Reinforced high-temperature nylon composite material as well as preparation method and application thereof

Abstract

According to the reinforced high-temperature nylon composite material as well as the preparation method and the application thereof, the composite material adopts the reinforced fiber to reinforce the bio-based high-temperature polyamide resin, and meanwhile, the toughening resin and the impact modifier are added, so that the composite material has very good mechanical properties; the material can be applied to the fields of aerospace, military, automobile materials, sports equipment, building materials or electronic appliances and the like.

Description

Technical Field

[0001] The invention belongs to the field of high-temperature nylon, and in particular relates to a reinforced high-temperature nylon composite material and a preparation method and application thereof. Background Art

[0002] With the development of science and technology, the application of plastics to replace wood and metal is expanding. Among them, high temperature resistant plastic materials can withstand continuous high temperatures of 180°C and maintain good dimensional stability. High temperature resistant plastics can bring higher temperature resistance to certain parts, or simply replace metal raw materials to produce these parts, which will increase the demand for high temperature resistant plastic materials, thereby driving market demand. The automotive industry has higher and higher requirements for engine efficiency, automobile fuel consumption and exhaust emissions. At the same time, with the development of surface mounting technology in the electronics industry, the requirements for high temperature resistance of materials are getting higher and higher. In order to solve such problems, materials need to have properties such as lightness, temperature resistance, high strength and dimensional stability. High temperature resistant nylon has become one of the more ideal materials. The development of high temperature resistant nylon makes it possible to miniaturize, lighten and strengthen the power of products, or simply replace the metal materials used in components.

[0003] High temperature resistant nylon products are generally prepared by melt polycondensation of dicarboxylic acids with aromatic rings and aliphatic diamines, mainly including 5T, 6T, 9T, 10T, 12T, etc. in semi-aromatic polyamides. The aromatic ring is introduced into the main chain of the polyamide molecule, thereby improving the heat resistance and mechanical properties and reducing the water absorption rate. However, all types of high temperature resistant plastic materials in the market currently have a common disadvantage: low impact and obvious brittleness, especially in sub-zero low temperature environments, they are more brittle. The existing fillers used to reinforce high temperature resistant nylon are mainly alkali-free glass fibers, but due to some shortcomings in the structure and performance of the glass fibers themselves, such as poor compatibility with the high temperature resistant nylon resin matrix, uneven distribution in the resin matrix, and easy exposure of the fiber reinforcement, the product has poor dimensional stability and low impact strength. These shortcomings have greatly limited the application scope of high temperature plastics to replace metals and wood.

[0004] Generally, the problem of low toughness of high-temperature resistant nylon products is solved by adding toughening agents. Patent CN101701105A compounded semi-aromatic polyamide and PA66 in the formula, and added 1% to 30% of elastomer. The prepared material has high notched impact strength, but the matrix material with a high mass ratio is PA66, not high-temperature nylon, which leads to a significant decrease in the thermal deformation temperature of the material, limiting its application. Patent CN104231616A adds 5% to 30% ultrafine barium sulfate to the formula for toughening, but the toughening effect of inorganic toughening agents is usually not as good as that of organic toughening agents, and the toughening effect is poor, which cannot meet the situation of ultra-high toughness. If rubber and elastomers are used to toughen high-temperature nylon, since the processing temperature of high-temperature nylon is 300-320°C, rubber and elastomers are easy to decompose at this time, so the toughening effect cannot be achieved. Summary of the invention

[0005] In order to overcome the deficiencies in the above-mentioned prior art, the present invention provides a reinforced high-temperature nylon composite material, a preparation method and application thereof. The composite material adopts reinforcing fibers to reinforce a bio-based high-temperature polyamide resin, and at the same time adds a toughening resin and an impact modifier, so as to improve the toughness of the high-temperature nylon, thereby obtaining a reinforced high-temperature nylon composite material with excellent mechanical properties, high heat resistance, dimensional stability, reliable performance and practicality.

[0006] In the present invention, if there is no special explanation, the content percentages are all weight percentages.

[0007] The present invention solves the above technical problems through the following technical solutions:

[0008] In the first aspect of the present invention, the present invention provides a reinforced high temperature nylon composite material, which comprises: 20-75wt% bio-based high temperature polyamide resin, 5-30wt% toughening resin, 15-50wt% reinforcing fiber, 5-20wt% impact modifier and 0-15wt% additive.

[0009] In some specific embodiments, the bio-based high temperature polyamide resin is prepared using diamine monomer A1, aliphatic diacid monomer A2 and aromatic diacid monomer A3. Preferably, the bio-based high temperature polyamide resin contains repeating structural units from bio-based pentamethylenediamine, has the advantage of being renewable in source, and can be commercially available, provided by Cathay Biotech Inc. A series of materials, such as 6638, 6308, 6300, 6290, 6635, 6632, 6520, 2260, 2262, etc.

