[0115] S22: The second solution is mixed with oxalohydrazide to react and obtain the first intermediate;

[0116] S23: Polydimethylsiloxane containing chlorine atom end groups and a second catalyst are mixed with a first intermediate to react and obtain a second functional polymer.

[0117] Specifically, the molecular structure of the first intermediate is as follows:

[0118]

[0119] Where m represents the degree of polymerization of polyurethane elastomer, which is an integer from 30 to 80.

[0120] In some embodiments, the molar ratio of polycaprolactone, diphenylmethane diisocyanate, and oxalohydrazide is (0.95–1.05):(1.95–2.05):(0.95–1.05), for example, 0.95:1.95:0.95, 1:2:1, 1.05:2.05:1.05, etc. When the molar ratio of polycaprolactone, diphenylmethane diisocyanate, and oxalohydrazide is within the aforementioned range, it is ensured that the reaction yields the target molecular structure.

[0121] In some embodiments, the reaction temperature for obtaining the first intermediate can be 50–80°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or any two of the above values; the reaction time for obtaining the first intermediate can be 2–8 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or any two of the above values. When the reaction temperature and reaction time are within the aforementioned ranges, the reaction efficiency can be guaranteed.

[0122] In some embodiments, the molar ratio of polydimethylsiloxane to diphenylmethane diisocyanate can be 1:(18-25), for example, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, etc., so that the amount of polydimethylsiloxane grafted can be controlled within a reasonable range.

[0123] In some embodiments, the reaction temperature for obtaining the second functional polymer can be -10 to 5°C, for example, -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, or any two of the above values. The reaction time for obtaining the second functional polymer can be 2 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or any two of the above values.

[0124] In some embodiments, the first catalyst may be selected from one or more of dibutyltin dilaurate, N,N-dimethylcyclohexylamine, triethylamine, and bis(2-dimethylaminoethyl) ether; the second catalyst may be selected from one or more of potassium tert-butoxide, sodium methoxide, potassium ethoxide, and alkyllithium.

[0125] In some embodiments, when mixing PMMA matrix material, ASA matrix material, first functional polymer and second functional polymer under heating and melting conditions, 0.5 to 1.5 parts of light stabilizer, 0.5 to 1.5 parts of ultraviolet absorber, 0.5 to 1.5 parts of primary antioxidant, 0.3 to 0.8 parts of secondary antioxidant and 0.5 to 1.5 parts of organic pigment are added.

[0126] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0127] Example 1

[0128] This embodiment provides a PMMA-ASA alloy material and its preparation method, wherein the preparation method includes the following steps:

[0129] S1: Weigh 90.1g of methyl methacrylate (0.9mol), 1g of azobisisobutyronitrile (AIBN, initiator), and 400ml of anhydrous acetonitrile into a 1L stainless steel reactor. Seal the reactor, evacuate, and purge with nitrogen 5 times to displace the air. Place the reactor in a liquid nitrogen bath for cooling. Introduce 15g of hexafluoropropylene into the reactor through a sealed gas path and cool it with the liquid nitrogen bath. Control the amount of hexafluoropropylene added by adjusting the gas flow rate and the introduction time. After the gas is collected in the reactor, separate the reactor from the gas path. Under nitrogen protection and reflux conditions, stir the reaction at 80℃ for 24h. After the reaction is complete, pour the reaction solution into a large amount of deionized water to precipitate a flocculent precipitate. Filter the product, wash it several times with deionized water, and then dry it in a vacuum oven at 80℃ for 12h to obtain a transparent flocculent product, which is the first functional polymer.

[0130] S2: Weigh 50g of polycaprolactone 2000 (PCL2000, 0.025mol) and 200g of anhydrous DMF into a 500ml three-necked flask, start stirring, heat to 60℃ until PCL2000 is completely dissolved, then add 12.5g of diphenylmethane diisocyanate (0.05mol) and 0.1g of dibutyltin dilaurate (catalyst), keep stirring, purge with nitrogen, react at 60℃ for 2h, then add 3g of oxalohydrazide (0.025mol), and carry out chain extension reaction at 60℃ under nitrogen protection for 4h. After the reaction is completed, a polyurethane elastomer / DMF solution is obtained.

