Composite resin for solvent-method prepreg production and preparation method thereof

Abstract

The invention discloses composite resin for solvent-method prepreg production and a preparation method of the composite resin. The composite resin is prepared from the following raw materials: 35-145 parts of modified amorphous polyaryletherketone; 8 to 35 parts of polycarbonate; 0.5-6 parts of a modified inorganic nano material; the modified amorphous polyaryletherketone comprises high molecular weight modified amorphous polyaryletherketone and low molecular weight modified amorphous polyaryletherketone, and the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is (3-30): 1. A low-molecular-weight modified amorphous polyaryletherketone and high-molecular-weight modified amorphous polyaryletherketone composite system is adopted, the interfacial compatibility of polycarbonate and the modified amorphous polyaryletherketone is improved by utilizing the solubility of the low-molecular-weight modified amorphous polyaryletherketone and utilizing the high specific surface area and surface energy of the modified inorganic nano material, and the high-molecular-weight modified amorphous polyaryletherketone is obtained. The toughness and the impact resistance of the composite material are improved; the requirements of aerospace, new energy automobiles, rail transit and other parts on the high-strength and high-toughness composite material are met.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a composite resin for producing solvent-process prepregs and a preparation method thereof. Background Art

[0002] Compared with thermosetting resin-based composites, thermoplastic resin-based composites have the advantages of good toughness, long prepreg storage time, short molding cycle, and easy repair; they are widely used in aerospace, automobiles, sporting goods, 3C and other fields. With the development of the aerospace field, it is increasingly urgent to reduce the weight of equipment and improve the overall performance, which puts higher requirements on the mechanical properties, heat resistance and harsh environment resistance of resin-based composites. Traditional general-purpose plastics and engineering plastics can no longer meet the requirements of operating conditions, and special engineering plastics thermoplastic resin-based composites represented by polyetherimide (PEI), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK) are widely used in the aerospace field due to their excellent performance.

[0003] This type of special engineering plastic thermoplastic resin-based composite material is mostly processed by pre-impregnation to prepare prepregs, and then prepare thermoplastic composite materials. However, currently industrialized thermoplastic resins are difficult to dissolve in conventional solvents, and prepregs are mostly prepared by melt impregnation. However, the melt viscosity after melting is high, which can easily lead to insufficient pre-impregnation of reinforcing fibers and gaps on the product surface. At the same time, in some special application conditions, there is also a need to further improve impact toughness. Therefore, it is of great significance to develop a composite resin that is easily soluble in solvents and has high toughness for the production of thermoplastic prepregs. Summary of the Invention

[0004] In order to overcome the above-mentioned shortcomings, the object of the present invention is to provide a composite resin for the production of solvent-based prepregs, which is used to prepare prepregs and can improve the tensile strength and toughness of the prepregs.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: a composite resin for producing solvent-process prepreg, wherein the raw materials for preparing the composite resin include, by weight:

[0006] 35-145 parts of modified amorphous polyaryletherketone;

[0007] 8-35 parts of polycarbonate;

[0008] 0.5-6 parts of modified inorganic nanomaterials;

[0009] 0.1-0.3 parts of antioxidant;

[0010] Preferably, the raw materials for preparing the composite resin include: 42-130 parts of modified amorphous polyaryletherketone, 12-30 parts of polycarbonate, 1.5-4.5 parts of modified inorganic nanomaterials, and 0.1-0.3 parts of antioxidant.

[0011] The molecular structure of the modified amorphous polyaryletherketone has a long alkyl chain end group, a monocyano side chain, and an aminosiloxane-modified amide side chain.

[0012] Furthermore, the modified amorphous polyaryletherketone includes a high molecular weight modified amorphous polyaryletherketone and a low molecular weight modified amorphous polyaryletherketone.

[0013] Furthermore, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 3-30:1.

[0014] Illustratively, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1 or a range consisting of any two thereof.

[0015] Preferably, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 6-15:1.

[0016] Furthermore, the average molecular weight of the high molecular weight modified amorphous polyaryletherketone is 20,000-40,000; the average molecular weight of the low molecular weight modified amorphous polyaryletherketone is 5,000-10,000.

[0017] Furthermore, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to polycarbonate is 2-6:1. Exemplarily, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to polycarbonate is 2:1, 3:1, 4:1, 5:1, 6:1, or a range consisting of any two thereof.

[0018] Preferably, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 3-4:1.

[0019] Furthermore, the preparation method of the modified amorphous polyaryletherketone is as follows:

[0020] Step (1), adding a side chain agent to a phenolphthalein monomer, heating to 160-200° C. and reacting for 30-60 hours to obtain a modified phenolphthalein;

[0021] Step (2), adding modified phenolphthalein, phenolphthalein monomer, 2,6-dichlorobenzonitrile, sulfolane, anhydrous potassium carbonate, and xylene into a reaction kettle, heating to 140-160° C. and keeping constant for 3-5 hours, then continuing to heat to 200-220° C. and reacting for 6-10 hours to obtain a viscous polymer product;

[0022] Step (3), adding halogenated hydrocarbon to the product obtained in step (2), heating to 190-210° C., stirring and reacting for 1.5-3 hours, and purifying to obtain modified amorphous polyaryletherketone.

