Continuous fiber reinforced composite material as well as preparation method and application thereof

Abstract

The invention provides a continuous fiber reinforced composite material as well as a preparation method and application thereof, and the continuous fiber reinforced composite material is prepared from the following raw materials in parts by weight: 20-80 parts of continuous fiber; 20 to 80 parts of high melt index resin; 0.5 to 3 parts of an anti-aging auxiliary agent; the melt index of the high melt index resin is 30 to 150 g / 10 min. According to the continuous fiber reinforced composite material provided by the invention, the high-melt-index resin is used as a matrix, the continuous fibers are used as a reinforcing material, and electron beam irradiation crosslinking is adopted, so that the composite material not only has high mechanical strength, but also has high heat resistance and high weather resistance, and the application range of the continuous fiber reinforced composite material is expanded.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and relates to a continuous fiber reinforced composite material and a preparation method and application thereof, and specifically relates to a continuous fiber reinforced composite material with high mechanical strength, high heat resistance and high weather resistance and a preparation method and application thereof. Background Art

[0002] Continuous fiber reinforced composites are composite materials made of resin as the matrix and continuous fibers as the reinforcement. They combine the comprehensive properties of the plastic matrix and the fiber bundles and have become an engineering material with superior performance and wide applications.

[0003] Existing continuous fiber reinforced composite materials are mainly based on thermoplastic resins, but the heat resistance and weather resistance of thermoplastic resins are limited, which limits the application of continuous fiber reinforced composite materials in high temperature and high humidity environments.

[0004] Therefore, it is desirable in the art to develop a continuous fiber reinforced composite material having not only high mechanical strength but also high heat resistance and high weather resistance. Summary of the invention

[0005] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a continuous fiber reinforced composite material and a preparation method and application thereof, and specifically to provide a continuous fiber reinforced composite material with high mechanical strength, high heat resistance and high weather resistance and a preparation method and application thereof. The present invention adopts a special resin formula and electron beam irradiation cross-linking to achieve high mechanical strength, high heat resistance, high weather resistance, etc. of the composite material, improve the heat resistance and weather resistance of the composite material, and expand the application range of the continuous fiber reinforced composite material.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a continuous fiber reinforced composite material, wherein the raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight:

[0008] Continuous fiber 20-80 parts;

[0009] 20-80 parts of high melt index resin;

[0010] 0.5-3 parts of anti-aging additives;

[0011] The high melt index resin has a melt index of 30-150 g / 10min, for example, 30 g / 10min, 35 g / 10min, 40 g / 10min, 45 g / 10min, 50 g / 10min, 55 g / 10min, 60 g / 10min, 65 g / 10min, 70 g / 10min, 75 g / 10min, 80 g / 10min, 85 g / 10min, 90 g / 10min, 95 g / 10min, 100 g / 10min, 105 g / 10min, 110 g / 10min, 115 g / 10min, 120 g / 10min, 125 g / 10min, 130 g / 10min, 135 g / 10min, 140 g / 10min, 145 g / 10min, 150 g / 10min, etc.

[0012] The continuous fiber reinforced composite material provided by the present invention uses a high melt index resin as a matrix, continuous fibers as a reinforcing material, and is cross-linked by electron beam irradiation, so that the composite material not only has high mechanical strength, but also has high heat resistance and high weather resistance, thereby expanding the application range of the continuous fiber reinforced composite material.

[0013] In the present invention, the raw materials for preparing the continuous fiber reinforced composite material are measured in parts by weight, and the amount of continuous fiber used can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, etc.

[0014] In the present invention, the raw materials for preparing the continuous fiber reinforced composite material are measured in parts by weight, and the amount of the high melt index resin can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, etc.

[0015] In the present invention, the raw materials for preparing the continuous fiber reinforced composite material are measured in parts by weight, and the amount of the anti-aging additive used can be 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, etc.