[0010] In some embodiments, the diamine monomer A1 includes at least one of butanediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecanediamine, dodecamethylenediamine, tridecanediamine, tetradecanediamine, pentamethylenediamine, and hexadecanediamine. Preferably, the diamine monomer A1 contains at least pentamethylenediamine.

[0011] In some embodiments, the pentamethylenediamine is derived from bio-based pentamethylenediamine, which refers to pentamethylenediamine synthesized from biomass-derived compounds such as glucose and lysine by enzyme reaction, yeast reaction or fermentation reaction in a monomer synthesis process. The biobased content of bio-based pentamethylenediamine can be determined by a method for measuring the radioactive C14 content, such as the American Society for Testing and Materials standard ASTM-D6866 method.

[0012] In some embodiments, the molar percentage of pentamethylenediamine in all diamine units A1 is 20-70%.

[0013] In some embodiments, the aliphatic diacid monomer A2 is derived from an aliphatic short-chain diacid, an aliphatic long-chain diacid or a combination thereof. The aliphatic short-chain diacid can be, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or a combination thereof; the aliphatic long-chain diacid can be, for example, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecane dibasic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane dibasic acid or a combination thereof.

[0014] In some embodiments, the aliphatic diacid unit is derived from a combination of an aliphatic short-chain diacid and an aliphatic long-chain diacid, wherein the aliphatic short-chain diacid is, for example, adipic acid, and the aliphatic long-chain diacid is, for example, selected from sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecane dicarboxylic acid, hexadecanedioic acid, or a combination thereof.

[0015] In some embodiments, the aromatic diacid unit A3 is derived from an aromatic diacid or a derivative thereof, such as terephthalic acid, isophthalic acid, phthalic acid or a combination of esters thereof. For example, terephthalic acid esters include dimethyl terephthalate and diethyl terephthalate.

[0016] In some embodiments, at least one of the diamine monomer A1, the aliphatic diacid monomer A2, and the aromatic diacid monomer A3 is prepared by a biological method.

[0017] In some embodiments, the molar ratio of the diamine monomer A1 to the sum of the aliphatic diacid monomer A2 and the aromatic diacid monomer A3 is (0.9-1.2):1, or further is (0.95-1.1):1.

[0018] In some embodiments, the molar ratio of the aliphatic diacid monomer A2 to the aromatic diacid monomer A3 is (10-50):(50-90), or further is (20-50):(50-75).

[0019] In some specific embodiments, the relative viscosity of the bio-based high temperature polyamide resin is 2.0 to 3.2. The relative viscosity is measured by an Ubbelohde viscometer using concentrated sulfuric acid (96%) method.

[0020] In some specific embodiments, the number average molecular weight of the bio-based high temperature polyamide resin is 20,000 to 70,000, preferably 20,000 to 50,000, for example, 30,000, 40,000, 60,000, etc.

[0021] In some specific embodiments, the water content of the bio-based high temperature polyamide resin is 300-1000 ppm, for example, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, etc.

[0022] In some specific embodiments, the melting point of the bio-based high temperature polyamide resin is 250-330°C, preferably 280-320°C, such as 260°C, 270°C, 290°C, 300°C, 310°C, etc.

[0023] In some specific embodiments, in the reinforced high-temperature nylon composite material, the content of bio-based high-temperature polyamide resin is 20-70wt%, for example, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, etc.

[0024] In some specific embodiments, the toughening resin comprises aliphatic nylon.

[0025] In some specific embodiments, the aliphatic nylon includes at least one of PA6, PA66 and PA56.

[0026] In some specific embodiments, the relative viscosity of the aliphatic nylon is 2.0-3.4, preferably 2.4-3.0, such as 2.2, 2.6, 2.8, 3.2, etc.

[0027] In some specific embodiments, the terminal amino group content of the aliphatic nylon is 30 to 200 mmol / kg, preferably 50 to 100 mmol / kg, such as 80 mmol / kg, 150 mmol / kg, etc.

[0028] In some specific embodiments, the melting point of the aliphatic nylon is 220-270°C, preferably 250-260°C, such as 254°C.

[0029] In some specific embodiments, the reinforcing fiber includes at least one of glass fiber, carbon fiber, aramid fiber, metal fiber, boron fiber, and basalt fiber.

[0030] In some specific embodiments, the reinforcing fiber is glass fiber, the monofilament diameter is 5-20 μm, and the linear density is 1000-3600 Tex.