[0023] Furthermore, the side chain agent in step (1) is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bisaminopropyl polydimethylsiloxane, and aminopropyl-terminated polydimethylsiloxane.

[0024] Furthermore, in step (1), the mass ratio of the phenolphthalein monomer to the side chain agent is 1:1.5-3.

[0025] Furthermore, the amounts of the substances used in steps (2) and (3) are respectively: 260-300 parts of phenolphthalein monomer, 50-130 parts of modified phenolphthalein, 140-200 parts of 2,6-dichlorobenzonitrile, 1-13 parts of halogenated hydrocarbon, 800-1300 parts of sulfolane, 120-290 parts of anhydrous potassium carbonate, and 20-100 parts of xylene.

[0026] Furthermore, the modified phenolphthalein accounts for 10-30% of the sum of the mass of the phenolphthalein monomer and the modified phenolphthalein.

[0027] Furthermore, the alkyl chain length of the halogenated hydrocarbon is C7-C10.

[0028] Preferably, the halogenated hydrocarbon is selected from at least one of 1-chlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane and 1-chlorodecane.

[0029] Furthermore, the mass ratio of the halogenated hydrocarbon to 2,6-dichlorobenzonitrile is 0.04-0.06:1.

[0030] Furthermore, the modified inorganic nanomaterial is a pretreated inorganic powder modified with a silane coupling agent.

[0031] Furthermore, the silane coupling agent is at least one of KH550, KH560, and KH570.

[0032] Furthermore, the pretreated inorganic powder is a product obtained by activating the inorganic powder at 300-600° C. for 3-7 hours.

[0033] Furthermore, the inorganic powder is at least one of silicon dioxide, montmorillonite, bentonite and kaolinite.

[0034] Furthermore, the mass ratio of the silane coupling agent to the pretreated inorganic powder is 1:20-30.

[0035] Furthermore, the preparation method of the modified inorganic nanomaterial includes the following steps: placing the pretreated inorganic powder and the silane coupling agent in toluene, ultrasonically dispersing for 5-15 minutes, and refluxing at 100-120°C for 2-4 hours, followed by cooling, centrifugation, washing, and drying to obtain the modified inorganic nanomaterial.

[0036] Furthermore, the antioxidant is at least one of antioxidant 1010 and antioxidant 168 .

[0037] Furthermore, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168.

[0038] Furthermore, in the antioxidant, the mass ratio of antioxidant 1010 to antioxidant 168 is 1:(0.8-1.2).

[0039] A method for preparing the composite resin for producing the above-mentioned solvent-based prepreg comprises the following steps:

[0040] S1. uniformly mixing a high molecular weight modified amorphous polyaryletherketone, a low molecular weight modified amorphous polyaryletherketone, polycarbonate, a modified inorganic nanomaterial, and an antioxidant to obtain a mixture;

[0041] S2, adding the mixture into a twin-screw extruder, extruding and granulating to obtain modified material particles;

[0042] S3. Freeze-crushing the modified particles to a particle size of 50-100 μm to obtain a composite resin.

[0043] Furthermore, in step S2, extrusion granulation is performed at 200-310°C.

[0044] Furthermore, in step S3, the freezing temperature is -120°C to -80°C.

[0045] The beneficial effects of the present invention are:

[0046] 1) The present invention adopts a composite system of low molecular weight modified amorphous polyaryletherketone and high molecular weight modified amorphous polyaryletherketone. By utilizing the easy solubility of the low molecular weight modified amorphous polyaryletherketone, the solid content of the prepreg solution can be increased while ensuring sufficient fiber impregnation, thereby improving the stability of the prepreg resin content. At the same time, the low molecular weight modified amorphous polyaryletherketone and the high molecular weight modified amorphous polyaryletherketone have similar molecular structures and can form relatively good mutual entanglement, thereby improving the interface performance.

[0047] By utilizing the high specific surface area and surface energy of modified inorganic nanomaterials, physical anchor points can be formed at the polymer interface, thereby improving the interfacial compatibility between polycarbonate and modified amorphous polyaryletherketone. While ensuring the heat resistance and tensile strength of the blended modified resin, the toughness of the blended modified resin is further improved; the toughness and impact resistance of the composite material can be significantly improved; and the requirements of aerospace, new energy vehicles, rail transit and other components for high-strength and high-toughness composite materials can be met.

[0048] 2) The present invention uses a modified amorphous polyaryletherketone resin and introduces aminosiloxane-modified amide ring large side groups on the amorphous polyaryletherketone molecular chain. While ensuring heat resistance, it can also increase the free volume and improve the flexibility of the molecular chain. It can significantly improve the solubility of the amorphous polyaryletherketone in some polar solvents, which is beneficial to the preparation of high-performance solution-process prepregs.

[0049] 3) The present invention uses a modified amorphous polyaryletherketone resin and improves the polarity of the amorphous polyaryletherketone by introducing cyano and siloxane groups into the resin molecular chain; it can enhance the bonding strength between the resin matrix and the reinforced fibers, thereby improving the mechanical properties of the composite material.

