Composite material as well as preparation method and application thereof

Abstract

The invention discloses a composite material as well as a preparation method and application thereof, and relates to the technical field of high polymer materials. The composite material comprises a polymer, glass fibers, silicone and an antioxidant. The composite material provided by the invention has excellent mechanical property, flame retardant property and surface electroplating capability, and has a wide application prospect in the fields of new energy automobiles, electronic appliances, buildings, military industry and the like and extreme environments such as a wide temperature range and the like.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a composite material and a preparation method and application thereof. Background Art

[0002] Polycarbonate (PC), one of the five major engineering plastics, boasts advantages such as high transparency, high impact strength, high dimensional stability, and strong flame retardancy, making it widely used in industries such as electronics, automotive manufacturing, and optical manufacturing. However, PC's inherent V-2 flame retardancy, sudden drop in impact strength at -15°C, and brittle cracking make it difficult to use in high-end applications such as new energy vehicles, high-end consumer electronics, and military applications.

[0003] Electroplating a metal layer on the surface of the PC substrate can achieve an efficient fusion of high strength and light weight. The metal plating provides additional wear resistance (reducing surface scratches), UV protection (blocking more than 90% of UV radiation) and electromagnetic shielding (suitable for 5G equipment), while improving chemical resistance (resistance to grease, dilute acid, etc.), so that the product is both beautiful and practical. However, due to the inertness of PC surface molecules and the tight arrangement of molecular chains, it is difficult to roughen the surface by etching, resulting in poor bonding between the coating and the PC substrate surface. It is usually necessary to blend and modify PC (such as using PC / ABS alloy) to improve the electroplating ability of the PC matrix; although the addition of ABS components improves the surface activity of the material, it reduces the impact strength and heat resistance of pure PC, limiting its application in extreme environments. Summary of the Invention

[0004] In view of this, the present application provides a composite material and a preparation method and application thereof.

[0005] The embodiments of the present application are implemented as follows. In a first aspect, the embodiments of the present application provide a composite material, comprising a polymer, glass fiber, silicone, and an antioxidant. The structural formula of the polymer is shown below:

[0006]

[0007] Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200;

[0008] R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100;

[0009] w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

[0010] Optionally, in some embodiments of the present application, in the composite material, the number of the polymer is 73.9 to 84.4 parts; the number of the glass fiber is 15 to 25 parts; the number of the silicone is 0.3 to 0.5 parts; and the number of the antioxidant is 0.3 to 0.6 parts.

[0011] Optionally, in some embodiments of the present application, the glass fiber is a glass fiber modified with 3-mercaptopropyltrimethoxysilane;

[0012] The glass fibers are chopped glass fibers.

[0013] Optionally, in some embodiments of the present application, the antioxidant includes a first antioxidant and a second antioxidant; wherein,

[0014] The first antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024;

[0015] The second antioxidant is selected from one or more of JYANO-168, antioxidant 923, antioxidant 2013, and antioxidant 1001;

[0016] In parts by mass, in the composite material, the amount of the first antioxidant is 0.2 to 0.4 parts; the amount of the second antioxidant is 0.1 to 0.2 parts.

[0017] In a second aspect, the present invention also provides a method for preparing a composite material.

[0018] Provide polymers, glass fibers, silicones, and antioxidants;

[0019] The polymer, the glass fiber, the silicone and the antioxidant are mixed and reacted to obtain a composite material.

[0020] Wherein, the structural formula of the polymer is shown below:

[0021]

[0022] Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200;

[0023] R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100;

[0024] w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

[0025] Optionally, in some embodiments of the present application, the method for preparing the polymer includes:

[0026] Providing a first mixed liquid and a second mixed liquid, wherein the first mixed liquid includes bisphenol A, a flame retardant ODOPB, an alkaline regulator, and a first solvent, and the second mixed liquid includes triphosgene and a second solvent, mixing the first mixed liquid and the second mixed liquid, and performing a first reaction to obtain a prepolymer mixed liquid, wherein the prepolymer mixed liquid includes a prepolymer;

[0027] A third mixed solution is provided, wherein the third mixed solution includes dual-terminal hydroxyl polydimethylsiloxane, terminal hydroxyl polybutadiene and a third solvent. The third mixed solution is mixed with the prepolymer mixed solution to perform a second reaction to obtain a polymer.

[0028] Optionally, in some embodiments of the present application, the first solvent, the second solvent, and the third solvent are each independently selected from one or more of deionized water, dichloromethane, chloroform, 1,2-dichloroethane, and tetrachloroethylene;

[0029] The alkaline regulator is selected from one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide;

[0030] In the first mixed solution, the molar concentration of bisphenol A is 1 mol / L to 3 mol / L;

[0031] In the first mixed solution, the molar concentration of the flame retardant ODOPB is 0.01 mol / L to 0.1 mol / L;

[0032] In the first mixed solution, the molar concentration of the alkaline regulator is 1 mol / L to 5 mol / L;

[0033] In the second mixed solution, the molar concentration of triphosgene is 1 mol / L to 2 mol / L;

[0034] In the third mixed solution, the molar concentration of the double-terminal hydroxyl polydimethylsiloxane is 0.01 mol / L to 0.1 mol / L;

[0035] In the third mixed solution, the molar concentration of the hydroxy-terminated polybutadiene is 0.01 mol / L to 0.1 mol / L;

[0036] The molar ratio of the bisphenol A, the flame retardant ODOPB, the triphosgene, the dihydroxy-terminated polydimethylsiloxane and the hydroxy-terminated polybutadiene is (1-3): (0.01-0.15): (0.36-1.15): (0.01-0.06): (0.01-0.06);

[0037] The reaction temperature of the first reaction is 20°C to 30°C, and the reaction time of the first reaction is 0.5h to 3h;

[0038] The reaction temperature of the second reaction is 20° C. to 30° C.; the reaction time of the second reaction is 0.5 h to 3 h.