[0131] S3: Take 5g of single-terminated hydroxymethyl polydimethylsiloxane (PDMS-OH, 0.0025mol) dried under vacuum at 120℃ for 2h, 0.3g of triethylamine (0.003mol), 0.26g of N,N'-dicyclohexylcarbodiimide (0.00125mol, desiccant), and 50ml of anhydrous toluene and add them to a 100ml three-necked flask. Stir and mix thoroughly, purge with flowing nitrogen for protection, and slowly add 0.35g of thionyl chloride (0.003mol) dropwise through a constant pressure funnel under ice bath conditions. As the reaction proceeds, a white insoluble product is produced, which is the desiccant product of N,N'-dicyclohexylcarbodiimide; at the same time, the flowing nitrogen carries away the sulfur dioxide byproduct. After reacting for 4 hours, the mixture was filtered to remove the precipitate. The filtrate was then dried using a rotary evaporator to remove toluene, excess triethylamine, and excess thionyl chloride. The resulting bright yellow oily liquid was PDMS containing chlorine-terminated groups. Its specific structural formula and reaction equation are shown in the figure below.

[0132]

[0133] S4: Add 0.28 g of potassium tert-butoxide (0.0025 mol) to the polyurethane elastomer / DMF solution obtained in S2, purge with flowing nitrogen for protection, and stir for 1 h under ice bath conditions. Add the chlorinated PDMS obtained in step 3 dropwise into a three-necked flask through a constant pressure funnel. After the addition is complete, maintain the reaction at low temperature for 4 h. Remove the ice bath and add saturated NH4Cl solution to quench the reaction. Remove most of the DMF using a rotary evaporator. Pour the concentrated solution into a tetrafluoroethylene tray and place it in a vacuum drying oven. Dry at 120 °C for 12 h to obtain the second functional polymer.

[0134] S5: Take 1.545 kg PMMA (CM207, purchased from Zhenjiang Qimei Chemical Co., Ltd.), 0.3 kg primary functional polymer, 0.9 kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 0.15 kg secondary functional polymer, 15 g light stabilizer UV120, 15 g ultraviolet absorber UV-234, 30 g primary antioxidant 1076, 15 g secondary antioxidant 168, and 30 g aniline black (purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd.). Mix them evenly in a medium-speed mixer, and then melt-extrude and granulate them using a twin-screw extruder to obtain the PMMA-ASA alloy material.

[0135] The specific temperature zones of the extruder are set as follows:

[0136] Zone 1: 200℃, Zone 2: 220℃, Zone 3: 230℃, Zone 4: 230℃, Zone 5: 225℃, Zone 6: 225℃, Zone 7: 225℃, Zone 8: 230℃, Zone 9: 230℃, Zone 10: 235℃; screw speed: 500 r / min; length-to-diameter ratio: 48:1. The extruded and granulated composite material was injection molded to obtain mechanical property test strips and color plates for subsequent performance testing.

[0137] The chemical structures of the first functional polymer prepared in S1 and the second functional polymer prepared in S4 were characterized by infrared spectroscopy. The characterization results are shown in [reference 1]. Figure 1 , Figure 2 .

[0138] Please see Figure 1 Located at 1729cm -1 and 1190cm -1 The absorption peak at 1062 cm⁻¹ corresponds to the stretching vibrations of the C=O and COC groups in MMA. -1 The absorption peak at 1148 cm⁻¹ corresponds to the stretching vibration peak of the CF bond in HFP. -1 The absorption peak at that location corresponds to the symmetric stretching vibration peak of the CF2 group in HFP. This indicates that the product obtained in step 1 is a copolymer of MMA and HFP with the target structure (the first functional polymer).

[0139] Please see Figure 2 Located at 3320cm -1 The infrared absorption peak at 2928 cm⁻¹ corresponds to the -NH₃ stretching vibration. -1 And 2860cm -1 The absorption peak at 1727 cm⁻¹ corresponds to the stretching vibration of the subunit in the PCL chain segment. -1 And 1092cm -1 The absorption peaks at 1260 cm⁻¹ correspond to the stretching vibrations of C=O and COC, respectively. -1 The peak that appears is a characteristic peak of Si-CH3, 1023 cm⁻¹. -1 The absorption peak at that location corresponds to the characteristic peak of Si-O-Si. This indicates that the product obtained in step 4 is PU-g-PDMS (secondary functional polymer) with the target structure.