[0050] 4) The present invention uses a flexible alkane chain on the modified amorphous polyaryletherketone molecular chain to improve the toughness of the amorphous polyaryletherketone. DETAILED DESCRIPTION

[0051] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0052] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to express the amounts of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art can appropriately change these approximate values ​​by utilizing the teachings disclosed herein to seek to obtain the desired properties. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0053] One embodiment of the present invention provides a method for preparing a composite resin for producing solvent-based prepregs, comprising the following steps:

[0054] S1. uniformly mixing the modified amorphous polyaryletherketone, polycarbonate, modified inorganic nanomaterial, and antioxidant to obtain a mixture;

[0055] In some embodiments, the molecular structure of the modified amorphous poly(aryletherketone) has a long alkyl chain end group, a monocyano side chain, and an aminosiloxane-modified amide side chain.

[0056] In some embodiments, the modified amorphous poly(aryletherketone) comprises a high molecular weight modified amorphous poly(aryletherketone) and a low molecular weight modified amorphous poly(aryletherketone).

[0057] In some embodiments, in step S1, the high molecular weight modified amorphous polyaryletherketone is 32-128 parts, the low molecular weight modified amorphous polyaryletherketone is 3-17 parts, the polycarbonate is 8-35 parts, the modified inorganic nanomaterial is 0.5-6 parts, and the antioxidant is 0.1-0.3 parts;

[0058] In some embodiments, in step S1, the high molecular weight modified amorphous polyaryletherketone is 37-120 parts, the low molecular weight modified amorphous polyaryletherketone is 5-10 parts, the polycarbonate is 12-30 parts, the modified inorganic nanomaterial is 1.5-4.5 parts, and the antioxidant is 0.1-0.3 parts.

[0059] In some embodiments, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 3-30:1.

[0060] In some embodiments, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 6-15:1.

[0061] In some embodiments, the average molecular weight of the high molecular weight modified amorphous poly(aryletherketone) is 20,000-40,000; the average molecular weight of the low molecular weight modified amorphous poly(aryletherketone) is 5,000-10,000.

[0062] In some embodiments, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 2-6:1.

[0063] In some embodiments, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 3-4:1.

[0064] In some embodiments, the raw materials for preparing the modified amorphous polyaryletherketone include 260-300 parts of phenolphthalein monomer, 50-130 parts of modified phenolphthalein, 140-200 parts of 2,6-dichlorobenzonitrile, 1-13 parts of halogenated hydrocarbon, 800-1300 parts of sulfolane, 120-290 parts of anhydrous potassium carbonate, and 20-100 parts of xylene.

[0065] In some embodiments, the raw materials for preparing the modified phenolphthalein include phenolphthalein monomer and a side chain agent, and the mass ratio of the phenolphthalein monomer to the side chain agent is 1:1.5-3.

[0066] In some embodiments, the side chain agent is selected from at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bisaminopropyl polydimethylsiloxane, and aminopropyl-terminated polydimethylsiloxane.

[0067] In some embodiments, the modified phenolphthalein accounts for 10-30% of the total mass of the phenolphthalein monomer and the modified phenolphthalein.

[0068] In some embodiments, the alkyl chain length of the halogenated hydrocarbon is C7-C10.

[0069] In some embodiments, the halogenated hydrocarbon is selected from at least one of 1-chlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, and 1-chlorodecane.

[0070] In some embodiments, the mass ratio of the halogenated hydrocarbon to 2,6-dichlorobenzonitrile is 0.04-0.06:1.

[0071] In some embodiments, the method for preparing the modified amorphous poly(aryletherketone) comprises the following steps:

[0072] Step (1), adding a side chain agent to a phenolphthalein monomer, heating to 160-200° C. and reacting for 30-60 hours to obtain a modified phenolphthalein;

[0073] Step (2), adding phenolphthalein, modified phenolphthalein, 2,6-dichlorobenzonitrile, sulfolane, anhydrous potassium carbonate, and xylene into a reaction kettle, heating to 140-160° C. and keeping constant for 3-5 hours, then continuing to heat to 200-220° C. and reacting for 6-10 hours to obtain a viscous polymer product;

[0074] Step (3), adding halogenated hydrocarbon to the viscous polymer product obtained in step (2), heating to 190-210° C., stirring and reacting for 1.5-3 hours, and purifying to obtain a modified amorphous polyaryletherketone.

[0075] In some embodiments, the modified inorganic nanomaterial is a pretreated inorganic powder modified with a silane coupling agent.

[0076] In some embodiments, the silane coupling agent is at least one of KH550, KH560, and KH570.

[0077] In some embodiments, the pretreated inorganic powder is a product obtained by activating the inorganic powder at 300-600° C. for 3-7 hours.

[0078] In some embodiments, the inorganic powder is at least one of silica, montmorillonite, bentonite, and kaolinite.

[0079] In some embodiments, the mass ratio of the silane coupling agent to the pretreated inorganic powder is 1:20-30.

[0080] In some embodiments, the preparation method of modified inorganic nanomaterials includes the following steps: placing pretreated inorganic powder and silane coupling agent in toluene, ultrasonically dispersing for 5-15 minutes, and refluxing at 100-120°C for 2-4 hours, followed by cooling, centrifugation, washing, and drying to obtain modified inorganic nanomaterials.

[0081] In some embodiments, the antioxidant is at least one of antioxidant 1010 and antioxidant 168 .

[0082] In some embodiments, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 .

[0083] In some embodiments, the mass ratio of the antioxidant 1010 to the antioxidant 168 in the antioxidant is 1:(0.8-1.2).

