Basalt fiber reinforced POK composite material as well as preparation method and application thereof

Abstract

The invention discloses a basalt fiber reinforced POK composite material as well as a preparation method and application thereof, the composite material comprises the following raw material components in parts by weight: 55-90 parts of polyketone, 10-40 parts of basalt fiber, 0.2-0.5 part of an antioxidant, 0.3-0.6 part of a lubricant and 0.5-1.5 parts of a coupling agent; wherein the polyketone comprises low-viscosity resin with the molecular weight of 120000 to 140000 and medium-viscosity resin with the molecular weight of 170000 to 190000, and the mass ratio of the low-viscosity resin to the medium-viscosity resin is (0.5 to 1): (0.8 to 1.5). The basalt fiber reinforced polyketone composite material with excellent mechanical properties is developed by optimizing and screening types and proportions of polyketone materials, scientifically compounding the polyketone materials with basalt fibers and combining reasonable selection and proportion design of auxiliaries such as a coupling agent and the like, and the basalt fiber reinforced polyketone composite material has the remarkable characteristics of high strength, high temperature resistance, wear resistance, aging resistance and the like.

Description

Technical Field

[0001] This invention relates to the field of polyketone composite materials technology, and more specifically, to a basalt fiber reinforced POK composite material, its preparation method, and its application. Background Technology

[0002] Polyketone (POK), a highly crystalline polymer, has a tightly crystalline structure formed by hydrocarbons in its main chain. This results in excellent abrasion resistance, hydrolysis resistance, and chemical resistance, along with good flowability and processability. This green polymer material, synthesized from carbon monoxide and olefins, shows broad application prospects in the field of engineering plastics. However, the relatively low mechanical strength of pure POK resin limits its application in certain high-strength applications. To improve the mechanical properties of POK, it is usually necessary to modify it by adding reinforcing fibers.

[0003] Basalt fiber, the fourth largest high-tech fiber, is a continuous fiber made from natural basalt through high-temperature melting and drawing. Compared to carbon fiber and aramid fiber, basalt fiber not only possesses basic properties such as high strength and high modulus, but also exhibits excellent high-temperature resistance, oxidation resistance, radiation resistance, and good thermal and sound insulation effects. Its production process is environmentally friendly, and the product has a long lifespan, making it a cost-effective inorganic non-metallic material. Currently, basalt fiber is widely used in aerospace, automotive manufacturing, building reinforcement, and many other fields, demonstrating superior performance characteristics compared to glass fiber in many applications.

[0004] In the field of polymer-based composites, fiber reinforcement is an effective way to improve the mechanical properties of the matrix material. By combining high-performance fibers with a polymer matrix, key performance indicators such as strength, stiffness, and heat resistance can be significantly improved. The composite of basalt fiber and polymer has been applied in the modification of polymer materials, but systematic research on the composite of polyketone resin and basalt fiber is still relatively limited. Currently, there is a lack of novel composite materials with excellent mechanical properties that combine these two environmentally friendly materials.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a basalt fiber reinforced POK composite material, its preparation method, and its application, so as to improve the above-mentioned technical problems.

[0007] This invention is implemented as follows: In a first aspect, the present invention provides a basalt fiber reinforced POK composite material, which, by weight, comprises: 55-90 parts of polyketone, 10-40 parts of basalt fiber, 0.2-0.5 parts of antioxidant, 0.3-0.6 parts of lubricant, and 0.5-1.5 parts of coupling agent; wherein the polyketone comprises a low-viscosity resin with a molecular weight of 120,000-140,000 and a medium-viscosity resin with a molecular weight of 170,000-190,000, and the mass ratio of the low-viscosity resin to the medium-viscosity resin is (0.5-1):(0.8-1.5).

[0008] In an optional embodiment, the mass ratio of the low-viscosity resin to the medium-viscosity resin is (20~30):(25~50). And / or, the mass of the coupling agent is 0.8% to 1.2% of the total mass of the raw material components.

[0009] In an optional embodiment, the coupling agent is selected from γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-methacryloyloxypropyltrimethoxysilane. Preferably, the coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0010] In an optional embodiment, the basalt fiber is a short-cut basalt fiber with a fiber diameter of 5μm to 15μm.

[0011] In an optional embodiment, the antioxidant includes at least one of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant DEOXS80, antioxidant 9228, antioxidant 608, antioxidant 168, and antioxidant MD697.

[0012] In an optional embodiment, the lubricant includes at least one of silicone powder, calcium stearate, zinc stearate, pentaerythritol stearate, ethylene bis-stearamide, OP wax, TAF, talc, and PE wax.

