A green novel nylon material and a preparation method thereof

Abstract

The application provides a green novel nylon material and a preparation method thereof, which comprises nylon 6, polypropylene, glass fiber, inorganic particles, modified compatilizer and the like, the modified compatilizer is prepared by blending polyacrylic acid, hydroxylated glass fiber and hydroxylated inorganic particles, ultrasonic heating, so that the glass fiber, the inorganic particles and the polyacrylic acid are crosslinked to form a product through a chemical bond, the obtained modified compatilizer contains polyacrylic acid groups on one hand, and the compatibility with polypropylene is good, meanwhile, the carboxyl groups can form hydrogen bonds with amide groups and the like in the nylon, on the other hand, the modified compatilizer also contains glass fiber and inorganic particles, and the polarity of the glass fiber and the inorganic particles is similar to that of a large amount of glass fiber and inorganic particles in the composite material, so that the bonding strength between the matrix resin and the filling material is strengthened, under the action of the modified compatilizer, the filling materials such as the toughening agent and polypropylene can form a synergistic effect, so that the application has better mechanical properties, chemical stability and thermal stability.

Description

Technical Field

[0001] This invention relates to the field of modified composite materials technology, specifically to a novel green nylon material and its preparation method. Background Technology

[0002] Nylon, as a high-performance engineering plastic, is widely used in automotive manufacturing, electronics, mechanical engineering, and packaging materials due to its good mechanical strength, abrasion resistance, processing fluidity, and cost advantages. However, pure nylon 6 (PA6) has its own performance shortcomings: such as insufficient toughness, making it difficult to meet the mechanical requirements of high-end structural components; strong hygroscopicity, easily causing dimensional expansion and performance degradation after absorbing water, limiting its application in humid or watery environments; and the low heat distortion temperature of pure PA6, requiring improvement in stability under high-temperature conditions. Therefore, performance optimization of PA6 through filler modification (such as introducing reinforcing or functional phases) has become a key technological direction for expanding its application range.

[0003] Currently, polypropylene is commonly used in the industry to suppress the hygroscopicity of PA6. However, a study by Wu Qinghe et al. in "Engineering Plastics Applications" found that although adding polypropylene to PA6 can effectively improve its water absorption, its mechanical properties decrease significantly. Therefore, to obtain stronger mechanical properties for PA6, compounding PA6 with inorganic particles and glass fibers is a common method in engineering plastics. However, glass fibers and inorganic particles usually have poor compatibility with PA6 and weak interfacial bonding, which can actually lead to a decrease in performance.

[0004] To address the aforementioned compatibility issues, existing technologies often employ compatibilizers to improve interfacial bonding. Commonly used types include maleic anhydride-grafted polyolefins and silane coupling agents. However, these traditional compatibilizers have significant limitations:

[0005] Maleic anhydride-grafted polyolefins are predominantly nonpolar polyolefin segments, which have poor compatibility with polar inorganic phases. Although maleic anhydride groups are polar, their interaction with the inorganic phase is weak hydrogen bonding and physical adsorption, resulting in weak adsorption capacity on the inorganic phase surface and difficulty in forming a uniform and robust interfacial bonding layer. While silane coupling agents can react with inorganic phases, their compatibility with polyolefins (PAs) is poor, easily forming a "weak boundary layer" at the interface, thus limiting the improvement in the mechanical properties of the composite material.

[0006] In conclusion, a new technical solution is urgently needed to address the problems existing in the current technology. Summary of the Invention

[0007] To address the shortcomings and deficiencies of the existing technology, this invention provides a novel green nylon material and its preparation method. This invention improves the physical properties of PA6 by adding polypropylene, inorganic particles, and glass fibers, and optimizes interfacial bonding using a modified compatibilizer. The novel green nylon material prepared by this invention effectively improves the hydrophobicity and strength of nylon composite materials.

[0008] One objective of this invention is to provide a novel green nylon material, which comprises the following components in parts by weight:

[0009]

[0010]

[0011] The modified compatibilizer is a product obtained by blending polyacrylic acid and hydroxylated glass fiber with hydroxylated inorganic particles and then ultrasonically heating it.

[0012] Furthermore, the polyacrylic acid is selected from polyacrylic acid with a molecular weight of 2000-6000.

[0013] Furthermore, the inorganic particles are selected from one or more of the following: metals, metal oxides, metal hydroxides, silicon dioxide, boron nitride, and silicon carbide.

[0014] Furthermore, the polypropylene is selected from polypropylene with a molecular weight of 80,000-150,000.

[0015] Furthermore, the toughening agent is obtained by reacting ethylene-1-octene copolymer, polypropylene, ethylene-acrylic acid copolymer and maleic anhydride.

[0016] The polypropylene molecular chain in this invention is composed of nonpolar carbon-carbon single bonds and carbon-hydrogen bonds. When PA6 is blended with polypropylene, polypropylene, as a nonpolar dispersed phase, is interspersed between the PA6 molecular chains, physically separating the polar regions of PA6, reducing the probability of contact between amide bonds and water molecules. Under the action of the modified compatibilizer, it forms a uniform and sufficient bond with glass fiber and inorganic particles, thereby further reducing the hygroscopicity of the composite material.