[0084] S2. Add the mixture into a twin-screw extruder, and extrude and granulate at 200-310° C. to obtain modified particles;

[0085] S3. Freeze-crushing the modified particles at -120°C to -80°C to a particle size of 50-100 μm to obtain a composite resin.

[0086] Example

[0087] The following examples more particularly describe the present disclosure, and these examples are intended to be illustrative only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used directly without further processing, and all instruments used in the examples are commercially available.

[0088] Example 1

[0089] A method for preparing a composite resin for solution-process prepreg production comprises the following steps:

[0090] S1. Evenly mixing 71 parts of a high molecular weight modified amorphous polyaryletherketone, 6.5 parts of a low molecular weight modified amorphous polyaryletherketone, 20 parts of polycarbonate, 2.7 parts of a modified inorganic nanomaterial, and 0.2 parts of an antioxidant (0.1 parts of antioxidant 1010 and 0.1 parts of antioxidant 168) to obtain a mixture;

[0091] S2. adding the mixture into a twin-screw extruder, and using the twin-screw extruder to extrude and granulate at the temperature conditions of "220° C., 285° C., 290° C., 295° C., 290° C., and 295° C. (die head)" to obtain modified particles;

[0092] S3. The modified particles are crushed at low temperature and high speed at -100°C to a particle size of 60 μm to obtain a composite resin for solvent-processed prepreg production.

[0093] According to calculation, the mass ratio of high molecular weight modified amorphous polyaryletherketone to low molecular weight modified amorphous polyaryletherketone is 71:6.5=10.92:1;

[0094] The mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 71:20=3.55:1.

[0095] in:

[0096] ① A method for preparing a low molecular weight modified amorphous polyaryletherketone, comprising the following steps:

[0097] Step (1), under nitrogen protection, phenolphthalein and 3-aminopropyltrimethoxysilane are mixed uniformly in a mass ratio of 1:2.4, heated to 180° C., and stirred for 45 hours; after the reaction is completed, the temperature is lowered to room temperature, ultrapure water is added to precipitate a solid, and then filtered, and the filtered solid is recrystallized with ethyl acetate to obtain a modified phenolphthalein;

[0098] Step (2): adding 273 parts of phenolphthalein monomer, 100 parts of modified phenolphthalein, 170 parts of 2,6-dichlorobenzonitrile, 1000 parts of sulfolane, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene to a reaction kettle, heating the mixture to 150° C. and maintaining the temperature for 4 hours, then heating the mixture to 210° C. and reacting the mixture for 8 hours to obtain a viscous polymer product; (the molar ratio of phenolphthalein (including phenolphthalein monomer and modified phenolphthalein) to 2,6-dichlorobenzonitrile is between 1.05-1.07:1, and a low molecular weight modified amorphous polyaryletherketone with a molecular weight of 5000-10000 can be obtained)

[0099] Step (3), adding 8 parts of 1-chlorooctane to the viscous polymer product obtained in step (2), stirring evenly, reacting at 200°C for 2 hours, cooling, adding 2500 parts of dimethylacetamide to dilute, and stirring evenly; under vigorous stirring, pouring the solution into a large amount of water for precipitation, filtering, and then crushing with a high-speed stirrer; then washing the product with dilute hydrochloric acid and pure water in sequence, and then drying to obtain a low molecular weight modified amorphous polyaryletherketone.

[0100] After calculation, the ratio of the mass of the modified phenolphthalein to the mass of the phenolphthalein monomer and the modified phenolphthalein is: 100 / (100+273)*100%=26.8%.

[0101] ② The preparation method of the high molecular weight modified amorphous polyaryletherketone is substantially the same as the preparation method of the low molecular weight modified amorphous polyaryletherketone, except that the raw materials for preparing the viscous polymer product in step (2) include 270.3 parts of phenolphthalein monomer, 99 parts of modified phenolphthalein, 173.7 parts of 2,6-dichlorobenzonitrile, 1000 parts of sulfolane, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene. (The molar ratio of phenolphthalein (including phenolphthalein monomer and modified phenolphthalein) to 2,6-dichlorobenzonitrile is between 1.02 and 1.04:1, and a high molecular weight modified amorphous polyaryletherketone with a molecular weight of 20,000 to 40,000 can be obtained.)

[0102] After calculation, the ratio of the mass of the modified phenolphthalein to the mass of the phenolphthalein monomer and the modified phenolphthalein is: 100 / (99+270.3)*100%=26.8%.

[0103] ③ A method for preparing modified inorganic nanomaterials, comprising the following steps: activating silica at 400°C for 5 hours to obtain pretreated silica; then uniformly mixing silica and KH-550 silane coupling agent in a mass ratio of 25:1, placing them together in toluene dehydrated by molecular sieves, ultrasonically dispersing for 10 minutes, refluxing at 110°C for 2 hours, stopping, and cooling; then centrifuging at 13,000 r / min, washing five times with anhydrous ethanol, and drying to obtain modified inorganic nanomaterials.

[0104] Example 2

[0105] The preparation processes of Example 2 and Example 1 are basically the same, the main difference being that the specific parts of the raw materials for preparing the composite resin in step S1 are different, specifically: 65.5 parts of high molecular weight modified amorphous polyaryletherketone, 10 parts of low molecular weight modified amorphous polyaryletherketone, 21.8 parts of polycarbonate, 2.6 parts of modified inorganic nanomaterials, and 0.2 parts of antioxidant.