[0140] Example 2

[0141] This embodiment provides a PMMA-ASA alloy material and its preparation method. The preparation method is basically the same as that in Example 1, except that the amount of S5 in the formulation is different. The specific amount is as follows:

[0142] 1.545kg PMMA (CM207, purchased from Zhenjiang Chimei Chemical Co., Ltd.), 0.3kg primary functional polymer, 0.9kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 0.15kg secondary functional polymer, 15g light stabilizer UV120, 15g ultraviolet absorber UV-234, 30g primary antioxidant 1076, 15g secondary antioxidant 168, 30g aniline black, purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd.

[0143] Example 3

[0144] This embodiment provides a PMMA-ASA alloy material and its preparation method. The preparation method is basically the same as that in Example 1, except that the amount of S5 in the formulation is different. The specific amount is as follows:

[0145] 1.545kg PMMA (CM207, purchased from Zhenjiang Chimei Chemical Co., Ltd.), 0.15kg primary functional polymer, 0.9kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 0.3kg secondary functional polymer, 15g light stabilizer UV120, 15g ultraviolet absorber UV-234, 30g primary antioxidant 1076, 15g secondary antioxidant 168, 30g aniline black, purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd.

[0146] Example 4

[0147] This embodiment provides a PMMA-ASA alloy material and its preparation method. The preparation method is basically the same as that in Example 1, except that the amount of S5 in the formulation is different. The specific amount is as follows:

[0148] 1.395kg PMMA (CM207, purchased from Zhenjiang Chimei Chemical Co., Ltd.), 0.3kg primary functional polymer, 0.9kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 0.3kg secondary functional polymer, 15g light stabilizer UV120, 15g ultraviolet absorber UV-234, 30g primary antioxidant 1076, 15g secondary antioxidant 168, 30g aniline black, purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd.

[0149] Comparative Example 1

[0150] This embodiment provides a PMMA-ASA alloy material and its preparation method. The preparation method is basically the same as step S5 in Example 1, as follows:

[0151] Take 2.1 kg PMMA (CM207, purchased from Zhenjiang Qimei Chemical Co., Ltd.), 0.9 kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 15 g light stabilizer UV120, 15 g ultraviolet absorber UV-234, 30 g primary antioxidant 1076, 15 g secondary antioxidant 168, and aniline black (purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd.). Mix them evenly in a medium-speed mixer, and then melt-extrude and granulate them using a twin-screw extruder to obtain the PMMA-ASA alloy material.

[0152] The specific temperature zones of the extruder are set as follows:

[0153] Zone 1: 200℃, Zone 2: 220℃, Zone 3: 230℃, Zone 4: 230℃, Zone 5: 225℃, Zone 6: 225℃, Zone 7: 225℃, Zone 8: 230℃, Zone 9: 230℃, Zone 10: 235℃; screw speed: 500 r / min; length-to-diameter ratio: 48:1. The extruded and granulated composite material was injection molded to obtain mechanical property test strips and color plates for subsequent performance testing.

[0154] Comparative Example 2

[0155] This embodiment provides a PMMA-ASA alloy material and its preparation method. The preparation method is basically the same as step S5 in Example 1, as follows:

[0156] Take 1.395 kg PMMA (CM207, purchased from Zhenjiang Qimei Chemical Co., Ltd.), 0.3 kg of the primary functional polymer, 0.9 kg ASA (LI941, purchased from LG Chem Enterprises Co., Ltd.), 0.27 kg of PMMA-specific transparent toughening granules RQT-PM7885 (purchased from Henan Qiruit Chemical Co., Ltd.), 0.03 kg of polydimethylsiloxane PDMS (silicone oil, purchased from Shandong Yingsheng Chemical Co., Ltd.), 15 g of light stabilizer UV120, 15 g of ultraviolet absorber UV-234, 30 g of primary antioxidant 1076, 15 g of secondary antioxidant 168, and 30 g of aniline black, purchased from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd. Mix them evenly using a medium-speed mixer, then melt-extrude and granulate them using a twin-screw extruder to obtain the PMMA-ASA alloy material.