[0016] Preferably, the high melt index resin includes any one of PP resin, PE resin, PC resin, EVA resin, EMA resin, EBA resin, EMMA resin, PA resin, ABS resin, PMMA resin, PVDF resin, ETFE resin, PVF resin, and epoxy resin, or a combination of at least two of them. The test conditions for the melt index of PE resin, EVA resin, EMA resin, EBA resin, and EMMA resin are 190°C and 2.16kg; the test conditions for the melt index of PP resin are 230°C and 2.16kg; the test conditions for the melt index of PA resin, ABS resin, PMMA resin, PVDF resin, ETFE resin, PVF resin, and epoxy resin are 260°C and 2.16kg.

[0017] Preferably, the continuous fibers include any one of carbon fibers, glass fibers, aramid fibers, and basalt fibers, or a combination of at least two of them.

[0018] Preferably, the anti-aging aid comprises a light stabilizer and / or an antioxidant.

[0019] Preferably, the light stabilizer includes any one of a light shielding agent light stabilizer, a quencher light stabilizer, a free radical scavenger light stabilizer, and a hydroperoxide decomposer light stabilizer, or a combination of at least two of them.

[0020] Preferably, the light stabilizer comprises UV770.

[0021] Preferably, the antioxidant includes any one of hindered phenol antioxidants, aromatic amine antioxidants, phosphite antioxidants, thioether antioxidants, and metal passivator antioxidants, or a combination of at least two thereof.

[0022] Preferably, the antioxidant includes antioxidant 1010 and / or antioxidant 168.

[0023] Preferably, the raw materials for preparing the continuous fiber reinforced composite material also include a compatibilizer.

[0024] Preferably, the compatibilizer includes cyclic anhydride grafts, carboxylic acid grafts, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, polyethylene grafted maleic anhydride, and binary or ternary copolymers of glycidyl methacrylate and BA, MA, VA, and EA.

[0025] Preferably, the amount of the compatibilizer is 0.1-20 parts, for example, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, etc.

[0026] Preferably, the raw materials for preparing the continuous fiber reinforced composite material also include a cross-linking aid.

[0027] Preferably, the auxiliary cross-linking agent includes any one of trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), ethylene glycol diacrylate (EGDA), ethylene glycol dimethacrylate (EGDMA), N,N'-p-phenylbismaleimide (PDM or HVA-2), zinc diacrylate (ZDA), zinc dimethacrylate (ZDMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), and 1,2-polybutadiene (1,2-PBR) or a combination of at least two thereof.

[0028] Preferably, the amount of the auxiliary cross-linking agent is 0.1-3 parts, for example, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts.

[0029] Preferably, the raw materials for preparing the continuous fiber reinforced composite material also include a processing aid.

[0030] Preferably, the processing aid includes any one of silicone, calcium stearate, zinc stearate, oleamide, erucamide, polyethylene wax, or a combination of at least two thereof.

[0031] Preferably, the amount of the processing aid is 0.1-5 parts, for example, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts.

[0032] In a second aspect, the present invention provides a method for preparing the continuous fiber reinforced composite material as described in the first aspect, the preparation method comprising the following steps:

[0033] (a) mixing a formula amount of a high melt index resin, an anti-aging aid, an optional compatibilizer, an optional co-crosslinking agent, and an optional processing aid, granulating, and then heating, melting, and extruding to a die;

[0034] (b) drawing the continuous fiber from the constant tension creel to the die head;

[0035] (c) coating the resin melt extruded from the die head on the unfolded continuous fibers, and then passing through a cooling and shaping roller system to obtain a continuous fiber reinforced composite prepreg tape;

[0036] (d) pretreating the continuous fiber reinforced composite material prepreg tape by electron beam irradiation to obtain the continuous fiber reinforced composite material.

[0037] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0038] (1) mixing a formulated amount of a high melt index resin, an anti-aging aid, an optional compatibilizer, an optional co-crosslinking agent, and an optional processing aid, and granulating to obtain a granulated material;

[0039] (2) adding the granulated material into an extruder, heating, melting, and extruding to a die;

[0040] (3) The continuous fiber is drawn out from the constant tension creel, and after constant pre-tension, combing device, online sizing agent wrapping treatment, drying, and tensioning process, the uniformly spread continuous fiber reaches the extruder die head;

[0041] (4) The resin melt extruded from the die head is evenly coated on the evenly spread continuous fibers. The continuous fibers coated with the melt pass through a plurality of heated staggered parallel impregnation rollers. Under the action of the impregnation rollers, the melt moves up and down along the flat continuous fibers, and is evenly wrapped on the continuous fibers.