[0031] In some specific embodiments, the reinforcing fiber is surface-grafted and modified with a silane coupling agent, wherein the silane coupling agent includes but is not limited to 3-[3-carboxyallylamide]propyltriethoxysilane.

[0032] In some specific embodiments, the impact modifier is a polar monomer graft polymer.

[0033] In some specific embodiments, the polymer includes at least one of polyethylene, polypropylene, ethylene-a-ethylene-octene copolymer, copolymer of styrene and butadiene, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer.

[0034] In some specific embodiments, the polar monomer includes at least one of maleic anhydride, fumaric acid, itaconic acid, citraconic acid, citraconic anhydride and vinyl succinic anhydride.

[0035] In some specific embodiments, the impact modifier is maleic anhydride grafted ethylene-propylene-butadiene terpolymer (EPDM-g-MAH).

[0036] In some specific embodiments, the additive includes at least one of a flow modifier, a lubricant, an antioxidant, a coupling agent, an antistatic agent, an anti-ultraviolet agent, a thermal stabilizer and a nucleating agent. Preferably, the additive includes a first additive and a second additive, which are added step by step during the preparation of the reinforced high temperature nylon composite material.

[0037] In some specific embodiments, the flow modifier includes a polyamide-specific flow modifier such as an organosilicon polymer, an ester resin, a long-chain dibasic acid, etc., such as a hyperbranched polyester or a long carbon chain dibasic acid.

[0038] In some specific embodiments, the long carbon chain dibasic acid includes undecanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid, and more preferably dodecanedioic acid and tridecanedioic acid.

[0039] In some specific embodiments, the lubricant includes at least one of stearate lubricants, fatty amide lubricants, silicone powder or silicone masterbatch, PE wax, and ethylene-acrylic acid copolymer, preferably silicone powder or silicone masterbatch, such as silicone powder.

[0040] In some specific embodiments, the antioxidant includes at least one of a hindered phenol antioxidant, a phosphite antioxidant, an amine antioxidant, and a thioester antioxidant, preferably a combination of a hindered amine antioxidant and a phosphite antioxidant. The hindered phenol antioxidant may be conventional in the art, such as antioxidant 1010 and antioxidant 1098. The phosphite antioxidant may be conventional in the art, such as antioxidant 168 and antioxidant 608.

[0041] In some specific embodiments, the antioxidant is a composition of antioxidant 1098 and antioxidant 608 in a mass ratio of 1:1.

[0042] In some specific embodiments, in the reinforced high temperature nylon composite material, the additives include 0-5% flow improver, 0-3% lubricant and 0-2% antioxidant.

[0043] In some specific embodiments, in the reinforced high temperature nylon composite material, the additives include 0.3-2.5% flow modifier, 0.4-2.5% lubricant, and 0.4-1% antioxidant.

[0044] In some specific embodiments, in the reinforced high temperature nylon composite material, the additives include 1.5% flow modifier, 1.0% lubricant, and 0.5% antioxidant.

[0045] In some specific embodiments, the tensile strength of the reinforced high temperature nylon composite material is 230 to 320 MPa, preferably 270 to 320 MPa.

[0046] In some specific embodiments, the flexural strength of the reinforced high temperature nylon composite material is 180 to 260 MPa, preferably 190 to 260 MPa.

[0047] In some specific embodiments, the flexural modulus of the reinforced high temperature nylon composite material is 8840 to 13500 MPa, preferably 9930 to 13500 MPa.

[0048] In some specific embodiments, the notched impact strength of the reinforced high temperature nylon composite material is 33 to 53 kJ / m 2 , preferably 39 to 53 kJ / m 2 .

[0049] In some specific embodiments, the reinforced high temperature nylon composite material has an unnotched impact strength of NB.

[0050] In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned reinforced high-temperature nylon composite material. According to a specific embodiment of the present invention, the method comprises:

[0051] S1. Extrude the toughening resin and impact modifier, cool, cut into pellets and dry to obtain toughening masterbatch

[0052] In this step, the toughening resin and the impact modifier are extruded, cooled, pelletized and dried to obtain the toughening masterbatch.

[0053] In some specific embodiments, based on the total weight of the reinforced high temperature nylon composite material, the toughening resin is added in an amount of 5-30wt%, and the impact modifier is added in an amount of 5-20wt%. Preferably, a first additive is also added in this step, and the first additive is added in an amount of 0-5wt%.

[0054] In some specific embodiments, based on the total mass of the reinforced high temperature nylon composite material, the first additive includes 0-1wt% antioxidant and 0-1.5wt% lubricant. Preferably, the first additive includes 0.1-0.4wt% antioxidant and 0-1wt% lubricant.