[0039] Optionally, in some embodiments of the present application, the glass fiber is a glass fiber modified with 3-mercaptopropyltrimethoxysilane, and the preparation method of the glass fiber modified with 3-mercaptopropyltrimethoxysilane comprises: providing a fourth mixed solution, wherein the fourth mixed solution comprises unmodified glass fiber and a fourth solvent; providing 3-mercaptopropyltrimethoxysilane, mixing the 3-mercaptopropyltrimethoxysilane and the fourth mixed solution, and performing a third reaction to obtain a glass fiber modified with 3-mercaptopropyltrimethoxysilane; wherein,

[0040] The unmodified glass fiber is chopped sand glass fiber;

[0041] The fourth solvent is selected from one or more of ethyl acetate, methyl acetate, butyl acetate, and isopropyl acetate;

[0042] In the fourth mixed solution, the mass concentration of the unmodified glass fiber is 300 g / L to 400 g / L;

[0043] The mass ratio of the unmodified glass fiber to the 3-mercaptopropyltrimethoxysilane is (300-400): (6-7);

[0044] The reaction temperature of the third reaction is 20° C. to 30° C., and the reaction time of the third reaction is 0.5 h to 3 h.

[0045] Optionally, in some embodiments of the present application, the antioxidant includes a first antioxidant and a second antioxidant; the first antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024; the second antioxidant is selected from one or more of JYANO-168, antioxidant 923, antioxidant 2013, and antioxidant 1001.

[0046] In parts by mass, the polymer comprises 73.9 to 84.4 parts, the glass fiber comprises 15 to 25 parts, the silicone comprises 0.3 to 0.5 parts, the first antioxidant comprises 0.2 to 0.4 parts, and the second antioxidant comprises 0.1 to 0.2 parts;

[0047] The reaction of the polymer, the glass fiber, the silicone and the antioxidant includes: melt extrusion granulation; the conditions of the melt extrusion granulation are: temperature of 150°C to 300°C, screw speed of 200r / min to 500r / min, and aspect ratio of (40 to 50):1.

[0048] In a third aspect, the embodiments of the present application further provide an application of the above-mentioned composite material, or the composite material prepared by the above-mentioned preparation method, in the fields of new energy vehicles, electronic appliances, construction, and military industry.

[0049] The composite material provided in the embodiment of the present application includes a polymer and glass fiber shown in the above structural formula. By designing the chemical structure of polycarbonate, a multi-component copolymer PC (polymer) is provided, wherein bisphenol A is used as the main dihydroxy unit to provide basic mechanical strength and rigidity; terminal hydroxy polydimethylsiloxane (PDMS) is used as a toughening unit to provide low-temperature toughness; reactive phosphorus flame retardant ODOPB and PDMS synergistically enhance the intrinsic flame retardant properties of PC; terminal hydroxy polybutadiene (HTPB) enhances the low-temperature toughness of PC while enhancing its etching ability. After roughening treatment, it can efficiently anchor the surface metal plating, giving PC excellent electroplating ability. Silicone can improve the chemical stability and high temperature resistance of the composite material; antioxidant can improve the antioxidant performance of the composite material, thereby improving the stability of the composite material. Through the combination of polymer and glass fiber, silicone and antioxidant, the composite material provided in the embodiment of the present application has excellent mechanical properties, flame retardant properties and the ability to be surface electroplated, and has broad application prospects in the fields of new energy vehicles, electronic appliances, construction, military industry, and extreme environments such as wide temperature ranges. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0051] Figure 1 This is a flow chart of a method for preparing a composite material provided in an embodiment of the present application;

[0052] Figure 2is an infrared spectrum of the polymer provided in Example 3 of the present application;

[0053] Figure 3 This is a sample picture of the injection molded part of the composite material provided in Example 3 of the present application after surface electroplating. DETAILED DESCRIPTION

[0054] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of this application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application and are not used to limit the present application.

[0055] In this application, unless otherwise indicated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of a device in actual use or operation, specifically in the drawing directions of the accompanying drawings; whereas "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "including" means "including but not limited to." Terms such as first, second, and third are used merely as designations and do not impose numerical requirements or establish a sequential order.

[0056] In this application, "and / or" describes the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0057] In this application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0058] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a hard limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numbers within the range. For example, the description of a range from 1 to 6 should be considered to have 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0059] The structural formulas and molecular weights of some chemical reagents used in this application are described below:

[0060] Bisphenol A: Molecular weight = 228.29;

[0061] Triphosgene: Molecular weight = 296.75;

[0062] Flame retardant ODOPB: Molecular weight = 324.27;

[0063] Double-terminated hydroxyl polydimethylsiloxane (HO-PDMS-OH): Wherein m represents the degree of polymerization of PDMS, which is an integer from 20 to 100, and the number average molecular weight of the double-terminated hydroxyl polydimethylsiloxane is 2000;

[0064] Hydroxyl-terminated polybutadiene (HTPB): HTPB-4200 was purchased from Tianyuan Aerospace Materials (Yingkou) Technology Co., Ltd., where a corresponds to the content of 1,4-cis structure, which is approximately 60%; b corresponds to the content of 1,2-vinyl structure, which is approximately 20% to 25%; c corresponds to the content of 1,4-trans structure, which is approximately 15% to 20%; p represents the degree of polymerization of hydroxy-terminated polybutadiene (HTPB), which is an integer of 50 to 100, and its number average molecular weight is 4200;

[0065] 3-Mercaptopropyltrimethoxysilane: Molecular weight = 196.34.