[0013] Secondly, the present invention provides a method for preparing basalt fiber reinforced POK composite material as described in any of the foregoing embodiments, comprising: extruding, cooling, granulating, drying, and injection molding a mixture of the polyketone, the basalt fiber, the antioxidant, the lubricant, and the coupling agent according to the raw material composition ratio.

[0014] In an optional embodiment, the temperatures of the 11 zones of the twin-screw extruder are set to 145~155℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~35℃, 220~235℃, and 220~235℃, respectively, and the main extruder speed is 200~300 rpm.

[0015] Thirdly, the present invention provides the application of basalt fiber reinforced POK composite materials as described in any of the foregoing embodiments in the preparation of industrial parts in the fields of aerospace, petrochemical, automotive or construction.

[0016] Fourthly, the present invention provides an industrial component comprising the basalt fiber reinforced POK composite material described in any of the foregoing embodiments.

[0017] This invention offers the following advantages: By optimizing the selection and proportion of polyketone materials and scientifically compounding them with basalt fibers, while also considering the rational selection and proportioning of coupling agents and other additives, a basalt fiber-reinforced polyketone composite material with excellent mechanical properties has been successfully developed. This material exhibits significant characteristics such as high strength, high temperature resistance, wear resistance, and aging resistance. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a photograph of the composite material sample of Example 1 of the present invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0021] Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0022] In the description of this invention, the terms "comprising," "including," etc., mean "including but not limited to." In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between related objects, indicating that three relationships may exist; for example, A and / or B can represent: A alone, A and B simultaneously, or B alone. A and B can be singular or plural. In this document, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.

[0023] Some embodiments of the present invention provide a basalt fiber reinforced POK composite material, which, by weight, comprises: 55-90 parts of polyketone, 10-40 parts of basalt fiber, 0.2-0.5 parts of antioxidant, 0.3-0.6 parts of lubricant, and 0.5-1.5 parts of coupling agent; wherein, the polyketone comprises a low-viscosity resin with a molecular weight of 120,000-140,000 and a medium-viscosity resin with a molecular weight of 170,000-190,000, and the mass ratio of the low-viscosity resin to the medium-viscosity resin is (0.5-1):(0.8-1.5).

[0024] First, by selecting medium-to-low viscosity polyketone (POK) resin, its excellent flowability in the molten state allows for effective filling of complex mold cavities during molding, facilitating the processing and manufacturing of irregularly shaped components. Simultaneously, this type of resin can fully wet the fiber surface in the molten state, significantly reducing the agglomeration of basalt fibers during the composite process and improving fiber dispersion uniformity. Second, by compounding medium-to-low viscosity POK resin in a specific ratio, the flowability of molecular chain segments is further optimized, making it easier to penetrate into the microporous structure of the basalt fiber surface. Combined with a specific ratio of coupling agent for fiber surface treatment, the interfacial compatibility between the resin matrix and the fiber is significantly enhanced, resulting in a stronger interfacial bond and improving the overall performance of the composite material.

[0025] In some embodiments, in order to further improve the overall performance of the composite material, the mass ratio of low viscosity resin to medium viscosity resin was optimized, that is, the mass ratio of low viscosity resin to medium viscosity resin was (20~30):(25~50).

[0026] In some embodiments, polyketone POK is a polymer synthesized from carbon monoxide and olefins (ethylene, propylene), exemplarily designated as M130F and M330F, purchased from Hyosung Group of South Korea.

[0027] In some embodiments, the coupling agent is used at a mass of 0.8% to 1.2% of the total mass of the raw material components. At this dosage, the inorganic-loving ends of the coupling agent molecules can fully cover the hydroxyl groups on the fiber surface, while the organic-loving ends form physical entanglement or chemical bonding with the POK molecular chains, constructing a stable interface layer with optimal stress transfer efficiency. This avoids insufficient interfacial bonding due to too low a dosage or "molecular bridge" aggregation caused by too high a dosage. Simultaneously, the addition of 0.8% to 1.2% does not significantly increase melt viscosity, and when combined with medium-to-low viscosity POK, it can maintain good flowability and reduce mold filling defects; it also avoids the "inflection point decline" in mechanical properties (such as reduced impact strength) caused by excessive coupling agent.

[0028] Specifically, in some embodiments, the coupling agent is selected from γ-aminopropyltriethoxysilane (K550), γ-glycidoxypropyltrimethoxysilane (K560), or γ-methacryloyloxypropyltrimethoxysilane (K570). These three silane coupling agents share the same inorganic-philic end, a trimethoxy / triethoxysilyl group, which hydrolyzes to generate silanol groups (-Si-OH). These silanol groups can undergo dehydration condensation with the hydroxyl groups (-OH) on the surface of basalt fibers to form strong Si-O-Si chemical bonds, achieving interfacial bridging between the fiber and the matrix. Furthermore, none of the three coupling agents significantly increases the melt viscosity, exhibiting good processing compatibility with medium- and low-viscosity POK.