[0055] In some specific embodiments, the extrusion is carried out in a single-screw extruder or a twin-screw extruder, preferably a twin-screw extruder.

[0056] In some specific embodiments, the aspect ratio of the twin-screw extruder is (20-50):1, further (20-40):1, and preferably 36:1.

[0057] In some specific embodiments, the twin-screw extruder adopts a six-zone heating mode. Preferably, the temperature of zone one is 180-240°C, the temperature of zone two is 200-260°C, the temperature of zone three is 240-270°C, the temperature of zone four is 250-280°C, the temperature of zone five is 250-280°C, the temperature of zone six is ​​260-290°C, and the head temperature is 260-290°C.

[0058] In some specific embodiments, the main screw speed of the twin-screw extruder is 300-500 r / min, for example, 300 r / min.

[0059] S2, extruding the bio-based high temperature polyamide resin, the toughening masterbatch, and the reinforcing fiber, cooling, pelletizing, and drying to obtain a reinforced high temperature nylon composite material

[0060] In this step, the bio-based high temperature polyamide resin, the toughening masterbatch, and the reinforcing fiber are extruded, cooled, pelletized, and dried to obtain a reinforced high temperature nylon composite material. Preferably, a second additive is also added in this step. By adopting the masterbatch method, the problem of toughening agent decomposition can be solved, and the toughness of high temperature nylon can be further improved.

[0061] In some specific embodiments, based on the total mass of the reinforced high-temperature nylon composite material, the bio-based high-temperature polyamide resin is added in an amount of 20-75wt%, the toughening masterbatch is added in an amount of 10-55wt%, the reinforcing fiber is added in an amount of 15-50wt% and the second additive is added in an amount of 0-10wt%.

[0062] In some specific embodiments, the second additive includes 0-5 wt % of a flow improver, 0-1.5 wt % of a lubricant, and 0-1 wt % of an antioxidant.

[0063] In some specific embodiments, the second additive includes 0.6-5 wt % of a flow improver, 0-1.5 wt % of a lubricant, and 0.4-1 wt % of an antioxidant.

[0064] In some specific embodiments, the extrusion is carried out in a twin-screw extruder, which includes a first feeding port and a second feeding port, the bio-based high temperature polyamide resin and the masterbatch are added from the first feeding port, and the reinforcing fiber is added from the second feeding port.

[0065] In some specific embodiments, the aspect ratio of the twin-screw extruder is (20-50):1, further (20-44):1, and preferably 40:1.

[0066] In some specific embodiments, the twin-screw extruder adopts a six-zone heating mode. Preferably, the temperature of zone one is 220-270°C, the temperature of zone two is 240-280°C, the temperature of zone three is 260-300°C, the temperature of zone four is 260-310°C, the temperature of zone five is 270-310°C, the temperature of zone six is ​​270-320°C, and the temperature of the die head is 270-320°C.

[0067] In some specific embodiments, the main screw speed of the twin-screw extruder is 300-500 r / min, for example, 300 r / min.

[0068] In the third aspect of the present invention, the present invention proposes an application of the above-mentioned reinforced high-temperature nylon composite material in plastic products, including aerospace fields, military fields, automotive materials, sports equipment, building materials or electronic appliances. For example, the application of plastic products in spare parts of automotive materials.

[0069] The positive progressive effect of the present invention is that the present invention strengthens the high-temperature nylon composite material, uses reinforcing fiber to reinforce the bio-based high-temperature polyamide resin, and adds toughening resin and impact modifier at the same time, which can improve the toughness of the high-temperature nylon. Furthermore, in the preparation process, the masterbatch method is used to solve the problem that the toughening agent decomposes and the toughness of the high-temperature nylon cannot be improved, thereby preparing a reinforced and toughened high-temperature nylon composite material with excellent mechanical properties, high heat resistance, dimensional stability, reliable performance and practicality. DETAILED DESCRIPTION

[0070] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0071] Unless otherwise specified, the raw materials in the following examples and comparative examples are commercially available:

[0072] PA66, PA56, and PA6 were purchased from Cathay (Jinxiang) Biomaterials Co., Ltd., and the impact modifier was purchased from DuPont Chemical Co., Ltd. of the United States; the glass fiber was purchased from Taishan Glass Fiber Co., Ltd., the flow modifier was purchased from Cathay (Jinxiang) Biomaterials Co., Ltd., the lubricant was purchased from Chengdu Silike Technology Co., Ltd., and the antioxidant was purchased from BASF Group of Germany.