[0066] The technical solution of this application is as follows:

[0067] In a first aspect, an embodiment of the present application provides a composite material. The composite material includes a polymer, glass fiber, silicone, and an antioxidant, wherein the structural formula of the polymer is as follows:

[0068]

[0069] Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200;

[0070] R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100;

[0071] w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

[0072] The composite material provided in the embodiment of the present application includes a polymer and glass fiber shown in the above structural formula. By designing the chemical structure of polycarbonate, a multi-component copolymer PC (polymer) is provided, wherein bisphenol A is used as the main dihydroxy unit to provide basic mechanical strength and rigidity; terminal hydroxy polydimethylsiloxane (PDMS) is used as a toughening unit to provide low-temperature toughness; reactive phosphorus flame retardant ODOPB and PDMS synergistically enhance the intrinsic flame retardant properties of PC; terminal hydroxy polybutadiene (HTPB) enhances the low-temperature toughness of PC while enhancing its etching ability. After roughening treatment, it can efficiently anchor the surface metal plating, giving PC excellent electroplating ability. Silicone can improve the chemical stability and high temperature resistance of the composite material; antioxidant can improve the antioxidant performance of the composite material, thereby improving the stability of the composite material. Through the combination of polymer and glass fiber, silicone and antioxidant, the composite material provided in the embodiment of the present application has excellent mechanical properties, flame retardant properties and the ability to be surface electroplated, and has broad application prospects in the fields of new energy vehicles, electronic appliances, construction, military industry, and extreme environments such as wide temperature ranges.

[0073] In some embodiments, the glass fiber is 3-mercaptopropyltrimethoxysilane-modified glass fiber. In the composite material, the 3-mercaptopropyltrimethoxysilane-modified glass fiber can undergo an addition reaction with the side chain double bonds of the HTPB unit in the polymer, forming a strong chemical connection between the glass fiber and the polymer, enhancing the interfacial bonding between the two and improving the mechanical properties.

[0074] In some embodiments, the glass fibers are chopped glass fibers. Chopped glass fibers, also known as chopped glass strands, are made from quartz sand, which is melted at high temperature, drawn into strands through a special sizing agent, and then wet-cut online or finished product to form a reinforcement material.

[0075] In some embodiments, in the composite material, the polymer comprises 73.9 to 84.4 parts by weight, such as 73.9, 75, 78, 80, 82, 84.4, or a range between any two of the above values; the glass fiber comprises 15 to 25 parts by weight, such as 15, 16, 18, 20, 22, 25, or a range between any two of the above values; the silicone comprises 0.3 to 0.5 parts by weight, such as 0.3, 0.4, 0.5, or a range between any two of the above values; and the antioxidant comprises 0.3 to 0.6 parts by weight, such as 0.3, 0.4, 0.5, 0.6, or a range between any two of the above values. Within the above ranges of the respective components, the polymer can cooperate with the glass fiber, the silicone, and the antioxidant to improve the performance of the composite material.

[0076] In some embodiments, the antioxidant includes a first antioxidant and a second antioxidant, wherein the first antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024, and the second antioxidant is selected from one or more of JYANO-168, antioxidant 923, antioxidant 2013, and antioxidant 1001.

[0077] Furthermore, in the composite material, the first antioxidant is present in an amount of 0.2 to 0.4 parts by mass, such as 0.2, 0.3, 0.4, or any range between the above two values; the second antioxidant is present in an amount of 0.1 to 0.2 parts by mass, such as 0.1, 0.12, 0.15, 0.18, 0.2, or any range between the above two values. Within the above ranges of the amounts of each component, the first and second antioxidants can cooperate with the polymer, the glass fiber, and the silicone to improve the antioxidant properties and stability of the composite material.

[0078] Second, see Figure 1 The present invention provides a method for preparing a composite material, comprising the following steps:

[0079] Step S11, providing polymer, glass fiber, silicone and antioxidant;

[0080] Step S12: mixing the polymer, the glass fiber, the silicone and the antioxidant, and reacting them to obtain a composite material.

[0081] Wherein, the structural formula of the polymer is shown below:

[0082]

[0083] Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200;

[0084] R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100;

[0085] w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

[0086] In the step S11:

[0087] In some embodiments, the method for preparing the polymer comprises:

[0088] Step S111: providing a first mixed liquid and a second mixed liquid, wherein the first mixed liquid includes bisphenol A, flame retardant ODOPB, an alkaline regulator, and a first solvent, and the second mixed liquid includes triphosgene and a second solvent, mixing the first mixed liquid and the second mixed liquid, and performing a first reaction to obtain a prepolymer mixed liquid, wherein the prepolymer mixed liquid includes a prepolymer;

[0089] Step S112: providing a third mixed solution, wherein the third mixed solution includes dihydroxy-terminated polydimethylsiloxane, hydroxy-terminated polybutadiene and a third solvent; mixing the third mixed solution with the prepolymer mixed solution; performing a second reaction to obtain a polymer.

[0090] In some embodiments, the first solvent, the second solvent, and the third solvent are each independently selected from one or more of deionized water, dichloromethane, chloroform, 1,2-dichloroethane, and tetrachloroethylene.

[0091] In some embodiments, the molar concentration of bisphenol A in the first mixed solution is 1 mol / L to 3 mol / L, for example, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, uniform dissolution and dispersion of bisphenol A is facilitated.

[0092] In some embodiments, the flame retardant ODOPB has a molar concentration in the first mixed solution of 0.01 mol / L to 0.1 mol / L, for example, 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, the flame retardant ODOPB is facilitated to be uniformly dissolved and dispersed.

