A polyphenylene sulfide composite material and a method for producing the same

Abstract

The application discloses a kind of polyphenylene sulfide composite, it is related to the field of polymer materials.Polyphenylene sulfide composite includes: polyphenylene sulfide 47.7~75 parts;Polyamide elastomer 3~8 parts;And fiber filler 20~40 parts by mass fraction;Chemical structure of polyamide elastomer is: Wherein, m indicates the polymerization degree of polyether amine structure, from the integer of 20~50;N indicates the polymerization degree of polyamide elastomer, n is the integer of 100~200;X, y indicates the molar content of corresponding structural unit in elastomer molecular structure, x=0.2~0.4, y=0.6~0.8.The polyphenylene sulfide composite is excellent in comprehensive performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a polyphenylene sulfide composite material and a preparation method thereof. BACKGROUND

[0002] Polyphenylene sulfide (PPS) is composed of benzene rings and sulfur atoms arranged alternately. Due to its excellent high-temperature resistance, excellent chemical stability and intrinsic flame-retardant properties, PPS has become a core material in high-end application fields such as aerospace, electronics and electrical appliances. However, the tensile strength and bending strength of pure PPS are not outstanding; and the high crystallization property (crystallinity of 70%) of PPS itself leads to poor impact toughness.

[0003] Therefore, in order to expand the application field of PPS, it is necessary to modify PPS in composite to realize the lightweight, high strength, low cost and multifunctionalization of PPS composite material. SUMMARY

[0004] Therefore, the present application provides a polyphenylene sulfide composite material which has excellent comprehensive performance.

[0005] In a first aspect, the present application provides a polyphenylene sulfide composite material, in terms of mass fraction, the polyphenylene sulfide composite material comprises:

[0006] 47.7-75 parts of polyphenylene sulfide;

[0007] 3-8 parts of polyamide elastomer; and

[0008] 20-40 parts of fibrous filler

[0009] The chemical structure of the polyamide elastomer is: .

[0010] wherein m represents the polymerization degree of the polyetheramine structure, and is an integer from 20 to 50; n represents the polymerization degree of the polyamide elastomer, and n is an integer from 100 to 200; x and y represent the molar content of the corresponding structural units in the elastomer molecular structure, x = 0.2-0.4, and y = 0.6-0.8.

[0011] Optionally, in some embodiments of the present application, the fibrous filler comprises:

[0012] 15-25 parts of glass fiber; and

[0013] 5-15 parts of carbon fiber.

[0014] Optionally, in some embodiments of the present application, the glass fiber is a glass fiber with urea groups on the surface; and / or

[0015] The carbon fiber is a carbon fiber with carbon nanotubes on the surface.

[0016] Optionally, in some embodiments of the present application, the composite material further comprises:

[0017] primary antioxidant 0.5-1.5 parts;

[0018] secondary antioxidant 0.5-0.8 parts; and

[0019] lubricant 1-2 parts.

[0020] In a second aspect, the present application provides a preparation method of the composite material, comprising the following steps:

[0021] providing polyphenylene sulfide, polyamide elastomer and fiber filler; and

[0022] mixing the polyphenylene sulfide, the polyamide elastomer and the fiber filler under heating conditions to obtain the composite material;

[0023] The chemical structure of the polyamide elastomer is: ;

[0024] wherein m represents the polymerization degree of the polyetheramine structure, and is an integer from 20 to 50; n represents the polymerization degree of the polyamide elastomer, and n is an integer from 100 to 200; x and y represent the molar content of the corresponding structural units in the elastomer molecular structure, x = 0.2-0.4, and y = 0.6-0.8.

[0025] Optionally, in some embodiments of the present application, the preparation method of the polyamide elastomer comprises:

[0026] mixing nylon salt, adipic acid, polyetheramine and water to obtain a first dispersion liquid; and

[0027] containing the first dispersion liquid in a reaction container, and reacting to obtain the polyamide elastomer;

[0028] wherein the chemical formula of the nylon salt is: .

[0029] Optionally, in some embodiments of the present application, the reaction to obtain the polyamide elastomer is carried out at a temperature of 180-300°C; and / or

[0030] the reaction time for the reaction to obtain the polyamide elastomer is 4-8h; and / or

[0031] the reaction to obtain the polyamide elastomer is carried out under the condition of a protective gas; and / or

[0032] the molar ratio of the nylon salt, the adipic acid and the polyetheramine is (1-2):(3-4):(3-4); and / or

[0033] The mass ratio of the nylon salt to water in the first dispersion is (1-2):10; and / or

[0034] The first dispersion further comprises an antioxidant, and the mass ratio of the antioxidant to the nylon salt is 1:(10-20).

[0035] Optionally, in some embodiments of the present application, the method for preparing the nylon salt comprises:

[0036] Providing p-aminobenzoic acid, p-phenylenediamine dichloride, and a first solvent;

[0037] Mixing the p-aminobenzoic acid, the p-phenylenediamine dichloride, and the first solvent to obtain a nylon salt intermediate;

[0038] Mixing the nylon salt intermediate with hexanediamine and water to obtain the nylon salt.