[0157] The specific temperature zones of the extruder are set as follows:

[0158] Zone 1: 200℃, Zone 2: 220℃, Zone 3: 230℃, Zone 4: 230℃, Zone 5: 225℃, Zone 6: 225℃, Zone 7: 225℃, Zone 8: 230℃, Zone 9: 230℃, Zone 10: 235℃; screw speed: 500 r / min; length-to-diameter ratio: 48:1. The extruded and granulated composite material was injection molded to obtain mechanical property test strips and color plates for subsequent performance testing.

[0159] Mechanical properties, surface hydrophobic / oleophobic properties, chemical resistance, and gloss of the PMMA / ASA alloy materials provided in Examples 1-4 and Comparative Examples 1-2 were tested. The test results are shown in Table 1.

[0160] The tensile strength test was performed according to standard GB / T 1040.2-2022; the flexural strength test was performed according to standard GB / T9341-2008; the room temperature cantilever beam notched impact strength test was performed according to standard GB / T1843-2008, with a test condition of 25°C; the water contact angle test, diiodomethane contact angle test, and surface energy calculation were performed according to standard ISO 19403-2:2024, using the WORK model to calculate the surface energy; according to "GB / T According to the standard JJG 696-2008 "Determination of Resistance to Liquid Chemical Reagents of Plastics", impact test strips prepared in different examples are weighed with an initial mass m1. They are then immersed in three commonly used chemical reagents with gradually decreasing polarity: ethanol, tetrahydrofuran, and ethyl acetate. After immersion at 25°C for 24 hours, the test strips are removed and dried in a forced-air drying oven at 80°C for 12 hours. The mass m2 is then weighed. The residual mass retention rate is used to characterize the chemical resistance of the materials prepared in different examples. The residual mass retention rate is calculated as (m2 / m1)*100%. In accordance with the requirements of JJG 696-2002 "Verification Procedure for Specular Gloss Meters and Gloss Plates", the surface gloss of PMMA / ASA composite materials obtained in different examples is measured using a three-angle gloss meter with an incident angle of 20°. A gloss level greater than 70° is considered a high gloss effect.

[0161] Table 1

[0162]

[0163] As shown in Table 1, the PMMA-ASA alloy material provided in this application exhibits significantly lower surface energy by increasing the fluorine and silicon content, demonstrating superior hydrophobic / oleophobic properties and chemical resistance compared to the PMMA-ASA alloy material in the comparative example. With increasing content of the second functional polymer, the tensile strength and flexural strength of the composite material slightly decrease, while the low-temperature impact toughness significantly increases. Comparing the test data of Example 4 and Comparative Example 2, it is evident that directly adding PDMS to the composite material is more effective in reducing surface energy than introducing PDMS branches into the second functional polymer. However, due to the poor compatibility of PDMS with the PMMA / ASA matrix, it is prone to precipitation, which can affect the appearance and performance stability of the product with long-term use. Furthermore, because PDMS is miscible with various organic reagents, the solvent resistance of the material reported in Comparative Example 2 is significantly weaker than that reported in Example 4. All materials reported in the examples exhibit excellent surface gloss (>75 GU). In summary, compared with the prior art, the PMMA-ASA alloy material provided in this application has excellent impact toughness, hydrophobic / oleophobic properties, chemical corrosion resistance, and high gloss, and has great application prospects.

Claims

1. A PMMA-ASA alloy material, characterized in that, The alloy material comprises, by mass parts: 45-60 parts of PMMA matrix material; 25-35 parts of ASA matrix material; 5-10 parts of the first functional polymer; and 5-10 parts of the second functional polymer; The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain. The molecular structure of the first functional polymer is as follows: Where x and y represent the molar contents of methyl methacrylate and hexafluoropropylene, respectively, x = 0.8~0.9 and y = 0.1~0.2; n represents the degree of polymerization of random copolymerization, an integer from 1000 to 1500; and / or The molecular structure of the second functional polymer is as follows: Where m represents the degree of polymerization of polyurethane elastomer, which is an integer from 30 to 80; and n represents the degree of polymerization of PDMS, which is an integer from 10 to 50.