[0093] In some embodiments, the molar concentration of the alkaline regulator in the first mixed solution is 1 mol / L to 5 mol / L, for example, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, the alkaline regulator is facilitated to uniformly dissolve and disperse, and to adjust the pH to a suitable value, thereby promoting subsequent reactions.

[0094] In some embodiments, the alkaline regulator is selected from one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0095] In some embodiments, the molar concentration of triphosgene in the second mixed liquid is 1 mol / L to 2 mol / L, for example, 1 mol / L, 1.2 mol / L, 1.5 mol / L, 1.8 mol / L, 2 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, uniform dissolution and dispersion of triphosgene is facilitated.

[0096] In some embodiments, the molar ratio of bisphenol A to the flame retardant ODOPB to triphosgene is (1-3):(0.01-0.15):(0.36-1.15), for example, 1:0.1:0.36, 2:0.01:0.7, 3:0.06:1.1, 1.5:0.02:0.55, 2.5:0.05:0.9, or a range between any two of the above ratios. Within this molar ratio range, the reaction yield of bisphenol A, the flame retardant ODOPB, and triphosgene is advantageously increased.

[0097] In some embodiments, mixing the first mixed liquid and the second mixed liquid includes: adding the second mixed liquid dropwise into the first mixed liquid.

[0098] Furthermore, the second mixed solution is added dropwise to the first mixed solution under ice bath conditions.

[0099] In some embodiments, the reaction temperature of the first reaction is 20° C. to 30° C., for example, 20° C., 22° C., 25° C., 28° C., 30° C., or a range between any two of the foregoing values; the reaction time of the first reaction is 0.5 h to 3 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or a range between any two of the foregoing values. Thus, under the reaction conditions of the first reaction, the prepolymer is efficiently produced.

[0100] In some embodiments, the prepolymer has the following structural formula:

[0101]

[0102] Wherein, q represents the degree of polymerization, which is any integer selected from 10 to 15; w represents the molar content, which is 77% to 90%; and x represents the molar content, which is 2% to 5%.

[0103] In some embodiments, the molar concentration of the bihydroxy-terminated polydimethylsiloxane in the third mixed solution is 0.01 mol / L to 0.1 mol / L, for example, 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, the bihydroxy-terminated polydimethylsiloxane is facilitated to be uniformly dissolved and dispersed.

[0104] In some embodiments, the molar concentration of the hydroxyl-terminated polybutadiene in the third mixed solution is 0.01 mol / L to 0.1 mol / L, for example, 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, the hydroxyl-terminated polybutadiene is facilitated to be uniformly dissolved and dispersed.

[0105] In some embodiments, the molar ratio of bisphenol A to the dihydroxy-terminated polydimethylsiloxane and the hydroxy-terminated polybutadiene is (1-3):(0.01-0.06):(0.01-0.06), for example, 1:0.01:0.01, 2:0.03:0.04, 3:0.06:0.03, 1.5:0.02:0.025, 2.5:0.05:0.04, or a range between any two of the above ratios. Within the above molar ratio range, the reaction yield of the prepolymer, the dihydroxy-terminated polydimethylsiloxane, and the hydroxy-terminated polybutadiene is improved.

[0106] In some embodiments, mixing the third mixed liquid and the prepolymer mixed liquid comprises: adding the third mixed liquid dropwise into the prepolymer mixed liquid.

[0107] In some embodiments, the reaction temperature of the second reaction is 20° C. to 30° C., for example, 20° C., 22° C., 25° C., 28° C., 30° C., or a range between any two of the foregoing values; the reaction time of the second reaction is 0.5 h to 3 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or a range between any two of the foregoing values. Thus, under the reaction conditions of the second reaction, a chain extension reaction is favorable for forming a polymer.

[0108] It should be noted that after the third mixed liquid and the prepolymer mixed liquid are mixed and subjected to the second reaction, the aqueous phase and the organic phase can be separated by a separatory funnel, and the organic phase can be repeatedly rinsed with deionized water until the pH is between 7 and 8, and then the organic phase is poured into excess methanol for precipitation to obtain a polymer.

[0109] This application adopts the safer and more environmentally friendly triphosgene method to synthesize a multi-component copolymer PC (polymer), in which bisphenol A is used as the main dihydroxy unit to provide basic mechanical strength and rigidity; terminal hydroxy polydimethylsiloxane (PDMS) is used as a toughening unit to provide low-temperature toughness; the reactive phosphorus-based flame retardant ODOPB and PDMS synergistically enhance the intrinsic flame retardant properties of PC; terminal hydroxy polybutadiene (HTPB) improves the low-temperature toughness of PC while enhancing its etching ability. After roughening treatment, it can efficiently anchor the surface metal plating, giving PC excellent electroplating ability.

[0110] In some embodiments, the glass fiber is 3-mercaptopropyltrimethoxysilane-modified glass fiber.

[0111] Furthermore, the preparation method of the 3-mercaptopropyltrimethoxysilane-modified glass fiber comprises:

[0112] Step S113, providing a fourth mixed solution, wherein the fourth mixed solution includes unmodified glass fiber and a fourth solvent;

[0113] Step S114: providing 3-mercaptopropyltrimethoxysilane, mixing the 3-mercaptopropyltrimethoxysilane with the fourth mixed solution, and performing a third reaction to obtain a glass fiber modified with 3-mercaptopropyltrimethoxysilane.

[0114] In some embodiments, the unmodified glass fibers are chopped sand glass fibers.

[0115] In some embodiments, the fourth solvent is selected from one or more of ethyl acetate, methyl acetate, butyl acetate, and isopropyl acetate.