[0106] According to calculation, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 65.5:10=6.55:1;

[0107] The mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 65.5:21.8=3.00:1.

[0108] Example 3

[0109] The preparation processes of Example 3 and Example 1 are basically the same, the main difference being that the specific parts of the raw materials for preparing the composite resin in step S1 are different, specifically: 73.5 parts of high molecular weight modified amorphous polyaryletherketone, 5 parts of low molecular weight modified amorphous polyaryletherketone, 18.5 parts of polycarbonate, 2.7 parts of modified inorganic nanomaterials, and 0.2 parts of antioxidant.

[0110] According to calculation, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 73.5:5=14.7:1;

[0111] The mass ratio of the high molecular weight modified amorphous polyaryletherketone to the polycarbonate is 73.5:18.5=3.97:1.

[0112] Example 4

[0113] The preparation processes of Example 4 and Example 1 are basically the same, the main difference being that in the raw materials for preparing the composite resin in step S1, the high molecular weight modified amorphous polyaryletherketone is 60 parts and the low molecular weight modified amorphous polyaryletherketone is 17.5 parts.

[0114] According to calculation, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 60:17.5=3.43:1.

[0115] Example 5

[0116] The preparation process of Example 5 is basically the same as that of Example 1, the main difference being that in step S1, the raw materials for preparing the composite resin include 73 parts of high molecular weight modified amorphous polyaryletherketone and 4.5 parts of low molecular weight modified amorphous polyaryletherketone.

[0117] According to calculation, the mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 73:4.5=16.22:1.

[0118] Example 6

[0119] The preparation process of Example 6 is basically the same as that of Example 1, the main difference being that in step S1, the raw materials for preparing the composite resin include 77.5 parts of high molecular weight modified amorphous polyaryletherketone and 13.5 parts of polycarbonate.

[0120] According to calculation, the mass ratio of the high molecular weight modified amorphous polyaryletherketone and the polycarbonate is 77.5:13.5=5.74:1.

[0121] Comparative Example 1

[0122] The preparation processes of Comparative Example 1 and Example 1 are basically the same, with the main difference being that in step S1, 77.5 parts of a medium molecular weight modified amorphous polyaryletherketone (molecular weight between 10,000 and 20,000) are added to replace the 71 parts of high molecular weight modified amorphous polyaryletherketone and 6.5 parts of low molecular weight modified amorphous polyaryletherketone in Example 1. The preparation method of the medium molecular weight modified amorphous polyaryletherketone is as follows:

[0123] Step (1), under nitrogen protection, phenolphthalein and 3-aminopropyltrimethoxysilane are mixed uniformly in a mass ratio of 1:2.4, heated to 180° C., and stirred for 45 hours; after the reaction is completed, the temperature is lowered to room temperature, ultrapure water is added to precipitate a solid, and then filtered, and the filtered solid is recrystallized with ethyl acetate to obtain a modified phenolphthalein;

[0124] Step (2): 271.8 parts of phenolphthalein monomer, 99.5 parts of modified phenolphthalein, 171.7 parts of 2,6-dichlorobenzonitrile, 1000 parts of sulfolane, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene are added to a reaction kettle, the temperature is raised to 150° C. and kept constant for 4 hours, then the temperature is further raised to 210° C. and the reaction is carried out for 8 hours to obtain a viscous polymer product; (the molar ratio of phenolphthalein (including phenolphthalein monomer and modified phenolphthalein) to 2,6-dichlorobenzonitrile is between 1.04-1.05:1, and a medium molecular weight modified amorphous polyaryletherketone with a molecular weight of 10,000-20,000 can be obtained)

[0125] Step (3), adding 8 parts of 1-chlorooctane to the viscous polymer product obtained in step (2), stirring evenly, reacting at 200°C for 2 hours, cooling, adding 2500 parts of dimethylacetamide to dilute, and stirring evenly; under vigorous stirring, pouring the solution into a large amount of water for precipitation, filtering, and then crushing with a high-speed stirrer; then washing the product with dilute hydrochloric acid and pure water in sequence, and then drying to obtain a medium molecular weight modified amorphous polyaryletherketone.

[0126] According to calculation, the ratio of the mass of the modified phenolphthalein to the mass of the phenolphthalein monomer and the modified phenolphthalein is: 99.5 / (99.5+271.8)*100%=26.8%.

[0127] Comparative Example 2

[0128] The preparation processes of Comparative Example 2 and Example 1 are basically the same, the main difference being that in step S1, the added low molecular weight modified amorphous polyaryletherketone and the high molecular weight modified amorphous polyaryletherketone are both modified amorphous polyaryletherketones that do not contain aminosilicone. The preparation methods of the two are as follows:

[0129] ① A method for preparing a low molecular weight modified amorphous polyaryletherketone, comprising the following steps:

[0130] Step (2), adding 373 parts of phenolphthalein monomer, 170 parts of 2,6-dichlorobenzonitrile, 1000 parts of sulfolane, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene into a reaction kettle, heating to 150° C. and holding the temperature for 4 hours, then continuing to heat to 210° C. and reacting for 8 hours to obtain a viscous polymer product;

[0131] Step (3), adding 8 parts of 1-chlorooctane to the viscous polymer product obtained in step (2), stirring evenly, reacting at 200°C for 2 hours, cooling, adding 2500 parts of dimethylacetamide to dilute, and stirring evenly; under vigorous stirring, pouring the solution into a large amount of water for precipitation, filtering, and then crushing with a high-speed stirrer; then washing the product with dilute hydrochloric acid and pure water in sequence, and then drying to obtain a low molecular weight modified amorphous polyaryletherketone.