[0029] Preferably, the coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0030] In some embodiments, the basalt fibers are short-cut basalt fibers with a diameter of 5μm to 15μm. This 5μm to 15μm diameter is highly compatible with the addition of 0.8% to 1.2% coupling agent, allowing the silanol groups from the hydrolysis of the silane coupling agent to fully condense with the hydroxyl groups on the fiber surface, forming a complete interface layer and preventing agglomeration of fine-diameter fibers or insufficient interfacial bonding of coarse-diameter fibers. At a diameter of 8μm to 15μm, rigidity is superior, and the flexural modulus is increased more significantly. Fibers in this diameter range exhibit good dispersion in the POK matrix, effectively preventing crack propagation, improving tensile strength, and reducing fiber breakage defects caused by excessively fine fibers or difficulties in mold filling caused by excessively thick fibers. When matched with medium- to low-viscosity POK, it balances strength and toughness, avoiding a situation where one property is outstanding while another is lacking.

[0031] In some embodiments, the antioxidant includes at least one of antioxidants 1098, 1076, 1010, DEOXS80, 9228, 608, 168, and MD697. After oxidative degradation, POK generates chromophores such as carbonyl and carboxyl groups, causing the product to yellow; simultaneously, molecular chain crosslinking makes the material brittle. Antioxidants can block the formation of oxidized chromophores, maintaining the stability of the product's appearance; and reduce crosslinking reactions, maintaining the toughness of the composite material. The amount of antioxidant added should not exceed 0.5%, as excessive amounts can lead to precipitation (blooming), affecting the surface properties and interfacial bonding of the product.

[0032] In some embodiments, the lubricant includes at least one of silicone powder, calcium stearate, zinc stearate, pentaerythritol stearate, ethylene bis-stearamide, OP wax, TAF, talc, and PE wax. Low-to-medium viscosity POK itself has good flowability, but the addition of chopped basalt fibers (5-15 μm) can cause a slight increase in melt viscosity due to friction between the fibers and the matrix, easily leading to problems such as insufficient mold filling and obvious weld lines. The lubricant can form a lubricating layer between molecular chains or at the fiber-matrix interface, reducing the friction between the melt and the equipment's metal surface, and between the fibers and the POK molecular chains, thereby increasing the melt flow rate and making it suitable for injection molding of thin-walled, complex-cavity parts. It also reduces processing energy consumption and screw wear. In unlubricated systems, chopped basalt fibers are prone to agglomeration due to surface tension; the lubricant can coat the fiber surface, reducing the agglomeration force between fibers, and, in conjunction with the screw shearing action, achieving uniform fiber dispersion and avoiding increased mechanical property dispersion caused by fiber agglomeration. Meanwhile, the lubricant can work synergistically with the silane coupling agent (KH550 / KH560 / KH570) without damaging the interfacial bonding between the coupling agent and the fiber and matrix. Instead, it reduces fiber breakage caused by friction during processing, ensuring the reinforcement effect.

[0033] Furthermore, some embodiments of the present invention also provide a method for preparing basalt fiber reinforced POK composite material as described in any of the foregoing embodiments, comprising: extruding a mixture of polyketone, basalt fiber, antioxidant, lubricant and coupling agent through a twin-screw extruder, cooling, granulating, drying and injection molding according to the raw material composition ratio.

[0034] In some embodiments, the temperatures of the 11 zones of the twin-screw extruder are set to 145~155℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~35℃, 220~235℃, and 220~235℃, respectively, and the main extruder speed is 200~300 rpm.

[0035] Some embodiments of the present invention also provide the application of basalt fiber reinforced POK composite materials as described in any of the foregoing embodiments in the manufacture of industrial parts for the aerospace, petrochemical, automotive or construction industries.

[0036] Some embodiments of the present invention also provide an industrial component comprising the basalt fiber reinforced POK composite material described in any of the foregoing embodiments.

[0037] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0038] In the following examples and comparative examples, the polyketone POK used was M130F or M330F, purchased from Hyosung Group, South Korea; the basalt fiber was 316AC, with a diameter of 13μm, purchased from Zhejiang Shijin Basalt Fiber Co., Ltd.; the antioxidants used were DEOX S80 and 608, purchased from Qitai Technology Co., Ltd.; the lubricant was pentaerythritol stearic acid (PETS-AHS), purchased from Faji Group; and the silane coupling agent was purchased from Hangzhou Jessica.