[0116] In some embodiments, the mass concentration of the unmodified glass fiber in the fourth mixed liquid is 300 g / L to 400 g / L, for example, 300 g / L, 320 g / L, 350 g / L, 380 g / L, 400 g / L, or a range between any two of the foregoing values. Within this mass concentration range, the unmodified glass fiber is facilitated to be uniformly dissolved and dispersed.

[0117] In some embodiments, the mass ratio of the unmodified glass fiber to the 3-mercaptopropyltrimethoxysilane is (300-400):(6-7), for example, 300:6, 400:6.2, 350:6.2, 380:6.5, 330:7, or a range between any two of the above ratios. Within the above mass ratio range, the 3-mercaptopropyltrimethoxysilane is conducive to promoting appropriate modification of the unmodified glass fiber.

[0118] In some embodiments, the reaction temperature of the third reaction is 20° C. to 30° C., for example, 20° C., 22° C., 25° C., 28° C., 30° C., or a range between any two of the above values; the reaction time of the third reaction is 0.5 h to 3 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or a range between any two of the above values. Thus, under the reaction conditions of the third reaction, the 3-mercaptopropyltrimethoxysilane-modified glass fiber is efficiently produced.

[0119] The silicone and antioxidant are mentioned above and will not be described in detail here.

[0120] In the step S12:

[0121] In some embodiments, the polymer comprises 73.9 to 84.4 parts by weight, the glass fiber comprises 15 to 25 parts by weight, the silicone comprises 0.3 to 0.5 parts by weight, the first antioxidant comprises 0.2 to 0.4 parts by weight, and the second antioxidant comprises 0.1 to 0.2 parts by weight. Within the aforementioned ranges of the components, the components cooperate with each other to improve the performance of the composite material.

[0122] In some embodiments, the reaction of the polymer, the glass fiber, the silicone, and the antioxidant comprises melt extrusion granulation, which can be performed using a twin-screw extruder.

[0123] Furthermore, the conditions for the melt extrusion granulation are as follows: the temperature is 150°C to 300°C, for example, it can be 150°C, 200°C, 250°C, 300°C or a range between any two values; the screw speed is 200r / min to 500r / min, for example, it can be 200r / min, 250r / min, 300r / min, 350r / min, 400r / min, 450r / min, 5200r / min or a range between any two values; the aspect ratio is (40 to 50):1, for example, it can be 40:1, 42:1, 45:1, 48:1, 50:1 or a range between any two of the above ratios.

[0124] In this way, under the conditions of melt extrusion granulation, the polymer, the glass fiber, the silicone and the antioxidant are fully mixed and reacted to obtain a high-performance composite material.

[0125] In a third aspect, embodiments of the present application further provide applications of the composite material or the composite material prepared by the above-mentioned preparation method.

[0126] Specifically, the above-mentioned composite materials have excellent mechanical properties, flame retardant properties and the ability to be surface electroplated, and have broad application prospects in new energy vehicles, electronic appliances, construction, military industry and other fields as well as extreme environments such as wide temperature ranges.

[0127] The present application will be described in detail below through specific examples. The following examples are only some examples of the present application and are not limitations of the present application.

[0128] Example 1

[0129] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0130] Step 1a: Weigh 0.97 mol of bisphenol A, 0.03 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the addition is completed, keep stirring for 0.5 hours, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0131]

[0132] Step 2a: Weigh 0.01 mol of double-terminated hydroxyl polydimethylsiloxane, 0.01 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane and add them to a 500 mL beaker, start stirring to mix them evenly, and obtain a third mixed solution. At 25 ° C, the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1a through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour; after the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8, and then the organic phase is poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0133]

[0134] Step 3a: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0135] Step 4a: Take 2.373 kg of the polymer obtained in step 2a, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3a, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set as follows: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0136] Example 2

[0137] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0138] Step 1b: Weigh 0.95 mol of bisphenol A, 0.05 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the addition is completed, keep stirring for 0.5 hours, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0139]

[0140] Step 2b: Weigh 0.01 mol of double-terminated hydroxyl polydimethylsiloxane, 0.01 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane into a 500 mL beaker, start stirring to mix evenly, and obtain a third mixed solution. At 25 ° C, the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1b through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour. After the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8. The organic phase is then poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0141]

[0142] Step 3b: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0143] Step 4b: Take 2.373 kg of the polymer obtained in step 2b, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3b, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set to: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0144] Example 3

[0145] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0146] Step 1c: Weigh 0.97 mol of bisphenol A, 0.03 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the addition is completed, keep stirring for 0.5 hours, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0147]

[0148] Step 2c: Weigh 0.02 mol of double-terminated hydroxyl polydimethylsiloxane, 0.01 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane and add them to a 500 mL beaker, start stirring to mix them evenly, and obtain a third mixed solution. At 25 ° C, the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1c through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour; after the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8, and then the organic phase is poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0149]

[0150] Step 3c: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0151] Step 4c: Take 2.373 kg of the polymer obtained in step 2c, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3c, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set to: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0152] Example 4

[0153] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0154] Step 1d: Weigh 0.95 mol of bisphenol A, 0.05 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the addition is completed, keep stirring for 0.5 hours, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0155]

[0156] Step 2d: Weigh 0.02 mol of double-terminated hydroxyl polydimethylsiloxane, 0.01 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane into a 500 mL beaker, start stirring to mix evenly, and obtain a third mixed solution. At 25 ° C, the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1d through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour. After the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8. The organic phase is then poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0157]

[0158] Step 3d: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0159] Step 4d: Take 2.373 kg of the polymer obtained in step 2d, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3d, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set to: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0160] Example 5