[0042] (5) The impregnated continuous fibers are fed into a cooling and shaping roller system to become a continuous fiber reinforced composite prepreg tape with a smooth appearance, and finally wound up by a winding system;

[0043] (6) Pre-treating the continuous fiber reinforced composite material prepreg tape by electron beam irradiation to obtain the continuous fiber reinforced composite material.

[0044] Preferably, the granulation in step (1) is carried out in a twin-screw extruder.

[0045] Preferably, the extruder in step (2) is a single-screw extruder.

[0046] Preferably, the plurality of groups in step (4) are at least two groups, such as two groups, three groups, four groups, six groups, etc.

[0047] Preferably, in the electron beam irradiation pretreatment in step (6), irradiation parameters include: voltage of 350-500KeV, for example, 350KeV, 360KeV, 380KeV, 400KeV, 420KeV, 440KeV, 460KeV, 480KeV, 500KeV, etc., and dose of 40-180KGy, for example, 40KGy, 60KGy, 80KGy, 100KGy, 120KGy, 140KGy, 160KGy, 180KGy, etc.

[0048] In the present invention, the step of electron beam irradiation pretreatment can improve the mechanical strength, heat resistance and weather resistance of the composite material.

[0049] In the present invention, a single-layer continuous fiber reinforced composite material can also be laid in multiple layers as required. The specific method is as follows: a single-layer continuous fiber reinforced composite material layer is stacked and hot-pressed at an angle of 0-90° (for example, 0, 10°, 20°, 30°, 40°, 50°, 60°, 70°, 80°, 90°, etc.) between adjacent fiber bundles to obtain a multi-layer continuous fiber reinforced composite material.

[0050] In a third aspect, the present invention provides an application of the continuous fiber reinforced composite material as described in the first aspect in photovoltaic and new energy vehicles.

[0051] Compared with the prior art, the present invention has at least the following beneficial effects:

[0052] The continuous fiber reinforced composite material provided by the present invention uses a high melt index resin as a matrix, continuous fibers as a reinforcing material, and is cross-linked by electron beam irradiation, so that the composite material not only has high mechanical strength, but also has high heat resistance and high weather resistance, thereby expanding the application range of the continuous fiber reinforced composite material. DETAILED DESCRIPTION

[0053] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0054] Unless otherwise specified, some of the raw materials used in the following examples and comparative examples of the present invention are as follows:

[0055] PE resin: The melt index at 190°C and 2.16kg is 100g / 10min;

[0056] EVA resin: The melt index at 190°C and 2.16kg is 150g / 10min;

[0057] Continuous glass fiber: SE4805, Owens Corning, USA;

[0058] Continuous carbon fiber: Carbon fiber tow, 1.5k, Anisoprint, Moscow;

[0059] PE grafted with maleic anhydride: W1H;

[0060] Wetting agent: AH-1618.

[0061] Example 1

[0062] In this embodiment, a continuous fiber reinforced composite material is provided. The raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight:

[0063]

[0064] The preparation method comprises the following steps:

[0065] (1) fully mixing all the above raw materials in a high-speed mixer and granulating them through a twin-screw extruder to obtain granulated materials;

[0066] (2) The granulated material is sucked into the hopper of the single screw extruder by the vacuum feeder, heated, melted, and accurately metered by the extruder to be transported to the die head;

[0067] (3) The glass fiber is unwound from the unwinding rack, and after pre-tensioning, combing, online sizing agent wrapping, drying, and tensioning, the glass fiber is evenly spread to the extruder die head;

[0068] (4) The resin melt extruded from the die head is evenly coated on the evenly spread continuous glass fibers, and the melt is evenly wrapped on the continuous glass fibers through multiple sets of heated staggered parallel impregnation rollers, and then impregnated, cooled, pulled, trimmed and rolled to obtain a continuous glass fiber reinforced composite prepreg tape;

[0069] (5) finally performing electron beam irradiation pretreatment on the above material to obtain the continuous fiber reinforced composite material;

[0070] Wherein, in the electron beam irradiation pretreatment, the irradiation voltage is 430KeV and the dose is 120KGy.