[0039] Optionally, in some embodiments of the present application, the reaction to obtain the nylon salt intermediate is performed at a temperature of -10-5°C; and / or

[0040] The reaction time for the reaction to obtain the nylon salt intermediate is 1-3h; and / or

[0041] The reaction to obtain the nylon salt intermediate is performed under a protective gas; and / or

[0042] The molar ratio of the p-aminobenzoic acid to the p-phenylenediamine dichloride is (4-6):1; and / or

[0043] The mass ratio of the p-aminobenzoic acid to the first solvent is 1:(4-6); and / or

[0044] The reaction to obtain the nylon salt is performed at a temperature of 50-80°C; and / or

[0045] The reaction time for the reaction to obtain the nylon salt is 0.5-3h; and / or

[0046] The final pH value of the nylon salt aqueous solution obtained by the reaction is 7.0-7.5; and / or

[0047] The first solvent is selected from one or more of N,N-dimethylacetamide, dioxane, and tetrahydrofuran.

[0048] Optionally, in some embodiments of the present application, the above method for preparing further comprises:

[0049] Before obtaining the composite material, mixing the polyphenylene sulfide, the polyamide elastomer, and the fiber filler with the primary antioxidant, the secondary antioxidant, and the lubricant;

[0050] The polyphenylene sulfide is 47.7-75 parts by mass, the polyamide elastomer is 3-8 parts, the fiber filler is 20-40 parts, the main antioxidant is 0.5-1.5 parts, the auxiliary antioxidant is 0.5-0.8 parts, and the lubricant is 1-2 parts.

[0051] The polyphenylene sulfide composite provided in the application is toughened by the polyamide thermoplastic elastomer to the polyphenylene sulfide material matrix. The molecular structure of the polyamide elastomer includes a soft segment molecular structure and a hard segment molecular structure. The hard segment structure has high-density amide groups and benzene rings, so that the polyamide elastomer can form strong interactions such as π-π stacking and dipole interaction with the polyphenylene sulfide matrix material, thereby improving the compatibility between the polyamide elastomer and the polyphenylene sulfide matrix material. The polyether amine soft segment structure gives the polyamide elastomer good flexibility, so that it has good toughening effect. BRIEF DESCRIPTION OF DRAWINGS

[0052] In order to more clearly illustrate the technical solutions in the embodiments of the application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0053] Figure 1 is the infrared spectrum of the nylon salt intermediate prepared in Example 1 of the application;

[0054] Figure 2 is the infrared spectrum of the nylon salt prepared in Example 1 of the application;

[0055] Figure 3 is the infrared spectrum of the polyamide elastomer prepared in Example 1 of the application. DETAILED DESCRIPTION

[0056] The technical solutions in the embodiments of the application will be described clearly and completely in the following with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only some embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the application, and are not used to limit the application.

[0057] In the present application, the orientation words such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, specifically the drawing surface direction in the drawings, unless otherwise specified. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order.

[0058] In the present application, the association relationship of the associated objects is described by "and / or", which means that there can be three kinds of relationships, for example, A and / or B can represent the following cases: A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural.

[0059] In the present application, "at least one" means one or more, and "multiple" means two or more. "One or more", "at least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0060] Various embodiments of the present application can exist in the form of a range; it should be understood that the description in the form of a range is only for the convenience and brevity, and should not be understood as a hard limit on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values within the 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated in the present application, it refers to any cited number (fraction or integer) within the indicated range.

[0061] The structure and molecular weight of some chemical reagents used in the present application are described as follows:

[0062] p-aminobenzoic acid: Molecular weight = 137.14;

[0063] p-Phthaloyl chloride: Molecular weight = 203.02;

[0064] Hexanediamine: Molecular weight = 116.2; Polyether amine:

[0065] , wherein m represents the polymerization degree of the polyether amine, m is an integer from 20 to 50, and the number average molecular weight of the polyether amine = 2000; Adipic acid:

[0066] , molecular weight = 146.14;

[0067] 3-ureidopropyl trimethoxysilane: , molecular weight = 222.31

[0068] The technical solution of the present application is as follows:

[0069] In a first aspect, the present application provides a polyphenylene sulfide composite material, in terms of mass parts, the polyphenylene sulfide composite material comprises:

[0070] Polyphenylene sulfide 47.7-75 parts;

[0071] Polyamide elastomer 3-8 parts; and

[0072] Fiber filler 20-40 parts

[0073] The chemical structure of the polyamide elastomer is: ;

[0074] , wherein m represents the polymerization degree of the polyether amine structure, and is an integer from 20 to 50; n represents the polymerization degree of the polyamide elastomer, n is an integer from 100 to 200; x, y represent the molar content of the corresponding structural units in the elastomer molecular structure, x = 0.2-0.4, y = 0.6-0.8.

[0075] Further, the molecular structure of the polyamide elastomer includes hard segment structure and soft segment structure, and the definition and distinction of the hard segment structure and the soft segment structure are common knowledge known to those skilled in the art, which will not be repeated here. It can be understood that the structural unit corresponding to x is a hard segment unit, and the structural unit corresponding to y is a soft segment unit, so the molar content represented by x and y is essentially the molar content of the hard segment unit and the soft segment unit in the polyamide elastomer molecule. When the molar content of the hard segment unit and the soft segment unit in the polyamide elastomer molecule is within the aforementioned range, the compatibility of the elastomer and the polyphenylene sulfide matrix material and the toughening effect can be considered.

[0076] It should be noted that in order to improve the mechanical properties of the polymer composite, the polymer components of the composite need to have good compatibility between each other. The molecular structure of the polyamide elastomer provided in the present application includes soft segment molecular structure and hard segment molecular structure, wherein the hard segment structure has high density of amide groups and benzene rings, so that the polyamide elastomer can form strong interactions such as π-π stacking and dipole interaction with the polyphenylene sulfide matrix material, thereby improving the compatibility between the polyamide elastomer and the polyphenylene sulfide matrix material. Further, the polyetheramine soft segment structure in the polyamide elastomer provided in the present application endows the polyamide elastomer molecule with good flexibility, so that it has good toughening effect. Therefore, the polyphenylene sulfide composite provided in the present application has excellent mechanical properties, especially impact resistance.