[0161] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0162] Step 1e: Weigh 0.95 mol of bisphenol A, 0.05 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the dropwise addition is completed, keep stirring for 0.5 hour, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0163]

[0164] Step 2e: Weigh 0.01 mol of double-terminated hydroxyl polydimethylsiloxane, 0.02 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane into a 500 mL beaker, start stirring to mix evenly, and obtain a third mixed solution. At 25° C., the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1e through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour. After the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8. The organic phase is then poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0165]

[0166] Step 3e: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0167] Step 4e: Take 2.373 kg of the polymer obtained in step 2e, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3e, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set as follows: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0168] Example 5

[0169] This embodiment provides a composite material, the preparation method of which includes the following steps:

[0170] Step 1f: Weigh 0.95 mol of bisphenol A, 0.05 mol of flame retardant ODOPB, 2 mol of sodium hydroxide and 500 mL of deionized water into a 1000 mL three-necked flask, start stirring, set the speed to 100 rpm, until the reactants are completely dissolved to obtain a first mixed solution; introduce circulating nitrogen protection; dissolve 0.35 mol of triphosgene in 200 mL of dichloromethane to obtain a second mixed solution, and under ice bath conditions, control the second mixed solution to be dropwise added to the three-necked flask of the first mixed solution through a constant pressure funnel over a period of about 1 hour. After the dropwise addition is completed, keep stirring for 0.5 hours, raise the reaction temperature to 25°C, adjust the speed to 300 rpm, and continue the reaction for 1 hour to obtain a prepolymer mixed solution, which includes a prepolymer. The structural formula of the prepolymer is shown below:

[0171]

[0172] Step 2f: Weigh 0.02 mol of double-terminated hydroxyl polydimethylsiloxane, 0.02 mol of hydroxyl-terminated polybutadiene and 200 mL of dichloromethane and add them to a 500 mL beaker, start stirring to mix them evenly, and obtain a third mixed solution. At 25 ° C, the third mixed solution is added dropwise to the prepolymer mixed solution obtained in step 1f through a constant pressure funnel. After the addition is completed, stirring is maintained to carry out a chain extension reaction for 1 hour. After the reaction is completed, the aqueous phase and the organic phase are separated by a separatory funnel, and the organic phase is repeatedly rinsed with deionized water until the pH is 7-8. The organic phase is then poured into excess methanol for precipitation, filtered, and dried to obtain a polymer. The structural formula of the polymer is shown below:

[0173]

[0174] Step 3f: 100 g of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.) and 300 g of ethyl acetate were added to a 1 L beaker; mechanical stirring and ultrasonic dispersion were performed at room temperature for 1 hour to obtain a uniform fourth mixed solution; 2 g of 3-mercaptopropyltrimethoxysilane was then added, mechanical stirring was maintained at 25° C. for 1 hour, and the mixture was filtered and dried to obtain chopped sand glass fiber with mercapto groups on the surface;

[0175] Step 4f: Take 2.373 kg of the polymer obtained in step 2f, 0.6 kg of chopped sand glass fiber with a mercapto group on the surface obtained in step 3f, 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168, mix them evenly with a medium-speed mixer, and then melt-extrude and granulate them through a twin-screw extruder. The temperature zones of the extruder are set as follows: Zone 1: 150°C, Zone 2: 250°C, Zone 3: 250°C, Zone 4: 260°C, Zone 5: 260°C, Zone 6: 250°C, Zone 7: 240°C, Zone 8: 240°C, Zone 9: 240°C, Zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain a composite material.

[0176] Comparative Example 1

[0177] This comparative example provides a composite material, and the preparation method is as follows:

[0178] Take 1.773kg of commercially available general-purpose polycarbonate (PC-110, purchased from Chimei Industrial Co., Ltd.), 0.6kg of chopped sand glass fiber (4.5mm, purchased from Shandong Taicheng Fiber Co., Ltd.), 0.15kg of bisphenol A-bis(diphenyl phosphate) (flame retardant BDP), 0.6kg of PC commonly used MBS low-temperature toughening agent (M-722), 12g of silicone, 9g of the first antioxidant 1076, and 6g of the second antioxidant JYAN O-168 is mixed evenly with a medium-speed mixer and then melt-extruded into granules through a twin-screw extruder. The temperature zones of the extruder are set as follows: zone 1: 150°C, zone 2: 250°C, zone 3: 250°C, zone 4: 260°C, zone 5: 260°C, zone 6: 250°C, zone 7: 240°C, zone 8: 240°C, zone 9: 240°C, zone 10: 290°C, the screw speed is 300 r / min, and the aspect ratio is 48:1 to obtain the composite material.

[0179] Comparative Example 2

[0180] This comparative example provides a composite material, and the preparation method is as follows:

[0181] Take 2.373 kg of the polymer obtained in step 2c of Example 3, 0.6 kg of chopped sand glass fiber (4.5 mm, purchased from Shandong Taicheng Fiber Co., Ltd.), 12 g of silicone, 9 g of the first antioxidant 1076, and 6 g of the second antioxidant JYANO-168. After mixing evenly with a medium-speed mixer, the mixture was melt-extruded and granulated through a twin-screw extruder. The temperature zones of the extruder were set to: Zone 1: 150 ° C, Zone 2: 250 ° C, Zone 3: 250 ° C, Zone 4: 260 ° C, Zone 5: 260 ° C, Zone 6: 250 ° C, Zone 7: 240 ° C, Zone 8: 240 ° C, Zone 9: 240 ° C, Zone 10: 290 ° C, the screw speed was 300 r / min, and the aspect ratio was 48: 1 to obtain the composite material.