2. The alloy material according to claim 1, characterized in that, The alloy material also includes: 0.5 to 1.5 parts of light stabilizer; 0.5 to 1.5 parts of ultraviolet absorber; 0.5-1.5 parts of the main antioxidant; 0.3-0.8 parts of co-antioxidant; and 0.5 to 1.5 parts organic pigment.

3. The alloy material according to claim 2, characterized in that, The light stabilizer is selected from one or more of the following: light stabilizer UV120, light stabilizer 783, light stabilizer 791, and light stabilizer 4050; and / or The ultraviolet absorber is selected from one or more of ultraviolet absorbers UV-234, UV-1577, UV-327, and UV-571; and / or The primary antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024; and / or The auxiliary antioxidant is selected from one or more of antioxidant 168, antioxidant 626, antioxidant 2013, and antioxidant 360; and / or The organic pigment is selected from aniline black.

4. The method for preparing the alloy material according to any one of claims 1 to 3, characterized in that, Includes the following steps: The product comprises, by weight, 45-60 parts of PMMA matrix material, 25-35 parts of ASA matrix material, 5-10 parts of the first functional polymer, and 5-10 parts of the second functional polymer. as well as The PMMA matrix material, the ASA matrix material, the first functional polymer, and the second functional polymer are mixed under heating and melting conditions to obtain the alloy material; The first functional polymer is selected from a copolymer of methyl methacrylate and hexafluoropropylene; the second functional polymer is selected from a polyurethane elastomer with hydrogen bond sites in the main molecular chain and hydrophobic groups in the side chain.

5. The preparation method according to claim 4, characterized in that, The method for preparing the first functional polymer includes: Methyl methacrylate, an initiator, and a first solvent are mixed to obtain a first solution; The first solution is contained in a sealed reaction vessel; and Hexafluoropropylene is introduced into the reaction vessel, and the reaction yields the first functional polymer.

6. The preparation method according to claim 5, characterized in that, The molar ratio of the methyl methacrylate to the hexafluoroethylene is (0.8~0.9):(0.2~0.1); and / or The reaction temperature for obtaining the first functional polymer is 70~90℃; and / or The reaction time to obtain the first functional polymer is 20-30 h; and / or The reaction to obtain the first functional polymer is carried out under protective gas conditions; and / or The initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, and diisopropyl peroxide; and / or The first solvent is selected from one or more of acetonitrile, toluene, cyclohexanone, and n-butanol.

7. The preparation method according to claim 4, characterized in that, The method for preparing the second functional polymer includes: A second solution is obtained by mixing polycaprolactone, diphenylmethane diisocyanate, a first catalyst, and a second solvent. The second solution was mixed with oxalohydrazide, and the reaction yielded the first intermediate. The first intermediate is mixed with a polydimethylsiloxane containing chlorine-terminated groups and a second catalyst to obtain a second functional polymer.

8. The preparation method according to claim 7, characterized in that, The molar ratio of the polycaprolactone, the diphenylmethane diisocyanate, and the oxalohydrazide is (0.95~1.05):(1.95~2.05):(0.95~1.05); and / or The reaction temperature for obtaining the first intermediate is 50–80 °C; and / or The reaction time to obtain the first intermediate is 2-8 hours; and / or The molar ratio of the polydimethylsiloxane to the diphenylmethane diisocyanate is 1:(18~25); and / or The reaction temperature for obtaining the second functional polymer is -10 to 5 °C; and / or The reaction time to obtain the second functional polymer is 2-6 hours; and / or The first catalyst is selected from one or more of dibutyltin dilaurate, N,N-dimethylcyclohexylamine, triethylamine, and bis(2-dimethylaminoethyl) ether; The second catalyst is selected from one or more of potassium tert-butoxide, sodium methoxide, potassium ethoxide, and alkyllithium.

9. The preparation method according to claim 4, characterized in that, When mixing the PMMA matrix material, the ASA matrix material, the first functional polymer, and the second functional polymer under heating and melting conditions, add 0.5-1.5 parts of light stabilizer, 0.5-1.5 parts of ultraviolet absorber, 0.5-1.5 parts of primary antioxidant, 0.3-0.8 parts of secondary antioxidant, and 0.5-1.5 parts of organic pigment.

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