[0077] In some embodiments, the fibrous filler can include:

[0078] 15-25 parts of glass fiber; and

[0079] 5-15 parts of carbon fiber.

[0080] The glass fiber can further reinforce the composite material, and the interface between the glass fiber and the polymer matrix can generate silver lines when the composite material is impacted, thereby absorbing the energy when the material is impacted. The carbon fiber can endow the composite material with conductivity due to its own conductivity.

[0081] In some embodiments, the glass fiber can be a glass fiber having urea groups on the surface. It can be understood that the urea end groups on the surface of the glass fiber can form strong hydrogen bonds with the polyamide elastomer, thereby enhancing the interface bonding between the glass fiber and the matrix resin, and improving the mechanical performance of the material.

[0082] In some embodiments, the carbon fiber can be a carbon fiber having carbon nanotubes on the surface. The carbon nanotubes on the surface of the carbon fiber can play a bridging role between the carbon fibers, thereby constructing a more efficient three-dimensional conductive network. Preferably, the carbon fiber can be a carbon fiber coated with multiple layers of multi-walled carbon nanotubes on the surface, so as to further realize the lightweight and high strength of the polyphenylene sulfide composite material.

[0083] Further, in order to obtain the glass fiber having urea groups on the surface and the carbon fiber having carbon nanotubes on the surface, the glass fiber and the carbon nanotubes can be surface treated, and the specific method is not limited herein.

[0084] In some embodiments, the above-mentioned composite material can further include:

[0085] 0.5-1.5 parts of primary antioxidant;

[0086] 0.5-0.8 parts of secondary antioxidant; and

[0087] Lubricant 1-2 parts.

[0088] Further, the primary antioxidant can be selected from one or more of antioxidant 1098, antioxidant 1010, antioxidant 1076, antioxidant 1024; preferably, the primary antioxidant can be antioxidant 1098. The secondary antioxidant can be selected from one or more of antioxidant Revonox 608, antioxidant 168, antioxidant 2013, antioxidant 626; preferably, the secondary antioxidant can be antioxidant Revonox 608. The lubricant can be pentaerythritol stearate (PETS). Further, other antioxidants and lubricants can be selected by those skilled in the art, which are not limited herein.

[0089] In a second aspect, the present application provides a method for preparing the composite material as described above, comprising the following steps:

[0090] S01: providing polyphenylene sulfide, polyamide elastomer, and fiber filler;

[0091] S02: mixing the polyphenylene sulfide, polyamide elastomer, and fiber filler under heating conditions to obtain a composite material;

[0092] The chemical structure of the polyamide elastomer is: ;

[0093] wherein m represents the polymerization degree of the polyetheramine structure, and is an integer from 20 to 50; n represents the polymerization degree of the polyamide elastomer, and is an integer from 100 to 200; x and y represent the molar content of the corresponding structural units in the elastomer molecular structure, x = 0.2-0.4, and y = 0.6-0.8.

[0094] In some embodiments, the heating conditions can be provided by a twin-screw extruder, an internal mixer, or the like, which are not limited herein. In order to mix the composite material and the components uniformly, the polymer components can be heated to a molten state, for example, in some embodiments of the present application, the aforementioned components can be mixed at a temperature of 270-300°C.

[0095] In some embodiments, the method for preparing the polyamide elastomer comprises:

[0096] S11: mixing nylon salt, adipic acid, polyetheramine, and water to obtain a first dispersion;

[0097] S12: containing the first dispersion in a reaction container, and reacting to obtain a polyamide elastomer;

[0098] wherein the chemical formula of the nylon salt is: .

[0099] In step S11:

[0100] In order to reduce the occurrence of side reactions and improve the reaction efficiency, the water can be selected from one or more of deionized water, distilled water, and reverse osmosis water.

[0101] In step S12:

[0102] In some embodiments, the reaction to obtain the polyamide elastomer can be carried out at a temperature of 180-300°C, for example, at 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, or a range between any two of the above values. When the reaction temperature is within the above range, the reaction can meet the requirements of chemical reaction kinetics and thermodynamics, thereby smoothly proceeding.

[0103] Further, the reaction to obtain the polyamide elastomer can be carried out by gradually increasing the reaction temperature.

[0104] In some embodiments, the reaction time to obtain the polyamide elastomer can be 4-8h, for example, 4h, 5h, 6h, 7h, 8h, or a range between any two of the above values. In this way, the reaction can be ensured to proceed sufficiently, thereby ensuring the reaction yield.

[0105] In some embodiments, the reaction to obtain the polyamide elastomer is carried out under the condition of a protective gas, for example, under the condition of nitrogen, helium, neon, or argon. In this way, the occurrence of side reactions can be reduced, and the reaction efficiency can be improved.

[0106] In some embodiments, the molar ratio of the nylon salt, adipic acid, and polyetheramine can be (1-2):(3-4):(3-4). When the molar ratio of the nylon salt, adipic acid, and polyetheramine is within the above range, the product with the target structure can be ensured to be obtained.

[0107] In some embodiments, the mass ratio of the nylon salt to water in the first dispersion liquid can be (1-2):10.

[0108] In some embodiments, the first dispersion liquid can further include an antioxidant, and the mass ratio of the antioxidant to the nylon salt is 1:(10-20). It can be understood that the antioxidant can further reduce or even prevent the side reactions between the reactants and oxygen, thereby improving the reaction quality and efficiency. Further, the antioxidant can be selected from one or more of the antioxidant Revonox 608 and the antioxidant 1098.