[0182] The polymer obtained in step 2c of Example 3 was tested by infrared spectroscopy. Figure 2 .

[0183] like Figure 2 As shown, located at 1773cm -1 The absorption peak at 1508 cm corresponds to the stretching vibration of the carbonyl group in the carbonate group; -1 The absorption peak at 1223 cm corresponds to the skeleton vibration of the benzene ring; -1 and 1191cm -1 The absorption peak at 2923 cm corresponds to the asymmetric stretching vibration of COC; -1 The absorption peak at 1299 cm is the characteristic peak of -CH3 in bisphenol A unit and PDMS unit; -1 The absorption peak at 840 cm is derived from the P=O stretching vibration of the phosphaphenanthrene group; -1 The absorption peak at 1600 cm is the characteristic peak of PO; -1 and 1500cm -1 The absorption peak near the benzene ring is the stretching vibration peak of C=C; located at 1091cm -1 The absorption peak at 1261cm is the characteristic peak of Si-O; -1 The absorption peak at 3066 cm corresponds to the deformation vibration of the methyl group in Si-CH3; -1 The absorption peak at 966 cm is the characteristic peak of unsaturated CH stretching vibration; -1 The absorption peak at 912 cm corresponds to the bending vibration of trans CH; -1 The absorption peak corresponds to the CH deformation vibration of the 1,2 addition product; it is located at 728 cm -1 The absorption peak corresponds to the cis-CH deformation vibration; the appearance of the above characteristic bands indicates the successful synthesis of copolymerized PC (polymer) containing flame retardant ODOPB, PDMS and HTPB units.

[0184] The composite materials of Examples 1 to 6 and Comparative Examples 1 to 2 were injection molded to prepare mechanical property test specimens and color plates, and subsequent performance tests were performed.

[0185] The composite materials of Examples 1 to 6 and the composite materials of Comparative Examples 1 to 2 were tested for density, heat deformation temperature, tensile strength, flexural modulus, room temperature notched impact strength, and flame retardancy. The test results are shown in Table 1.

[0186] Among them, the density test is carried out in accordance with the standard ISO 1183; the heat deformation temperature 1.8MPa is carried out in accordance with the standard ISO 75; the tensile strength test is carried out in accordance with the standard ISO 527; the flexural modulus test is carried out in accordance with the standard ISO 178; the Izod notched impact strength test is carried out in accordance with the standard GB / T 1843-2008; the flame retardant performance test is carried out in accordance with the standard UL94, and the specimen thickness is 1.6mm.

[0187] Table 1

[0188]

[0189] As can be seen from Table 1, the polymer in the composite material provided by the embodiment of the present application introduces highly flexible polydimethylsiloxane (PDMS) and polybutadiene molecular chain (HTPB), and its loose stacking state makes the polymer density lower, which is conducive to material lightweighting. At the same time, as the content of PDMS and HTPB increases, the heat deformation temperature, mechanical strength, and flexural strength of the material decrease, but are still better than those of Comparative Example 1.

[0190] The introduction of PDMS and HTPB molecular chains with excellent low-temperature flexibility through chemical copolymerization significantly improves the impact toughness of PC; its impact resistance is also very good at low temperatures. Compared with the composite material reported in Comparative Example 1, the toughening effect of the chemical copolymerization flexible chain segment is better than that of the composite material with the addition of an elastomer toughening agent. This is because the flexible components introduced by chemical copolymerization are more evenly dispersed in the PC material, which can more effectively absorb energy and avoid stress concentration when encountering impact.

[0191] At the same time, the composite material in Example 3 exhibits better mechanical properties than the composite material in Comparative Example 2. This is because the glass fiber has a thiol group on its surface, which reacts with the side chain double bond in the HTPB unit during melt blending with the polymer, forming a strong chemical connection between the glass fiber and the matrix, enhancing the interfacial bonding between the two, and improving its mechanical properties.

[0192] In addition, by introducing the reactive flame retardant ODOPB and the high-silicon content PDMS into the PC molecular chain, the excellent synergistic flame retardant effect between the two can give PC excellent intrinsic flame retardant properties. Example 1 contains only 3 mol% of ODOPB, and the material flame retardant grade is V1 level; Example 2 contains only 5 mol% of ODOPB, and the material flame retardant grade is V0 level.

[0193] In addition, the surface electroplating experiment was conducted on the injection molded parts of the composite material provided in Example 3 of the present application, and the results were as follows: Figure 3 As shown in the figure, after electroplating, the coating on the surface of the parts is uniform in color, bright as a mirror, without any visible defects, and the surface is smooth and dense.

[0194] In summary, the composite materials provided in the embodiments of the present application have excellent mechanical properties, flame retardant properties and the ability to be surface electroplated, and have broad application prospects in the fields of new energy vehicles, electronic appliances, construction, military industry, and extreme environments such as wide temperature ranges.

[0195] The above is a detailed introduction to the technical solutions provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for those skilled in the art, based on the ideas of the present application, there may be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A composite material, characterized in that The composite material includes a polymer, glass fiber, silicone and an antioxidant, and the structural formula of the polymer is shown below: Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200; R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100; w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

2. The composite material according to claim 1, characterized in that In parts by mass, in the composite material, the polymer accounts for 73.9 to 84.4 parts; the glass fiber accounts for 15 to 25 parts; the silicone accounts for 0.3 to 0.5 parts; and the antioxidant accounts for 0.3 to 0.6 parts.

3. The composite material according to claim 1, characterized in that The glass fiber is a glass fiber modified with 3-mercaptopropyltrimethoxysilane; The glass fibers are chopped glass fibers.