[0132] ② The preparation method of the high molecular weight modified amorphous polyaryletherketone is basically the same as the preparation method of the low molecular weight modified amorphous polyaryletherketone, except that: the raw materials for preparing the viscous polymer product in step (2) include 369.3 parts of phenolphthalein monomer, 173.7 parts of 2,6-dichlorobenzonitrile, 1000 parts of cyclopentane sulfone, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene.

[0133] Comparative Example 3

[0134] The preparation processes of Comparative Example 3 and Example 1 are basically the same, the main difference being that in step S1, the added low molecular weight modified amorphous polyaryletherketone and high molecular weight modified amorphous polyaryletherketone are both modified amorphous polyaryletherketones that do not contain long-chain alkyl groups. The preparation methods of the two are as follows:

[0135] ① A method for preparing a low molecular weight modified amorphous polyaryletherketone, comprising the following steps:

[0136] Step (1), under nitrogen protection, phenolphthalein and 3-aminopropyltrimethoxysilane are mixed uniformly in a mass ratio of 1:2.4, heated to 180° C., and stirred for 45 hours; after the reaction is completed, the temperature is lowered to room temperature, ultrapure water is added to precipitate a solid, and then filtered, and the filtered solid is recrystallized with ethyl acetate to obtain a modified phenolphthalein;

[0137] Step (2), adding 273 parts of phenolphthalein monomer, 100 parts of modified phenolphthalein, 170 parts of 2,6-dichlorobenzonitrile, 1000 parts of sulfolane, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene into a reaction kettle, heating to 150° C. and holding the temperature for 4 hours, then continuing to heat to 210° C. and reacting for 8 hours to obtain a viscous polymer product;

[0138] Step (3), add 2500 parts of dimethylacetamide to step (2) to dilute and stir evenly; pour the solution into a large amount of water under vigorous stirring to precipitate, filter and crush with a high-speed stirrer; then wash the product with dilute hydrochloric acid and pure water in sequence, and then dry it to obtain a low molecular weight modified amorphous polyaryletherketone.

[0139] After calculation, the ratio of the mass of the modified phenolphthalein to the mass of the phenolphthalein monomer and the modified phenolphthalein is: 100 / (100+273)*100%=26.8%.

[0140] ② The preparation method of the high molecular weight modified amorphous polyaryletherketone is basically the same as the preparation method of the low molecular weight modified amorphous polyaryletherketone, except that: the raw materials for preparing the viscous polymer product in step (2) include 270.3 parts of phenolphthalein monomer, 99 parts of modified phenolphthalein, 173.7 parts of 2,6-dichlorobenzonitrile, 1000 parts of cyclopentane sulfone, 160 parts of anhydrous potassium carbonate, and 70 parts of xylene.

[0141] After calculation, the ratio of the mass of modified phenolphthalein to the mass of phenolphthalein monomer and modified phenolphthalein is: 100 / (99+270.3)*100%=26.8%

[0142] Comparative Example 4

[0143] The preparation processes of Comparative Example 4 and Example 1 are basically the same, the main difference being that in step S1, 1-chlorobutane is added to the viscous polymer product obtained in step (3) to replace the 1-chlorooctane in Example 1.

[0144] Comparative Example 5

[0145] The preparation processes of Comparative Example 5 and Example 1 are basically the same, the main difference being that in step S1, 1-chlorohexadecane is added to the viscous polymer product obtained in step (3) to replace the 1-chlorooctane in Example 1.

[0146] Comparative Example 6

[0147] The preparation processes of Comparative Example 6 and Example 1 are basically the same, the main difference being that in step (1), 1-aminopropane is used as the raw material for preparing modified phenolphthalein to replace the 3-aminopropyltrimethoxysilane in Example 1.

[0148] Comparative Example 7

[0149] The preparation processes of Comparative Example 7 and Example 1 are basically the same, the main difference being that in step (2), m-dichlorobenzene is added to replace the 2,6-dichlorobenzonitrile in Example 1.

[0150] Experimental Example 1

[0151] The performance of the composite resins for the production of solvent-process prepregs prepared in Examples 1-6 and Comparative Examples 1-7 was tested, wherein:

[0152] The glass transition temperature of the sample was tested according to GB / T19466.2-2004 "Plastics Differential Scanning Calorimetry (DSC) Part 2 - Determination of Glass Transition Temperature";

[0153] The tensile strength of the sample is tested in accordance with GB / T1040.2-2022 "Determination of tensile properties of plastics Part 2: Test conditions for molded and extruded plastics";

[0154] The notched impact strength of the sample is tested in accordance with GB / T1043.2-2018 "Determination of impact properties of plastics - Part 2: Instrumented impact test";

[0155] The flexural strength of the sample was tested in accordance with GB / T9341-2008 “Determination of flexural properties of plastics”.