[0109] In some embodiments, the preparation method of the nylon salt includes:

[0110] S121: providing p-aminobenzoic acid, p-phenyldicarboxylic acid chloride, and a first solvent;

[0111] S122: mixing p-aminobenzoic acid, terephthaloyl chloride and the first solvent to obtain a nylon salt intermediate;

[0112] S123: mixing the nylon salt intermediate, hexanediamine and water to obtain a nylon salt.

[0113] In step S121:

[0114] The first solvent can be selected from one or more of N,N-dimethylacetamide, dioxane, tetrahydrofuran; preferably, the first solvent can be N,N-dimethylformamide. Further, in order to improve the quality of the reaction and reduce the occurrence of side reactions, the first solvent can be a solvent treated by water removal.

[0115] In step S122:

[0116] The amino group of the p-aminobenzoic acid can undergo a substitution reaction with the chlorine atom of the terephthaloyl chloride to obtain the nylon salt intermediate. Specifically, in some embodiments, the chemical reaction equation of the reaction of the p-aminobenzoic acid with the terephthaloyl chloride to obtain the nylon salt intermediate is as follows:

[0117]

[0118] In some embodiments, the reaction to obtain the nylon salt intermediate can be carried out at a temperature condition of -10-5°C, for example, can be carried out at -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 a range between any two of the above values. When the reaction temperature is within the above range, it can ensure that the reaction proceeds smoothly, the product is not decomposed and other side reactions do not occur.

[0119] Specifically, in some embodiments, the reaction to obtain the nylon salt intermediate can be carried out under ice bath conditions.

[0120] In some embodiments, the reaction time for the reaction to obtain the nylon salt intermediate is 1-3h, for example, can be 1h, 1.5h, 2h, 2.5h, 3h or a range between any two of the above values. When the reaction time is within the above range, it can ensure that the reaction proceeds sufficiently, thereby ensuring the yield of the reaction.

[0121] In some embodiments, the reaction to obtain the nylon salt intermediate is carried out under the condition of a protective gas. The type and role of the protective gas have been described above and will not be repeated here.

[0122] In some embodiments, the molar ratio of the p-aminobenzoic acid to the terephthaloyl chloride can be (4-6):1.

[0123] It should be noted that the reaction of obtaining the nylon salt intermediate only needs 2 times of p-aminobenzoic acid equivalent of terephthaloyl chloride, but since the substitution reaction of p-aminobenzoic acid and terephthaloyl chloride generates hydrochloric acid by-product, which affects the reaction, therefore, at least 2 times of p-aminobenzoic acid equivalent of terephthaloyl chloride needs to be added as an acid-binding agent to combine with the generated hydrochloric acid by-product to ensure the smooth progress of the reaction.

[0124] In some embodiments, the mass ratio of p-aminobenzoic acid to the first solvent can be 1: (4~6).

[0125] In step S123:

[0126] The carboxyl group of the nylon salt intermediate can react with the amino group of hexamethylenediamine to generate a nylon salt. In some embodiments, the chemical reaction equation of the reaction of the nylon salt intermediate and hexamethylenediamine to generate a nylon salt is as follows:

[0127]

[0128] Further, in order to reduce the occurrence of side reactions and improve the reaction efficiency, the water can be selected from one or more of deionized water, distilled water, and reverse osmosis water.

[0129] In some embodiments, the reaction of obtaining the nylon salt can be carried out at a temperature of 50~80℃, for example, at 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, or in a range between any two of the above values.

[0130] In some embodiments, the reaction time for obtaining the nylon salt is 0.5~3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, or in a range between any two of the above values.

[0131] In some embodiments, the final pH value of the nylon salt aqueous solution can be controlled in the range of 7.0~7.5, for example, the pH value can be controlled to be 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, or in a range between any two of the above values. Preferably, the final pH value of the nylon salt aqueous solution is controlled to be 7.2. Controlling the appropriate pH value range of the obtained nylon salt aqueous solution can ensure the smooth progress of the reaction.

[0132] In some embodiments, the molar ratio of hexamethylenediamine to the nylon salt intermediate can be 1: 0.98~1;

[0133] In some embodiments, the above preparation method further comprises:

[0134] Before obtaining the composite material, the polyphenylene sulfide, the polyamide elastomer, and the fiber filler are mixed with the primary antioxidant, the secondary antioxidant, and the lubricant.

[0135] The polyphenylene sulfide is 47.7-75 parts by mass, the polyamide elastomer is 3-8 parts, the fiber filler is 20-40 parts, the main antioxidant is 0.5-1.5 parts, the auxiliary antioxidant is 0.5-0.8 parts, and the lubricant is 1-2 parts.

[0136] The application will be specifically described below through specific examples. The following examples are only part of the application and are not a limitation of the application. Example 1

[0137] The embodiment provides a polyphenylene sulfide composite material and a preparation method thereof, and the preparation method comprises the following steps.