[0071] Example 2

[0072] In this embodiment, a continuous fiber reinforced composite material is provided. The raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight:

[0073]

[0074] The preparation method is similar to that of Example 1, except that, in the electron beam irradiation pretreatment, the irradiation voltage is 400 KeV and the dose is 90 KGy.

[0075] Example 3

[0076] In this embodiment, a continuous fiber reinforced composite material is provided. The raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight:

[0077]

[0078] The preparation method is similar to that of Example 1, except that, in the electron beam irradiation pretreatment, the irradiation voltage is 400 KeV and the dose is 150 KGy.

[0079] Comparative Example 1

[0080] In this comparative example, a continuous fiber reinforced composite material is provided. The raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight:

[0081]

[0082] The preparation method is similar to that of Example 1, except that the step of electron beam irradiation pretreatment is not included.

[0083] Comparative Example 2

[0084] The only difference between this comparative example and Example 1 is that the PE resin is replaced by an equal weight portion of SP1071C (PE resin, melt index is 10 g / 10 min).

[0085] The continuous fiber reinforced composite materials provided in the examples and comparative examples were tested for performance, and the test method was as follows:

[0086] (1) Heat resistance: Place the continuous fiber reinforced composite material sample in an oven at 200°C for 3 h. If the sample does not deform, it is judged as "OK", otherwise it is judged as "NG";

[0087] (2) Tensile strength: tested in accordance with GB13022;

[0088] (3) PCT 48h appearance: The specific conditions of PCT aging are: 121°C, 1 atmosphere, 100% humidity. After aging, if the sample is not deformed, it is judged as "OK", otherwise it is judged as "NG".

[0089] The performance test results are shown in Table 1.

[0090] Table 1

[0091] Heat resistance Tensile strength(MPa) PCT 48h Appearance Example 1 OK 210 OK Example 2 OK 170 OK Example 3 OK 180 OK Comparative Example 1 NG 100 OK Comparative Example 2 NG 120 NG

[0092] It can be seen from Table 1 that the continuous fiber reinforced composite materials provided by the embodiments of the present invention have relatively high mechanical strength (tensile strength: 170-210 MPa), and have high heat resistance and high weather resistance.

[0093] Compared with Example 1, the heat resistance of the continuous fiber reinforced composite materials provided by Comparative Examples 1 and 2 deteriorates, the tensile strength is significantly reduced, and the appearance of the continuous fiber reinforced composite material provided by Comparative Example 2 deteriorates after PCT 48h.

[0094] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the continuous fiber reinforced composite material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A continuous fiber reinforced composite material, characterized in that: The raw materials for preparing the continuous fiber reinforced composite material include the following components in parts by weight: Continuous fiber 20-80 parts; 20-80 parts of high melt index resin; 0.5-3 parts of anti-aging additives; The high melt index resin has a melt index of 30-150 g / 10 min.

2. The continuous fiber reinforced composite material according to claim 1, characterized in that: The high melt index resin includes any one of PP resin, PE resin, PC resin, EVA resin, EMA resin, EBA resin, EMMA resin, PA resin, ABS resin, PMMA resin, PVDF resin, ETFE resin, PVF resin, and epoxy resin, or a combination of at least two thereof; Preferably, the continuous fibers include any one of carbon fibers, glass fibers, aramid fibers, and basalt fibers, or a combination of at least two of them.

3. The continuous fiber reinforced composite material according to claim 1 or 2, characterized in that: The anti-aging aids include light stabilizers and / or antioxidants; Preferably, the light stabilizer includes any one of a light shielding agent light stabilizer, a quencher light stabilizer, a free radical scavenger light stabilizer, and a hydroperoxide decomposer light stabilizer, or a combination of at least two thereof; Preferably, the light stabilizer comprises UV770; Preferably, the antioxidant includes any one of hindered phenol antioxidants, aromatic amine antioxidants, phosphite antioxidants, thioether antioxidants, and metal passivator antioxidants, or a combination of at least two thereof; Preferably, the antioxidant includes antioxidant 1010 and / or antioxidant 168.