[0156] The test results are shown in Table 1.

[0157]

[0158]

[0159] As can be seen from Table 1, the glass transition temperature of the composite resin obtained in Examples 1-3 is within 211.4-214.3°C, the tensile strength is ≥90.1MPa, the flexural strength is ≥130.8MPa, and the notched impact strength is ≥50.3KJ / m 2 .

[0160] Compared with Example 1, the tensile strength, flexural strength and notched impact strength of the composite resin obtained in Example 4 are all reduced. The reason may be that the amount of high molecular weight modified amorphous polyaryletherketone in the system is relatively low, and its contribution to improving the mechanical strength of the composite resin is insufficient. Therefore, the overall mechanical strength of the obtained composite resin is reduced.

[0161] Compared with Example 1, the amount of high molecular weight modified amorphous polyaryletherketone in Examples 5 and 6 is relatively large. Although the tensile strength and flexural strength remain high, the notched impact strength of the resulting composite resin is significantly reduced compared with Example 1.

[0162] Compared with Example 1, the tensile strength, flexural strength, and notched impact strength of the composite resin obtained in Comparative Example 1 are reduced. The reason may be that the molecular weight distribution range of the single medium molecular weight modified amorphous polyaryletherketone is relatively narrow, and compared with the compounding of high molecular weight modified amorphous polyaryletherketone and low molecular weight modified amorphous polyaryletherketone, the combined effect of mechanical strength and wetting effect is relatively poor, so the mechanical properties of the obtained composite resin are reduced.

[0163] Compared to Example 1, the composite resin obtained in Comparative Example 2 exhibited an increased glass transition temperature, while its tensile strength, flexural strength, and notched impact strength decreased. This may be due to the lack of the large side groups on the aminosiloxane-modified amide rings in Comparative Example 2, which reduced the free volume and molecular chain flexibility of the polymer and its compatibility with the modified inorganic nanomaterials, resulting in a decrease in the overall performance of the composite resin. In contrast, in Comparative Example 6, which lacked only the siloxane groups, the resulting composite resin exhibited slightly better mechanical properties than those of Comparative Example 2.

[0164] Compared to Example 1, the composite resin obtained in Comparative Example 3 exhibited an increased glass transition temperature, while exhibited decreased tensile strength, flexural strength, and notched impact strength. This may be due to the lack of long-chain alkyl end groups in the polymer structure of Comparative Example 3, which reduced the free volume and toughness of the system, thereby affecting the glass transition temperature and mechanical properties of the composite resin. The shorter end-capped alkyl segments in Comparative Example 4 resulted in a weaker increase in polymer free volume and toughness than in Example 1, potentially leading to decreased tensile strength, flexural strength, and notched impact strength of the resulting composite resin. The longer end-capped alkyl segments in Comparative Example 5, while significantly increasing the free volume and toughness of the polymer, also resulted in entanglement and stacking of long chains, which in turn affected the mechanical properties of the resulting composite resin.

[0165] Compared with Example 1, the composite resin of Comparative Example 7 does not contain cyano groups, and the tensile strength, flexural strength, notched impact strength, etc. do not show significant changes, but the performance shows a decline in subsequent applications.

[0166] Application Examples

[0167] Prepregs were prepared using the composite resins prepared in Examples 1-6 and Comparative Examples 1-7, and the prepregs were subjected to performance tests according to GB / T 1447-2005 Test method for tensile properties of fiber reinforced plastics. The test results are shown in Table 2.

[0168] Taking prepreg tape as an example, the preparation steps of prepreg tape are as follows:

[0169] Step 1: Dissolve the composite resins obtained in Examples 1-6 and Comparative Examples 1-7 in acetophenone respectively, prepare a solution with a mass concentration of 35%, and pour it into a dipping tank;

[0170] Step 2: The T700-12K carbon fiber was impregnated through a glue tank at a speed of 0.5 m / min, and then passed through a mixed solution of acetone and toluene (the volume ratio of acetone to toluene was 4:1), and then passed through two drying channels of "220°C, 15 min and 350°C, 15 min" to melt the resin;

[0171] Step 3: The molten resin is passed through a hot pressing roller at 330° C. and compacted under a pressure of 5 MPa to obtain a prepreg tape with a fiber volume fraction of 60%.

[0172] Table 2

[0173] Application Examples Tensile strength / MPa Tensile modulus / GPa Elongation at break / % Application Example 1 2180 115 2.10 Application Example 2 2110 108 1.84 Application Example 3 2300 119 2.21 Application Example 4 2000 104 2.25 Application Example 5 2150 117 1.73 Application Example 6 2060 118 1.67 Comparative Application Example 1 1870 93 1.55 Comparative Application Example 2 1690 84 1.32 Comparative Application Example 3 1720 87 1.36 Comparative Application Example 4 1840 94 1.51 Comparative Application Example 5 1800 92 1.45 Comparative Application Example 6 1770 89 1.40 Comparative Application Example 7 1910 99 1.60

[0174] As can be seen in Table 2, the trends in the comprehensive mechanical properties of the resulting prepregs, as demonstrated by their tensile strength, tensile modulus, and elongation at break, are consistent with those of the composite resins. While the composite resin prepared in Comparative Example 7 exhibits superior performance, the prepregs prepared using it perform significantly worse than those in Application Examples 1-6. This is likely due to the strong polarity of the active cyano groups, which enhances their ability to bond with other components (e.g., carbon fiber) while maintaining the polymer's high-temperature resistance and toughness.