[0138] Step S1: 54.9g of p-aminobenzoic acid (0.4mol) and 200ml of anhydrous DMF are weighed and added to a 500ml three-necked flask, and stirring is performed at room temperature to make the p-aminobenzoic acid completely dissolved. The three-necked flask is transferred to an ice bath and is protected by flowing nitrogen. 20.3g of terephthaloyl chloride (0.1mol) is dissolved in 50ml of anhydrous DMF, and the terephthaloyl chloride solution is added dropwise into the three-necked flask through a constant-pressure funnel. Precipitation gradually occurs during the dropwise addition process. After the dropwise addition is completed, the reaction is continued for 2h under the ice bath. After the reaction is completed, filtration is performed, the precipitate is washed with deionized water and ethanol for 5 times, and drying is performed to obtain a white powder product, which is a p-aminobenzoic acid-terminated terephthaloyl chloride product (a nylon salt intermediate with a molecular weight of 404.3);

[0139] Step S2: 6g of hexanediamine (0.052mol) and 100g of deionized water are weighed and added to a 150ml three-necked flask, and stirring is started to make them uniformly mixed, and the temperature is increased to 60℃. About 21g of the nylon salt intermediate obtained in step S1 (0.052mol) is gradually added in batches to perform a salt formation reaction, and the reaction is monitored by a pH meter. A trace amount of reactant is added to control the pH value of the salt solution to be stable at 7.2. After the reaction is performed for 1h, concentration is performed by rotary evaporation, and the concentrated solution is precipitated in anhydrous ethanol to obtain a white powder product, which is a nylon salt (with a molecular weight of 520.5);

[0140] Step S3: Take 15.6 g of the nylon salt obtained in step S2 (0.03 mol), 10.2 g of adipic acid, 140 g of polyetheramine D2000, 200 g of deionized water, 0.5 g of antioxidant Revonox 608, and 0.5 g of antioxidant 1098 into a 500 ml high-pressure reactor, seal the high-pressure reactor, vacuumize, and circulate nitrogen for 5 times; start mechanical stirring at a speed of 30 Hz; heat to 200°C, and keep the temperature constant for 1.5 h after reaching the temperature; heat to 240°C, and keep the temperature constant for 1.5 h after reaching the temperature; slowly release the pressure in the reactor to 0.15 MPa through the exhaust condenser pipeline within 1 h; heat to 280°C, and keep the temperature constant for 1 h after reaching the temperature; reduce the pressure in the reactor to 0.01 MPa at 280°C by circulating the water pump, keep vacuum, and melt for 1.5 h; after the reaction is completed, open the discharge valve at the bottom of the reactor, put the material into the water tank for drawing and granulating, and obtain a translucent polyamide elastomer; repeat steps S1-S3 to obtain a sufficient amount of polyamide elastomer for subsequent experiments;

[0141] Step S4: Take 1.935 kg of polyphenylene sulfide (34100, purchased from Zhejiang Xinhewo Special Material Co., Ltd.), 0.09 kg of the polyamide elastomer obtained in step S3, 0.6 kg of glass fiber with urea end groups on the surface, 0.3 kg of carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30 g of primary antioxidant 1098, 15 g of auxiliary antioxidant Revonox 608, and 30 g of lubricant PETS (purchased from Dongguan Xingyuan Chemical Co., Ltd.) uniformly mixed by a medium-speed mixer, and then melt-extruded and granulated by a twin-screw extruder to obtain a polyphenylene sulfide composite material; the specific settings of each temperature zone of the extruder are as follows: zone 1: 280°C, zone 2: 280°C, zone 3: 285°C, zone 4: 285°C, zone 5: 290°C, zone 6: 295°C, zone 7: 290°C, zone 8: 285°C, zone 9: 280°C, and zone 10: 280°C; the screw rotation speed is 300 r / min, and the length-diameter ratio is 48:1. The extruded and granulated composite material is injection molded to obtain mechanical property test samples and electrically conductive property test samples for subsequent performance testing.

[0142] The preparation method of the glass fiber with urea end groups on the surface is as follows:

[0143] Take 100 g of chopped sand glass fiber (T443R, purchased from Taishan Glass Fiber Co., Ltd.) and 300 g of anhydrous tetrahydrofuran into a 1 L beaker; mechanically stir and ultrasonically disperse for 1 h at room temperature to obtain a uniform glass fiber dispersion liquid; then add 2 g of 3-ureidopropyl trimethoxysilane, and keep mechanical stirring for 1 h to fully react the hydroxyl groups on the surface of the glass fiber with the siloxyl groups; filter and dry to obtain chopped sand glass fiber with urea end groups on the surface.

[0144] A method for preparing carbon fibers with a multi-walled carbon nanotube (MWCNT) coating on the surface comprises the following steps:

[0145] Take 100 g of bundled chopped carbon fibers (W10N-06F, purchased from Jiangsu Zengtuo Composites Co., Ltd.), 0.5 g of liquid branched polyethyleneimine (PEI, surface treatment agent), and 500 ml of deionized water into a 1 L beaker, mechanically stir for 10 min at room temperature, and then filter to obtain carbon fibers with positive charges on the surface; prepare a uniform dispersion of poly sodium 4-styrene sulfonate (PSS) wrapped multi-walled carbon nanotubes (MWCNT), specifically: take 2 g of poly sodium 4-styrene sulfonate (PSS), 5 g of multi-walled carbon nanotubes (MWCNT, GC-23, purchased from Shanghai Dazhan Times Nanotechnology Co., Ltd.), and 500 g of deionized water into a 1 L beaker, and ultrasonically disperse for 2 h at room temperature to obtain a uniform dispersion; add the 100 g of carbon fibers with positive charges on the surface obtained above into the uniform dispersion of poly sodium 4-styrene sulfonate (PSS) wrapped multi-walled carbon nanotubes (MWCNT), and mechanically stir for 10 min at room temperature; the multi-walled carbon nanotubes (MWCNT) are coated on the surface of the carbon fibers by electrostatic adsorption; and then filter to obtain carbon fibers with a multi-walled carbon nanotube (MWCNT) coating on the surface. Example Two