[0039] Example 1 This invention provides a method for preparing basalt fiber reinforced POK composite material. The composition of the raw materials for this composite material is shown in Table 1, and the preparation steps include: POK resin, antioxidant, lubricant, and coupling agent are mixed at high speed according to the specified ratio, then extruded, cooled, granulated, dried, and injection molded into standard test strips to obtain basalt fiber reinforced POK composite material. Figure 1 As shown.

[0040] The temperatures of the 11 zones of the twin-screw extrusion stage are set to 150℃, 230℃, 230℃, 225℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, and 220℃ respectively, and the main extruder speed is 200 rpm.

[0041] Examples 2 to 8 The raw material components of Examples 2 to 8 are shown in Table 1, and their specific preparation methods are the same as those of Example 1.

[0042] Comparative Examples 1-2 The raw material components of Comparative Examples 1 and 2 are shown in Table 1, and their specific preparation methods are the same as those of Example 1.

[0043] Basalt fiber reinforced POK composite materials from the respective examples and comparative examples were injection molded into standard specimens, and their tensile strength, flexural strength, notched impact strength (simply supported beam), and final properties were tested. Specific testing methods were as follows: tensile strength was tested according to ISO 527 using a universal tensile testing machine; impact strength was tested according to ISO 180 using an impact testing machine; and flexural strength and flexural modulus were tested according to ISO 178 using a universal tensile testing machine.

[0044] The test results are shown in Table 1.

[0045] Table 1

[0046] Analysis of the data in Table 1 shows that incorporating basalt fiber into the POK resin system significantly improves the mechanical strength of the composite material and effectively enhances its heat resistance, wear resistance, and anti-aging properties. Experimental results indicate that the material strength continuously increases with the increase in the proportion of basalt fiber. Furthermore, adding an appropriate amount of coupling agent significantly strengthens the interfacial bonding between the fiber and the resin matrix, thereby further improving the composite material's strength; however, when the amount of coupling agent exceeds the optimal ratio, its reinforcing effect tends to saturate. By optimizing the amount of coupling agent added, a basalt fiber-reinforced POK composite material with excellent mechanical properties was successfully prepared.

[0047] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A basalt fiber reinforced POK composite material, characterized in that, By weight, its raw material components include: 55-90 parts of polyketone, 10-40 parts of basalt fiber, 0.2-0.5 parts of antioxidant, 0.3-0.6 parts of lubricant, and 0.5-1.5 parts of coupling agent; wherein, the polyketone comprises a low-viscosity resin with a molecular weight of 120,000-140,000 and a medium-viscosity resin with a molecular weight of 170,000-190,000, and the mass ratio of the low-viscosity resin to the medium-viscosity resin is (0.5-1):(0.8-1.5).

2. The basalt fiber reinforced POK composite material according to claim 1, characterized in that, The mass ratio of the low-viscosity resin to the medium-viscosity resin is (20~30):(25~50). And / or, the mass of the coupling agent is 0.8% to 1.2% of the total mass of the raw material components.

3. The basalt fiber reinforced POK composite material according to claim 1, characterized in that, The coupling agent is selected from γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane or γ-methacryloxypropyltrimethoxysilane; Preferably, the coupling agent is γ-glycidoxypropyltrimethoxysilane.

4. The basalt fiber reinforced POK composite material according to any one of claims 1 to 3, characterized in that, The basalt fiber is a short-cut basalt fiber with a fiber diameter of 5μm~15μm.

5. The basalt fiber reinforced POK composite material according to any one of claims 1 to 3, characterized in that, The antioxidants include at least one of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant DEOXS80, antioxidant 9228, antioxidant 608, antioxidant 168, and antioxidant MD697.

6. The basalt fiber reinforced POK composite material according to any one of claims 1 to 3, characterized in that, The lubricant includes at least one of the following: silicone powder, calcium stearate, zinc stearate, pentaerythritol stearate, ethylene bis-stearamide, OP wax, TAF, talc, and PE wax.

7. A method for preparing a basalt fiber reinforced POK composite material as described in any one of claims 1 to 6, characterized in that, It includes: according to the raw material composition ratio, extruding, cooling, granulating, drying and injection molding a mixture of the polyketide, the basalt fiber, the antioxidant, the lubricant and the coupling agent through a twin-screw extruder.

8. The method for preparing basalt fiber reinforced POK composite material according to claim 7, characterized in that, The temperatures of the 11 zones of the twin-screw extruder are set to 145~155℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~235℃, 220~35℃, 220~235℃, and 220~235℃ respectively, and the main extruder speed is 200~300 rpm.

9. The application of the basalt fiber reinforced POK composite material as described in any one of claims 1 to 6 in the preparation of industrial parts in the fields of aerospace, petrochemical, automotive or construction.

10. An industrial component, characterized in that, It contains the basalt fiber reinforced POK composite material as described in any one of claims 1 to 6.

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