[0175] The present invention uses the above-described embodiments to illustrate the detailed process equipment and process flow of the present invention. However, the present invention is not limited to the above-described detailed process equipment and process flow, and does not mean that the present invention must rely on the above-described detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacement of raw materials of the present invention, changes in structural form, addition of auxiliary ingredients, selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

[0176] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0177] The above embodiments are only for illustrating the technical concept and features of the present invention. Its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it. It cannot be used to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A composite resin for producing solvent-based prepregs, characterized in that: The raw materials for preparing the composite resin include, by weight: 35-145 parts of modified amorphous polyaryletherketone; 8-35 parts of polycarbonate; 0.5-6 parts of modified inorganic nanomaterials; 0.1-1 part of antioxidant; The molecular structure of the modified amorphous polyaryletherketone has a long alkyl chain end group, a monocyano side chain, and an aminosiloxane-modified amide side chain; The modified amorphous polyaryletherketone includes high molecular weight modified amorphous polyaryletherketone and low molecular weight modified amorphous polyaryletherketone.

2. The composite resin according to claim 1, characterized in that The raw materials for preparing the composite resin include: 42-130 parts of modified amorphous polyaryletherketone, 12-30 parts of polycarbonate, 1.5-4.5 parts of modified inorganic nanomaterials, and 0.1-0.3 parts of antioxidant; The mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone in the modified amorphous polyaryletherketone is 3-30:

1.

3. The composite resin according to claim 1, characterized in that The average molecular weight of the high molecular weight modified amorphous polyaryletherketone is 20,000-40,000; the average molecular weight of the low molecular weight modified amorphous polyaryletherketone is 5,000-10,000.

4. The composite resin according to claim 1, characterized in that The mass ratio of the high molecular weight modified amorphous polyaryletherketone to polycarbonate is 2-6:

1.

5. The composite resin according to claim 1, characterized in that The mass ratio of the high molecular weight modified amorphous polyaryletherketone to the low molecular weight modified amorphous polyaryletherketone is 6-15:1; The mass ratio of the high molecular weight modified amorphous polyaryletherketone to polycarbonate is 3-4:

1.

6. The composite resin according to claim 1, characterized in that The preparation method of the modified amorphous polyaryletherketone is as follows: Step (1), adding a side chain agent to a phenolphthalein monomer, heating to 160-200° C. and reacting for 30-60 hours to obtain a modified phenolphthalein; Step (2), adding modified phenolphthalein, phenolphthalein monomer, 2,6-dichlorobenzonitrile, sulfolane, anhydrous potassium carbonate, and xylene into a reaction kettle, heating to 140-160° C. and keeping constant for 3-5 hours, then continuing to heat to 200-220° C. and reacting for 6-10 hours to obtain a viscous polymer product; Step (3), adding a halogenated hydrocarbon to the product obtained in step (2), heating to 190-210° C., stirring and reacting for 1.5-3 hours, and purifying to obtain a modified amorphous polyaryletherketone; The side chain agent in step (1) is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bisaminopropyl polydimethylsiloxane, and aminopropyl-terminated polydimethylsiloxane.

7. The composite resin according to claim 6, characterized in that In the step (1), the mass ratio of phenolphthalein monomer to side chain agent is 1:1.5-3; The amounts of the substances used in steps (2) and (3) are: 260-300 parts of phenolphthalein monomer, 50-130 parts of modified phenolphthalein, 140-200 parts of 2,6-dichlorobenzonitrile, 800-1300 parts of sulfolane, 120-290 parts of anhydrous potassium carbonate, 20-100 parts of xylene, and 5-13 parts of halogenated hydrocarbon; The modified phenolphthalein accounts for 10-30% of the total mass of the phenolphthalein monomer and the modified phenolphthalein.

8. The composite resin according to claim 1, wherein The modified inorganic nanomaterial is a pretreated inorganic powder modified with a silane coupling agent; The silane coupling agent is at least one of KH550, KH560, and KH570; The pretreated inorganic powder is the product of activating the inorganic powder at 300-600°C for 3-7h; The inorganic powder is at least one of silicon dioxide, montmorillonite, bentonite, and kaolinite; The mass ratio of the silane coupling agent to the pretreated inorganic powder is 1:20-30.

9. A method for preparing the composite resin according to any one of claims 1 to 8, characterized in that: The steps include: S1. uniformly mixing a high molecular weight modified amorphous polyaryletherketone, a low molecular weight modified amorphous polyaryletherketone, polycarbonate, a modified inorganic nanomaterial, and an antioxidant to obtain a mixture; S2, adding the mixture into a twin-screw extruder, extruding and granulating to obtain modified material particles; S3. Freeze-crushing the modified particles to a particle size of 50-100 μm to obtain a composite resin.

10. The method for preparing the composite resin according to claim 9, characterized in that: In the step S2, extrusion granulation is performed at 200-310°C; In step S3, the freezing temperature is -120°C to -80°C.

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