[0073] Bio-based high temperature polyamide resin A: For raw materials and preparation methods, refer to comparative example 4 of the patent publication CN 112029090A, and obtain bio-based high temperature polyamide resin A (number average molecular weight of 30,000, relative viscosity of 2.7, water content of 850 ppm after drying, melting point of 282°C).

[0074] Bio-based high temperature polyamide resin B: 10.2 mol of bio-based pentamethylenediamine, 2.9 mol of dodecanedioic acid and 6.9 mol of terephthalic acid are used as raw materials. The preparation method is as shown in Example 7 of the patent publication CN 112029090A to obtain bio-based high temperature polyamide resin B (number average molecular weight of 25,800, relative viscosity of 2.43, water content of 690 ppm after drying, melting point of 302°C);

[0075] Bio-based high temperature polyamide resin C: 7.05 mol bio-based pentamethylenediamine, 7 mol terephthalic acid, 3 mol 1,6-hexanodioic acid, 3 mol 1,6-hexanediamine, 0.03% sodium hypophosphite and water were mixed evenly, the stirring speed was set to 80 rpm, the temperature was raised to 80°C in a nitrogen atmosphere and maintained at this temperature for 1 hour to obtain a 50wt% polyamide salt solution, the temperature was raised to 130°C, the water was drained and concentrated to a concentration of 65wt%; the temperature was raised to 240°C again, and the pressure was maintained at 2.5MPa for reaction for 1 hour; the pressure in the reaction system was reduced to 0MPa by draining water, and the temperature of the reaction system was 340°C after the pressure reduction was completed; the vacuum was evacuated to -0.08MPa and maintained for 40s to obtain a polyamide melt; the polyamide melt was water-cooled and pelletized to obtain a bio-based high-temperature polyamide resin C (number average molecular weight of 21,000, relative viscosity of 2.23, water content of 1045ppm after drying, melting point of 308°C).

[0076] Example 1

[0077] 1. The raw materials of each component of the reinforced high-temperature nylon composite material include: 27wt% bio-based high-temperature polyamide resin A (number average molecular weight of 30,000, relative viscosity of 2.7, water content of 850ppm after drying, melting point of 299°C), 20wt% toughening resin PA56 (relative viscosity of 2.75, terminal amino content of 50mmol / kg, melting point of 253°C), 40wt% glass fiber (diameter of 13μm, linear density of 2000Tex), 10wt% impact modifier maleic anhydride grafted ethylene propylene rubber (EPDM-g-MAH), 1.5wt% flow modifier dodecanedioic acid, 1wt% lubricant silicone powder, 0.5wt% antioxidant (compounded by antioxidant 1098 and antioxidant 608 in a mass ratio of 1:1).

[0078] 2. Preparation method of reinforced high temperature nylon composite material:

[0079] (1) 20 wt% of toughening resin PA56, 10 wt% of impact modifier maleic anhydride grafted EPDM rubber, 0.5 wt% of lubricant silicone powder and 0.2 wt% of antioxidant (compounded by antioxidant 1098 and antioxidant 608 in a mass ratio of 1:1) are stirred and mixed, and then heated, melted and plasticized by a twin-screw extruder and extruded, and then cooled, pelletized and dried to obtain a toughening masterbatch;

[0080] Among them, the length-to-diameter ratio of the twin-screw extruder is 36:1. The twin-screw extruder adopts a six-zone heating mode. The processing temperatures from zone 1 to zone 6 to the die head are 200°C, 230°C, 250°C, 270°C, 280°C, 290°C, and 290°C respectively, and the main screw speed is 400r / min.

[0081] (2) 27 wt% of bio-based high temperature polyamide resin A, toughening masterbatch, 40 wt% of glass fiber, 1.5 wt% of flow modifier dodecane dicarboxylic acid, 0.5% of lubricant silicone powder, and 0.3 wt% of antioxidant (compounded by antioxidant 1098 and antioxidant 608 in a mass ratio of 1:1) were stirred and mixed, extruded, and then cooled, pelletized, and dried to obtain a reinforced high temperature nylon composite material;

[0082] Among them, the length-to-diameter ratio of the twin-screw extruder is 40:1. The twin-screw extruder adopts a six-zone heating mode. The processing temperatures from zone 1 to zone 6 to the die head are 250°C, 270°C, 290°C, 300°C, 310°C, 320°C, and 320°C respectively, and the main screw speed is 300r / min.

[0083] Example 2

[0084] The contents of the bio-based high-temperature polyamide resin A and the toughening resin PA56 in the raw materials of each component of the reinforced high-temperature nylon composite material are 37wt% and 10wt% respectively, and the rest are the same as in Example 1.