[0146] This embodiment provides a kind of polyphenyl sulfide composite material and preparation method thereof, wherein, preparation method is basically identical with example 1, its difference is only in the different amount of each component in step S4, as follows:

[0147] 1.875 kg of polyphenyl sulfide (34100, purchased from Zhejiang Xinhengcheng Special Material Co., Ltd.), 0.15 kg of polyamide elastomer obtained in step S3, 0.6 kg of glass fiber with urea end group on the surface, 0.3 kg of carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30 g of primary antioxidant 1098, 15 g of auxiliary antioxidant Revonox 608, and 30 g of lubricant PETS. Example Three

[0148] This embodiment provides a kind of polyphenyl sulfide composite material and preparation method thereof, wherein, preparation method is basically identical with example 1, its difference is only in the different amount of each component in step S4, as follows:

[0149] 1.815 kg of polyphenyl sulfide (34100, purchased from Zhejiang Xinhengcheng Special Material Co., Ltd.), 0.21 kg of polyamide elastomer obtained in step S3, 0.6 kg of glass fiber with urea end group on the surface, 0.3 kg of carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30 g of primary antioxidant 1098, 15 g of auxiliary antioxidant Revonox 608, and 30 g of lubricant PETS. Example Four

[0150] This example provides a kind of polyphenylene sulfide composite material and its preparation method, wherein, preparation method is basically identical with example 1, its difference is only in the different amount of use of each component in step S4, as follows:

[0151] 2.025kg polyphenylene sulfide (34100, purchased from Zhejiang Xinhengcheng Special Material Co., Ltd.), 0.15kg polyamide elastomer obtained in step S3, 0.6kg glass fiber with urea end group on the surface, 0.15kg carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30g primary antioxidant 1098, 15g auxiliary antioxidant Revonox 608, 30g lubricant PETS. Example Five

[0152] This example provides a kind of polyphenylene sulfide composite material and its preparation method, wherein, preparation method is basically identical with example 1, its difference is only in the different amount of use of each component in step S4, as follows:

[0153] 1.725kg polyphenylene sulfide (34100, purchased from Zhejiang Xinhengcheng Special Material Co., Ltd.), 0.15kg polyamide elastomer obtained in step S3, 0.6kg glass fiber with urea end group on the surface, 0.45kg carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30g primary antioxidant 1098, 15g auxiliary antioxidant Revonox 608, 30g lubricant PETS. Example Six

[0154] This example provides a kind of polyphenylene sulfide composite material and its preparation method, wherein, preparation method is basically identical with example 1, its difference is only in the different amount of use of each component in step S4, as follows:

[0155] 1.725kg polyphenylene sulfide (34100, purchased from Zhejiang Xinhengcheng Special Material Co., Ltd.), 0.15kg polyamide elastomer obtained in step S3, 0.75kg glass fiber with urea end group on the surface, 0.3kg carbon fiber with multi-walled carbon nanotube (MWCNT) coating on the surface, 30g primary antioxidant 1098, 15g auxiliary antioxidant Revonox 608, 30g lubricant PETS. Comparative Example One

[0156] This example provides a kind of polyphenylene sulfide composite material and its preparation method, wherein, preparation method is as follows:

[0157] Take 1.875 kg PPS (34100, purchased from Zhejiang Xinhewang Special Material Co., Ltd.), 0.15 kg toughening agent (Elvaloy® PTW, purchased from Dow Chemical Company, USA), 0.6 kg glass fiber with surface coated with urea end group obtained in Example 1, 0.3 kg carbon fiber with surface coated with multi-walled carbon nanotube (MWCNT) obtained in Example 1, 30 g primary antioxidant 1098, 15 g secondary antioxidant Revonox 608, 30 g lubricant PETS (purchased from Dongguan Xingyuan Chemical Co., Ltd.), after being uniformly mixed by a medium-speed mixer, melt-extrusion granulation by a twin-screw extruder to obtain the PPS composite material; the specific temperature zones of the extruder are set as follows: 1 zone: 280℃, 2 zone: 280℃, 3 zone: 285℃, 4 zone: 285℃, 5 zone: 290℃, 6 zone: 295℃, 7 zone: 290℃, 8 zone: 285℃, 9 zone: 280℃, 10 zone: 280℃, the screw rotation speed is 300 r / min, and the length-diameter ratio is 48:1. The composite material after extrusion granulation is injection molded to prepare mechanical property test samples and electric conductivity test samples for subsequent performance tests. Comparative Example Two

[0158] The present embodiment provides a polyphenylene sulfide composite material and a preparation method thereof, wherein the preparation method is as follows:

[0159] Take 1.875 kg PPS (34100, purchased from Zhejiang Xinhewang Special Material Co., Ltd.), 0.15 kg toughening agent (Elvaloy® PTW, purchased from Dow Chemical Company, USA), 0.6 kg glass fiber with surface coated with urea end group obtained in Example 1, 0.3 kg carbon fiber with surface coated with multi-walled carbon nanotube (MWCNT) obtained in Example 1, 30 g primary antioxidant 1098, 15 g secondary antioxidant Revonox 608, 30 g lubricant PETS (purchased from Dongguan Xingyuan Chemical Co., Ltd.), after being uniformly mixed by a medium-speed mixer, melt-extrusion granulation by a twin-screw extruder to obtain the PPS composite material; the specific temperature zones of the extruder are set as follows: 1 zone: 280℃, 2 zone: 280℃, 3 zone: 285℃, 4 zone: 285℃, 5 zone: 290℃, 6 zone: 295℃, 7 zone: 290℃, 8 zone: 285℃, 9 zone: 280℃, 10 zone: 280℃, the screw rotation speed is 300 r / min, and the length-diameter ratio is 48:1. The composite material after extrusion granulation is injection molded to prepare mechanical property test samples and electric conductivity test samples for subsequent performance tests. Comparative Example Three