4. The continuous fiber reinforced composite material according to any one of claims 1 to 3, characterized in that: The raw materials for preparing the continuous fiber reinforced composite material also include a compatibilizer; Preferably, the compatibilizer includes cyclic anhydride grafts, carboxylic acid grafts, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, polyethylene grafted maleic anhydride, di- or ternary copolymers of glycidyl methacrylate and BA, MA, VA, or EA; Preferably, the amount of the compatibilizer is 0.1-20 parts.

5. The continuous fiber reinforced composite material according to any one of claims 1 to 4, characterized in that: The raw materials for preparing the continuous fiber reinforced composite material also include a cross-linking aid; Preferably, the auxiliary cross-linking agent includes any one of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, N,N'-p-phenyl bismaleimide, zinc diacrylate, zinc dimethacrylate, triallyl cyanurate, triallyl isocyanurate, and 1,2-polybutadiene, or a combination of at least two thereof; Preferably, the amount of the auxiliary cross-linking agent is 0.1-3 parts.

6. The continuous fiber reinforced composite material according to any one of claims 1 to 5, characterized in that: The raw materials for preparing the continuous fiber reinforced composite material also include processing aids; Preferably, the processing aid includes any one or a combination of at least two of silicone, calcium stearate, zinc stearate, oleamide, erucamide, and polyethylene wax; Preferably, the amount of the processing aid is 0.1-5 parts.

7. A method for preparing a continuous fiber reinforced composite material according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: (a) mixing a formula amount of a high melt index resin, an anti-aging aid, an optional compatibilizer, an optional co-crosslinking agent, and an optional processing aid, granulating, and then heating, melting, and extruding to a die; (b) drawing the continuous fiber from the constant tension creel to the die head; (c) coating the resin melt extruded from the die head on the unfolded continuous fibers, and then passing through a cooling and shaping roller system to obtain a continuous fiber reinforced composite prepreg tape; (d) pretreating the continuous fiber reinforced composite material prepreg tape by electron beam irradiation to obtain the continuous fiber reinforced composite material.

8. The preparation method according to claim 7, characterized in that: The preparation method comprises the following steps: (1) mixing a formulated amount of a high melt index resin, an anti-aging aid, an optional compatibilizer, an optional co-crosslinking agent, and an optional processing aid, and granulating to obtain a granulated material; (2) adding the granulated material into an extruder, heating, melting, and extruding to a die; (3) The continuous fiber is drawn out from the constant tension creel, and after constant pre-tension, combing device, online sizing agent wrapping treatment, drying, and tensioning process, the uniformly spread continuous fiber reaches the extruder die head; (4) The resin melt extruded from the die head is evenly coated on the evenly spread continuous fibers. The continuous fibers coated with the melt pass through a plurality of heated staggered parallel impregnation rollers. Under the action of the impregnation rollers, the melt moves up and down along the flat continuous fibers, and is evenly wrapped on the continuous fibers. (5) The impregnated continuous fibers are fed into a cooling and shaping roller system to become a continuous fiber reinforced composite prepreg tape with a smooth appearance, and finally wound up by a winding system; (6) Pre-treating the continuous fiber reinforced composite material prepreg tape by electron beam irradiation to obtain the continuous fiber reinforced composite material.

9. The preparation method according to claim 8, characterized in that: The granulation in step (1) is carried out in a twin-screw extruder; Preferably, the extruder in step (2) is a single screw extruder; Preferably, the plurality of groups in step (4) is at least two groups; Preferably, in the electron beam irradiation pretreatment in step (6), the irradiation parameters include: voltage of 350-500 KeV, and dose of 40-180 KGy.

10. Use of the continuous fiber reinforced composite material according to any one of claims 1 to 6 in photovoltaic and new energy vehicles.

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