[0085] Example 3

[0086] The contents of the bio-based high-temperature polyamide resin A and the toughening resin PA56 in the raw materials of each component of the reinforced high-temperature nylon composite material are 17wt% and 30wt% respectively, and the rest are the same as in Example 1.

[0087] Example 4

[0088] The contents of bio-based high-temperature polyamide resin A, toughening resin PA56 and glass fiber in the raw materials of each component of the reinforced high-temperature nylon composite material are 21.3wt%, 15.7wt% and 50wt% respectively, and the rest are the same as in Example 1.

[0089] Example 5

[0090] The contents of bio-based high-temperature polyamide resin A, toughening resin PA56 and impact modifier maleic anhydride grafted EPDM rubber in the raw materials of each component of the reinforced high-temperature nylon composite material are 30wt%, 22wt% and 5wt% respectively, and the rest are the same as in Example 1.

[0091] Example 6

[0092] The contents of bio-based high-temperature polyamide resin A, toughening resin PA56 and impact modifier maleic anhydride grafted ethylene-propylene-butadiene terpolymer in the raw materials of each component of the reinforced high-temperature nylon composite material are 24.2wt%, 17.8wt% and 15wt% respectively, and the rest are the same as in Example 1.

[0093] Example 7

[0094] The impact modifier is POE-g-MAH, and the content is 10 wt %. Others are the same as in Example 1.

[0095] Example 8

[0096] The impact modifier is ethylene-methyl acrylate copolymer (EMA), and the content is 10 wt %. Others are the same as in Example 1.

[0097] Example 9

[0098] The toughening resin is PA66 (relative viscosity of 2.70, terminal amino content of 52 mmol / kg, melting point of 222° C.), and the rest is the same as in Example 1.

[0099] Example 10

[0100] The toughening resin is PA6 (relative viscosity of 2.80, terminal amino content of 54 mmol / kg, melting point of 223° C.), and the rest is the same as in Example 1.

[0101] Embodiment 11

[0102] The bio-based high temperature polyamide resin A is replaced by the bio-based high temperature polyamide resin B, and the rest is the same as in Example 1.

[0103] Example 12

[0104] The bio-based high temperature polyamide resin A is replaced by the bio-based high temperature polyamide resin C, and the rest is the same as in Example 1.

[0105] Comparative Example 1

[0106] The raw materials of each component of the reinforced high-temperature nylon composite material: the bio-based high-temperature polyamide resin A is 47wt%, and no toughening resin is added, and the rest is the same as in Example 1.

[0107] All materials are weighed in proportion and then stirred and mixed, extruded through a twin-screw extruder, and then cooled, pelletized, and dried to obtain a reinforced high-temperature nylon composite material;

[0108] Among them, the length-to-diameter ratio of the twin-screw extruder is 40:1. The twin-screw extruder adopts a six-zone heating mode. The processing temperatures from zone 1 to zone 6 to the die head are 250°C, 270°C, 290°C, 300°C, 310°C, 320°C, and 320°C respectively, and the main screw speed is 300r / min.

[0109] Comparative Example 2

[0110] All materials in Example 1 were weighed in proportion and stirred and mixed, extruded through a twin-screw extruder, and then cooled, pelletized, and dried to obtain a reinforced high-temperature nylon composite material;

[0111] Among them, the length-to-diameter ratio of the twin-screw extruder is 40:1. The twin-screw extruder adopts a six-zone heating mode. The processing temperatures from zone 1 to zone 6 to the die head are 250°C, 270°C, 290°C, 300°C, 310°C, 320°C, and 320°C respectively, and the main screw speed is 300r / min.

[0112] Comparative Example 3

[0113] The raw materials of each component of the reinforced high-temperature nylon composite material: the bio-based high-temperature polyamide resin A is 57wt%, and no impact modifier and toughening resin are added, and the rest is the same as Example 1.

[0114] All materials are weighed in proportion, stirred and mixed, extruded, cooled, pelletized and dried to obtain a reinforced high-temperature nylon composite material;

[0115] Among them, the length-to-diameter ratio of the twin-screw extruder is 40:1. The twin-screw extruder adopts a six-zone heating mode. The processing temperatures from zone 1 to zone 6 to the die head are 250°C, 270°C, 290°C, 300°C, 310°C, 320°C, and 320°C respectively, and the main screw speed is 300r / min.

[0116] Comparative Example 4

[0117] The raw materials of each component of the reinforced high-temperature nylon composite material are: 7wt% of bio-based high-temperature polyamide resin A, 40wt% of toughening resin PA56, and the rest are the same as in Example 1.