[0160] The present embodiment provides a polyphenylene sulfide composite material and a preparation method thereof, wherein the preparation method is as follows:

[0161] Take 1.875 kg PPS (34100, purchased from Zhejiang Xinhewang Special Material Co., Ltd.), 0.15 kg of the polyamide elastomer obtained in Example 1, 0.6 kg of glass fiber obtained in Example 1, 0.3 kg of bundled short carbon fiber (W10N-06F, purchased from Jiangsu Zengtuo Composite Material Co., Ltd.), 30 g of primary antioxidant 1098, 15 g of auxiliary antioxidant Revonox 608, 30 g of lubricant PETS (purchased from Dongguan Xingyuan Chemical Co., Ltd.), uniformly mixed by a medium-speed mixer, and then melt-extruded and pelletized by a twin-screw extruder to obtain the PPS composite material; the specific temperature zones of the extruder are set as follows: 1 zone: 280°C, 2 zone: 280°C, 3 zone: 285°C, 4 zone: 285°C, 5 zone: 290°C, 6 zone: 295°C, 7 zone: 290°C, 8 zone: 285°C, 9 zone: 280°C, 10 zone: 280°C, the screw rotation speed is 300 r / min, and the length-diameter ratio is 48:1. The composite material after extrusion and pelletization is injection molded to prepare mechanical property test samples and electric conductivity test samples for subsequent performance tests.

[0162] The nylon salt intermediate prepared in step S1, the nylon salt prepared in step S2, and the polyamide elastomer prepared in step 3 in Example 1 were subjected to infrared characterization of their chemical structures, and the characterization results are shown in Figure 1 , Figure 2 and Figure 3 , respectively.

[0163] Please refer to Figure 1 , the absorption peaks at 3432 cm -1 and 3337 cm -1 correspond to the stretching vibration peaks of O-H in the carboxylic acid group and N-H in the amide group, the absorption peaks at 1680 cm -1 and 1652 cm -1 correspond to the stretching vibration peaks of C=O in the carboxylic acid group and C=O in the amide group, the absorption peaks near 1600 cm -1 and 1500 cm -1 are the stretching vibration peaks of C=C in the benzene ring, and the characteristic peak at 1527 cm -1 corresponds to the bending vibration of N-H in the amide group. The infrared results show that the product obtained in step 1 is a capped product (nylon salt intermediate) with the target structure.

[0164] Please refer to Figure 2 , the characteristic absorption peak of N-H bond appears at 3311 cm -1 , the peaks at 2927 cm -1 and 2859 cm -1 come from the stretching vibration of methylene C-H in hexanediamine, and compared with Figure 1 , the absorption peaks at 1680 cm-1 carboxylic acid carbonyl peak disappeared, only the characteristic absorption peak of C=O bond at 1651 cm -1 -1 -1 -1 nearby were the stretching vibration peaks of C=C in benzene ring, the characteristic peaks of basic functional groups in nylon salt were all found in infrared spectrum, which proved the success of synthesis of nylon salt.

[0165] See Figure 3 , the stretching vibration peak of N-H bond appeared at 3321 cm -1 -1 -1 -1 -1 -1 -1 -1 the stretching vibration of C-O-C in polyether amine segment, the infrared results showed that the product obtained in step 3 was a polyamide elastomer with the target structure.

[0166] The basic physical properties, temperature resistance, mechanical properties and electrical conductivity of the polyphenylene sulfide composite materials provided in Examples 1-6 and Comparative Examples 1-3 were tested, and the test results are shown in Table 1. Among them, the density test was performed according to the standard ISO 1183; the heat distortion temperature 1.8 MPa was performed according to the standard ISO 75; the tensile strength test was performed according to the standard ISO 527; the bending modulus test was performed according to the standard ISO 178; the cantilever beam notched impact strength test was performed according to the standard GB / T 1843-2008; the volume resistivity and surface resistivity test was performed according to the standard IEC 60093.

[0167] Table 1

[0168] Performance name Density g / cm 3 ]] Heat deflection temperature °C Tensile strength MPa Flexural modulus GPa Notched Charpy Impact Strength KJ / m 2 ]] Volume resistivity kΩ*cm Surface resistivity kΩ Example 1 1.514 278 176 15.86 9.9 4.259 0.831 Example 2 1.501 271 173 14.52 14.4 3.748 0.625 Example 3 1.493 265 168 13.75 18.7 3.543 0.606 Example 4 1.557 262 158 12.29 16.5 8249 663 Example 5 1.439 280 191 15.88 11.8 0.735 0.024 Example 6 1.582 287 187 15.54 11.3 5.861 1.215 Comparative Example 1 1.498 267 141 14.11 7.4 3.975 0.737 Comparative Example 2 1.503 264 139 13.87 12.2 4.168 0.779 Comparative Example 3 1.507 270 160 14.26 13.7 18.262 4.378

[0169] ​​​​​​​​​​From the data in Table 1, it can be seen that the polyamide elastomer provided by the present application is used to toughen the polyphenylene sulfide composite material. Because the elastomer has excellent compatibility with PPS, and the glass fiber after surface treatment is used to reinforce the PPS composite material, the urea end group on the surface of the glass fiber can form strong hydrogen bonding with the polyamide elastomer. Therefore, the notched impact strength of Example 2 is increased by 94.6% compared with Comparative Example 1; the tensile strength of Example 2 is increased by 24.5% compared with Comparative Example 2; the heat distortion temperature and the flexural modulus of Example 2 are also slightly improved. In addition, the carbon fiber with a multi-walled carbon nanotube (MWCNT) coating on the surface can significantly improve the electrical conductivity of the composite material. The volume resistivity and surface resistivity of Example 2 are both decreased by an order of magnitude compared with Comparative Example 3.