4. The composite material according to claim 1 or 2, characterized in that The antioxidant includes a first antioxidant and a second antioxidant; wherein, The first antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024; The second antioxidant is selected from one or more of JYANO-168, antioxidant 923, antioxidant 2013, and antioxidant 1001; In parts by mass, in the composite material, the amount of the first antioxidant is 0.2 to 0.4 parts; the amount of the second antioxidant is 0.1 to 0.2 parts.

5. A method for preparing a composite material, characterized in that: The steps include: Provide polymers, glass fibers, silicones, and antioxidants; mixing the polymer, the glass fiber, the silicone and the antioxidant, and reacting them to obtain a composite material; Wherein, the structural formula of the polymer is shown below: Wherein, m represents the degree of polymerization, which is selected from any integer between 20 and 100; n represents the degree of polymerization, which is selected from any integer between 150 and 200; R is a represents the molar content, which is 55% to 65%, b represents the molar content, which is 20% to 25%, and c represents the molar content, which is 15% to 20%; p represents the degree of polymerization, which is any integer selected from 50 to 100; w represents the molar content, which is 77% to 90%; x represents the molar content, which is 2% to 5%; y represents the molar content, which is 1% to 2%; and z represents the molar content, which is 1% to 2%.

6. The preparation method according to claim 5, characterized in that The preparation method of the polymer comprises: Providing a first mixed liquid and a second mixed liquid, wherein the first mixed liquid includes bisphenol A, a flame retardant ODOPB, an alkaline regulator, and a first solvent, and the second mixed liquid includes triphosgene and a second solvent, mixing the first mixed liquid and the second mixed liquid, and performing a first reaction to obtain a prepolymer mixed liquid, wherein the prepolymer mixed liquid includes a prepolymer; A third mixed solution is provided, wherein the third mixed solution includes dual-terminal hydroxyl polydimethylsiloxane, terminal hydroxyl polybutadiene and a third solvent. The third mixed solution is mixed with the prepolymer mixed solution to perform a second reaction to obtain a polymer.

7. The preparation method according to claim 6, characterized in that The first solvent, the second solvent, and the third solvent are each independently selected from one or more of deionized water, dichloromethane, chloroform, 1,2-dichloroethane, and tetrachloroethylene; The alkaline regulator is selected from one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide; In the first mixed solution, the molar concentration of bisphenol A is 1 mol / L to 3 mol / L; In the first mixed solution, the molar concentration of the flame retardant ODOPB is 0.01 mol / L to 0.1 mol / L; In the first mixed solution, the molar concentration of the alkaline regulator is 1 mol / L to 5 mol / L; In the second mixed solution, the molar concentration of triphosgene is 1 mol / L to 2 mol / L; In the third mixed solution, the molar concentration of the double-terminal hydroxyl polydimethylsiloxane is 0.01 mol / L to 0.1 mol / L; In the third mixed solution, the molar concentration of the hydroxy-terminated polybutadiene is 0.01 mol / L to 0.1 mol / L; The molar ratio of the bisphenol A, the flame retardant ODOPB, the triphosgene, the dihydroxy-terminated polydimethylsiloxane and the hydroxy-terminated polybutadiene is (1-3): (0.01-0.15): (0.36-1.15): (0.01-0.06): (0.01-0.06); The reaction temperature of the first reaction is 20°C to 30°C, and the reaction time of the first reaction is 0.5h to 3h; The reaction temperature of the second reaction is 20° C. to 30° C.; the reaction time of the second reaction is 0.5 h to 3 h.

8. The preparation method according to claim 5, characterized in that The glass fiber is a glass fiber modified with 3-mercaptopropyltrimethoxysilane. The preparation method of the glass fiber modified with 3-mercaptopropyltrimethoxysilane comprises: providing a fourth mixed liquid, wherein the fourth mixed liquid comprises unmodified glass fiber and a fourth solvent; providing 3-mercaptopropyltrimethoxysilane, mixing the 3-mercaptopropyltrimethoxysilane and the fourth mixed liquid, and performing a third reaction to obtain a glass fiber modified with 3-mercaptopropyltrimethoxysilane; wherein, The unmodified glass fiber is chopped sand glass fiber; The fourth solvent is selected from one or more of ethyl acetate, methyl acetate, butyl acetate, and isopropyl acetate; In the fourth mixed solution, the mass concentration of the unmodified glass fiber is 300 g / L to 400 g / L; The mass ratio of the unmodified glass fiber to the 3-mercaptopropyltrimethoxysilane is (300-400): (6-7); The reaction temperature of the third reaction is 20° C. to 30° C., and the reaction time of the third reaction is 0.5 h to 3 h.

9. The preparation method according to claim 5, characterized in that The antioxidant includes a first antioxidant and a second antioxidant; the first antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant 1098, and antioxidant 1024; the second antioxidant is selected from one or more of JYANO-168, antioxidant 923, antioxidant 2013, and antioxidant 1001 In parts by mass, the polymer comprises 73.9 to 84.4 parts, the glass fiber comprises 15 to 25 parts, the silicone comprises 0.3 to 0.5 parts, the first antioxidant comprises 0.2 to 0.4 parts, and the second antioxidant comprises 0.1 to 0.2 parts; The reaction of the polymer, the glass fiber, the silicone and the antioxidant includes: melt extrusion granulation; the conditions of the melt extrusion granulation are: temperature of 150°C to 300°C, screw speed of 200r / min to 500r / min, and aspect ratio of (40 to 50):

1.

10. Use of the composite material according to any one of claims 1 to 4, or the composite material prepared by the preparation method according to any one of claims 5 to 9 in the fields of new energy vehicles, electronic appliances, construction, and military industry.

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