[0118] Comparative Example 5

[0119] The raw materials of the components of the reinforced high-temperature nylon composite material are: 15.5wt% of bio-based high-temperature polyamide resin A, 11.5wt% of toughening resin PA56, 30wt% of impact modifier maleic anhydride grafted ethylene propylene diene rubber, and the rest are the same as in Example 1.

[0120] The samples prepared in the above Examples 1-12 and Comparative Examples 1-5 were tested for mechanical properties respectively. The test methods are as follows, and the test results are shown in Table 1 below.

[0121] (1) Tensile strength: tested according to ISO527-1-2012 standard;

[0122] (2) Flexural strength and modulus: tested according to ISO178-2010 standard;

[0123] (3) Notched impact strength: tested according to ISO179-1-2008 standard.

[0124] (4) Unnotched impact strength: tested according to ISO179-1-2008 standard.

[0125] Table 1 Performance test results of composite boards prepared in Examples 1-12 and Comparative Examples 1-5

[0126]

[0127]

[0128] Note: "NB" in Table 1 means beyond the measurement range, that is, the composite sheet is continuous within the measurement range and can be considered to have high impact resistance.

[0129] As shown in Table 1, by comparing Examples 1-12 with Comparative Examples 1-5, it can be found that the mechanical properties of the Examples are better than those of the Comparative Examples, especially the simply supported beam notched impact strength and the simply supported beam unnotched impact strength are much higher than those of the Comparative Examples. The inventors found that since the impact modifier will degrade at a higher temperature, thus affecting the toughening effect, when the masterbatch method is adopted, the impact modifier is grafted onto the toughening resin at a lower temperature to form a masterbatch, which improves the thermal stability, thereby being able to withstand higher temperatures, and the toughness of the matrix is ​​improved after the toughening resin is added, which is more conducive to toughening.

[0130] Although the specific embodiments of the present invention are described above, it should be understood by those skilled in the art that this is only for illustration and the protection scope of the present invention is defined by the appended claims. Those skilled in the art may make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but these changes and modifications all fall within the protection scope of the present invention.

Claims

1. A reinforced high temperature nylon composite material, characterized in that: The reinforced high-temperature nylon composite material comprises: 20-75wt% of bio-based high-temperature polyamide resin, 5-30wt% of toughening resin, 15-50wt% of reinforcing fiber, 5-20wt% of impact modifier and 0-15wt% of additives.

2. The reinforced high temperature nylon composite material according to claim 1, characterized in that: The bio-based high temperature polyamide resin is prepared by using a diamine monomer A1, an aliphatic diacid monomer A2 and an aromatic diacid monomer A3; and / or, The diamine monomer A1 includes at least one of butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine and hexadecanediamine; and / or, the aliphatic diacid monomer A2 includes at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid and octadecanedicarboxylic acid; and / or, The aromatic diacid monomer A3 includes at least one of terephthalic acid, isophthalic acid and phthalic acid; and / or, At least one of the diamine monomer A1, the aliphatic diacid monomer A2 and the aromatic diacid monomer A3 is prepared by a biological method; and / or, The molar ratio of the diamine monomer A1 to the sum of the aliphatic diacid monomer A2 and the aromatic diacid monomer A3 is (0.9-1.2):1, and further (0.95-1.1):1; and / or, the molar ratio of the aliphatic diacid monomer A2 to the aromatic diacid monomer A3 is (10-50):(50-90), and preferably (20-50):(50-75).

3. The reinforced high temperature nylon composite material according to claim 1 or 2, characterized in that: The relative viscosity of the bio-based high temperature polyamide resin is 2.0 to 3.2; and / or, the number average molecular weight of the bio-based high temperature polyamide resin is 20,000 to 70,000, preferably 20,000 to 50,000; and / or, The water content of the bio-based high temperature polyamide resin is 300-1000 ppm; and / or the melting point of the bio-based high temperature polyamide resin is 250-330°C, preferably 280-320°C.

4. The reinforced high temperature nylon composite material according to claim 1, characterized in that: The toughening resin comprises aliphatic nylon; preferably, The aliphatic nylon includes at least one of PA6, PA66 and PA56; and / or, the terminal amino content of the aliphatic nylon is 30 to 200 mmol / kg, preferably 50 to 100 mmol / kg; and / or, The relative viscosity of the aliphatic nylon is 2.0-3.4, preferably 2.4-3.0; and / or the melting point of the aliphatic nylon is 220-270°C, preferably 250-260°C.