[0170] In summary, the polyphenylene sulfide composite material provided by the present application has excellent mechanical strength, impact toughness and high electrical conductivity, and has broad application prospects in the field of electronic and electrical appliances (such as new energy automobile battery pack shell, electromagnetic shielding material, etc.).

[0171] The above describes the technical solutions provided by the embodiments of the present application in detail. The principles and implementation modes of the present application are described by applying specific examples. The above description of the 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, according to the idea of the present application, the specific implementation mode and application range will be changed, and the above description of the present application should not be understood as a limitation.

Claims

1. A polyphenylene sulfide composite material, characterized in that, The polyphenylene sulfide composite material comprises, by parts by weight: 47.7~75 parts of polyphenylene sulfide; 3-8 parts of polyamide elastomer; and 20-40 parts of fiber filler The chemical structure of the polyamide elastomer is as follows: ； Where m represents the degree of polymerization of the polyetheramine structure, which is an integer from 20 to 50; n represents the degree of polymerization of the polyamide elastomer, which is an integer from 100 to 200; x and y represent the molar content of the corresponding structural units in the molecular structure of the polyamide elastomer, where x = 0.2 to 0.4 and y = 0.6 to 0.

8. The fiber filler comprises: 15-25 parts glass fiber and 5-15 parts carbon fiber; The glass fiber is a glass fiber with urea groups on its surface, and the carbon fiber is a carbon fiber with carbon nanotubes on its surface.

2. The composite material according to claim 1, characterized in that, The composite material also includes: 0.5-1.5 parts of the main antioxidant; 0.5-0.8 parts of co-antioxidant; and 1-2 parts lubricant.

3. The method for preparing the composite material according to any one of claims 1 to 2, characterized in that, The preparation method includes the following steps: Provides polyphenylene sulfide, polyamide elastomers, and fiber fillers; and The polyphenylene sulfide, the polyamide elastomer, and the fiber filler are mixed under heating conditions to obtain the composite material. The chemical structure of the polyamide elastomer is as follows: ； Where m represents the degree of polymerization of the polyetheramine structure, which is an integer from 20 to 50; n represents the degree of polymerization of the polyamide elastomer, which is an integer from 100 to 200; x and y represent the molar content of the corresponding structural units in the elastomer molecule, where x = 0.2 to 0.4 and y = 0.6 to 0.

8.

4. The preparation method according to claim 3, characterized in that, The method for preparing the polyamide elastomer includes: Nylon salt, adipic acid, polyetheramine, and water were mixed to obtain a first dispersion; and The first dispersion is contained in a reaction vessel, and the reaction yields the polyamide elastomer; The chemical formula of the nylon salt is: .

5. The preparation method according to claim 4, characterized in that, The reaction to obtain the polyamide elastomer was carried out at a temperature of 180~300°C; and / or The reaction time for obtaining the polyamide elastomer is 4-8 hours; and / or The reaction to obtain the polyamide elastomer was carried out under protective gas conditions; and / or The molar ratio of the nylon salt, the adipic acid, and the polyetheramine is (1~2):(3~4):(3~4); and / or The mass ratio of the nylon salt to the water in the first dispersion is (1~2):10; and / or The first dispersion also includes an antioxidant, and the mass ratio of the antioxidant to the nylon salt is 1:(10~20).

6. The preparation method according to claim 4, characterized in that, The method for preparing the nylon salt includes: Provides p-aminobenzoic acid, terephthaloyl chloride, and a first solvent; The p-aminobenzoic acid, the terephthaloyl chloride, and the first solvent are mixed and reacted to obtain a nylon salt intermediate; and The nylon salt intermediate is mixed with hexamethylenediamine and water to react and obtain the nylon salt.

7. The preparation method according to claim 6, characterized in that, The reaction to obtain the nylon salt intermediate was carried out at a temperature of -10 to 5°C; and / or The reaction time to obtain the nylon salt intermediate is 1-3 h; and / or The reaction to obtain the nylon salt intermediate was carried out under protective gas conditions; and / or The molar ratio of the p-aminobenzoic acid to the terephthaloyl chloride is (4~6):1; and / or The mass ratio of p-aminobenzoic acid to the first solvent is 1:(4~6); and / or The reaction to obtain the nylon salt is carried out at a temperature of 50-80°C; and / or The reaction time to obtain the nylon salt is 0.5~3 h; and / or The reaction yields an aqueous solution of the nylon salt with a final pH of 7.0–7.5; and / or The molar ratio of the hexamethylenediamine to the nylon salt intermediate is 1:0.98~1; and / or The first solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, and tetrahydrofuran.

8. The preparation method according to claim 3, characterized in that, The preparation method further includes: Before obtaining the composite material, the polyphenylene sulfide, the polyamide elastomer, and the fiber filler are mixed with the primary antioxidant, the secondary antioxidant, and the lubricant. By weight, the polyphenylene sulfide is 47.7-75 parts, the polyamide elastomer is 3-8 parts, the fiber filler is 20-40 parts, the primary antioxidant is 0.5-1.5 parts, the secondary antioxidant is 0.5-0.8 parts, and the lubricant is 1-2 parts.

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