5. The reinforced high temperature nylon composite material according to claim 1, characterized in that: The reinforcing fiber includes at least one of glass fiber, carbon fiber, aramid fiber, metal fiber, boron fiber, and basalt fiber; preferably, The reinforcing fiber is glass fiber, the monofilament diameter is 5-20 μm, and the linear density is 1000-3600 Tex; and / or, The reinforcing fiber is a reinforcing fiber whose surface is grafted and modified by a silane coupling agent, and the silane coupling agent includes 3-[3-carboxyallylamide]propyltriethoxysilane.

6. The reinforced high temperature nylon composite material according to claim 1, characterized in that: The impact modifier is a polar monomer grafted polymer, preferably, the polymer includes at least one of polyethylene, polypropylene, ethylene-a-ethylene-octene copolymer, copolymer of styrene and butadiene, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer, and / or, the polar monomer includes at least one of maleic anhydride, fumaric acid, itaconic acid, citraconic acid, citraconic anhydride and vinyl succinic anhydride, and the impact modifier is preferably maleic anhydride grafted ethylene-propylene-butadiene terpolymer; and / or, The additive comprises at least one of a flow modifier, a lubricant, an antioxidant, a coupling agent, an antistatic agent, an anti-ultraviolet agent, a heat stabilizer and a nucleating agent.

7. The reinforced high temperature nylon composite material according to claim 1, characterized in that: The tensile strength of the reinforced high temperature nylon composite material is 230 to 320 MPa, preferably 270 to 320 MPa; and / or, The flexural strength of the reinforced high temperature nylon composite material is 180 to 260 MPa, preferably 190 to 260 MPa; and / or, The flexural modulus of the reinforced high temperature nylon composite material is 8840 to 13500 MPa, preferably 9930 to 13500 MPa; and / or, The notched impact strength of the reinforced high-temperature nylon composite material is 33 to 53 kJ / m 2 , preferably 39 to 53 kJ / m 2 and / or, The unnotched impact strength of the reinforced high temperature nylon composite material is NB.

8. A method for preparing the reinforced high temperature nylon composite material according to any one of claims 1 to 7, characterized in that: The method comprises: (1) Extruding a toughening resin and an impact modifier, cooling, pelletizing, and drying to obtain a toughening masterbatch; (2) The bio-based high temperature polyamide resin, the toughening masterbatch and the reinforcing fiber are extruded, and the reinforced high temperature nylon composite material is obtained after cooling, pelletizing and drying.

9. The method according to claim 8, characterized in that In step (1), based on the total mass of the reinforced high-temperature nylon composite material, the toughening resin is added in an amount of 5 to 30 wt%, and the impact modifier is added in an amount of 5 to 20 wt%; Optionally, in step (1), the extrusion is carried out in a single-screw extruder or a twin-screw extruder, preferably a twin-screw extruder; Optionally, in step (1), the aspect ratio of the twin-screw extruder is (20-50):1, further (20-40):1, preferably 36:1; Optionally, in step (1), the twin-screw extruder adopts a six-zone heating mode, preferably, the temperature of zone 1 is 180-240°C, the temperature of zone 2 is 200-260°C, the temperature of zone 3 is 240-270°C, the temperature of zone 4 is 250-280°C, the temperature of zone 5 is 250-280°C, the temperature of zone 6 is 260-290°C, and the temperature of the die head is 260-290°C; Optionally, in step (1), the main screw speed of the twin-screw extruder is 300 to 500 r / min, for example, 300 r / min; Optionally, in step (2), based on the total mass of the reinforced high-temperature nylon composite material, the bio-based high-temperature polyamide resin is added in an amount of 20-75wt%, the toughening masterbatch is added in an amount of 10-55wt%, and the reinforcing fiber is added in an amount of 15-50wt%; Optionally, in step (2), the extrusion is performed in a twin-screw extruder, the twin-screw extruder comprises a first feeding port and a second feeding port, the bio-based high temperature polyamide resin and the masterbatch are added from the first feeding port, and the reinforcing fiber is added from the second feeding port; Optionally, in step (2), the aspect ratio of the twin-screw extruder is (20-50):1, further (20-44):1, preferably 40:1; Optionally, in step (2), the twin-screw extruder adopts a six-zone heating mode, preferably, the temperature of zone 1 is 220-270°C, the temperature of zone 2 is 240-280°C, the temperature of zone 3 is 260-300°C, the temperature of zone 4 is 260-310°C, the temperature of zone 5 is 270-310°C, the temperature of zone 6 is 270-320°C, and the temperature of the die head is 270-320°C; Optionally, in step (2), the main screw speed of the twin-screw extruder is 300 to 500 r / min.

10. Use of the reinforced high temperature nylon composite material according to any one of claims 1 to 7 in a plastic product, characterized in that: The applications include the aerospace field, the military field, automotive materials, sports equipment, building materials, and the field of electronic and electrical facilities.

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