[0017] Another object of the present invention is to provide a method for preparing a novel green nylon material, the method comprising the following steps:

[0018] S1. Hydroxylating glass fiber and inorganic particles to obtain hydroxylated glass fiber and hydroxylated inorganic particles;

[0019] S2. Blend hydroxylated glass fiber, hydroxylated inorganic particles and polyacrylic acid, add catalyst, and heat and react under ultrasonic conditions to obtain modified compatibilizer;

[0020] S3. Mix the modified compatibilizer with the remaining components, melt-extrude, and obtain a new type of green nylon material.

[0021] Further, in step S2, the mass ratio of the polyacrylic acid, hydroxylated glass fiber and hydroxylated inorganic particles is (10-25):(5-7):(2-4).

[0022] Furthermore, in step S2, the temperature of the heating reaction is 60-100℃.

[0023] Furthermore, in step S3, the temperature of the melt extrusion is 220-250°C.

[0024] The present invention has the following beneficial effects:

[0025] This invention provides a novel green nylon material comprising nylon 6, polypropylene, glass fiber, inorganic particles, and a modified compatibilizer. The modified compatibilizer is a product obtained by blending polyacrylic acid, hydroxylated glass fiber, and hydroxylated inorganic particles, followed by ultrasonic heating. This process crosslinks the glass fiber and inorganic particles with the polyacrylic acid through chemical bonds. The resulting modified compatibilizer contains polyacrylic acid groups, exhibiting good compatibility with polypropylene. Simultaneously, its carboxyl groups can form hydrogen bonds with amide groups and other groups in nylon. Furthermore, it contains glass fiber and inorganic particles, which have similar polarity and good affinity to the abundant glass fiber and inorganic particles in the composite material. This enhances the compatibility between various components and strengthens the bonding strength between the matrix resin and the filler material, resulting in improved mechanical properties, chemical stability, water resistance, and thermal stability.

[0026] Meanwhile, the present invention also uses ethylene-1-octene copolymer, polypropylene, ethylene-acrylic acid copolymer and maleic anhydride to react to obtain a toughening agent. This material has good compatibility with nylon and polypropylene. Under the action of the modified compatibilizer, it can further form a cross-linked structure with glass fiber and inorganic particles. Thus, multiple components can form a synergistic effect and improve the comprehensive performance of green new nylon material. Detailed Implementation

[0027] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0028] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0029] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0030] In the examples and comparative examples, the following raw materials were used:

[0031] Nylon 6, grade CM1026, was purchased from Dongguan Tianniu Plastic Raw Materials Co., Ltd.

[0032] Polypropylene, grade HP500N, with a molecular weight of approximately 80,000-150,000, was purchased from Dongguan Ruijiahu Plastics Co., Ltd.

[0033] Polyacrylic acid, with a molecular weight of approximately 2000-5000, was purchased from Shanghai Haohong Biomedical Technology Co., Ltd.

[0034] The fiberglass, brand name ER13-2000-988A, was purchased from Jushi Group.

[0035] Inorganic particles, nano-titanium dioxide, with a particle size ≤100nm.

[0036] The toughening agent is prepared in-house, and the preparation method includes the following steps: 60 parts of ethylene-1-octene copolymer, 30 parts of polypropylene, 8 parts of ethylene-acrylic acid copolymer, 0.8 parts of maleic anhydride, and 0.2 parts of dicumyl peroxide are mixed evenly and added to the main feed port of the extruder. Then, 0.8 parts of maleic anhydride and 0.2 parts of dicumyl peroxide are added through the side feed port. The mixture is extruded and granulated at 180-200°C and dried to obtain the toughening agent described in this invention.

[0037] The antioxidant is antioxidant 1010.

[0038] The anti-aging agent is DPPD.

[0039] Example 1

[0040] A novel green nylon material comprises the following components in parts by weight:

[0041]

[0042] The preparation method of the green novel nylon material includes the following steps:

[0043] (1) Preparation of modified compatibilizer

[0044] S1. The inorganic particles were calcined at 500℃ for 1 hour, then added to a 2 mol / L sodium hydroxide solution and ultrasonically treated for 8 hours to obtain hydroxylated inorganic particles.

[0045] Glass fibers were treated at 450℃ for 1 hour, washed and dried, and then added to a 5 mol / L hydrochloric acid solution at 100℃ for 8 hours to obtain hydroxylated glass fibers.

[0046] S2. Using cyclohexane as a solvent, 6 parts of hydroxylated glass fiber and 3 parts of hydroxylated inorganic particles were placed in 10 parts of polyacrylic acid, and 0.2 parts of 4-dimethylaminopyridine were added. The mixture was heated to 80°C under ultrasonic conditions and reacted for 4 hours. After filtration and drying, the modified compatibilizer was obtained.

[0047] (2) Preparation of green novel nylon materials

[0048] S3. Mix the modified compatibilizer with nylon 6, polypropylene, glass fiber, inorganic particles, toughening agent, antioxidant, and anti-aging agent in the above-mentioned mass proportions, add the mixture to a twin-screw extruder, and melt-extrude at 240°C to obtain the product.

[0049] Example 2

[0050] A novel green nylon material comprises the following components in parts by weight:

[0051]

[0052]

[0053] The preparation method of the green novel nylon material includes the following steps:

[0054] (1) Preparation of modified compatibilizer

[0055] S1. The inorganic particles were calcined at 500℃ for 1 hour, then added to a 2 mol / L sodium hydroxide solution and ultrasonically treated for 8 hours to obtain hydroxylated inorganic particles.

[0056] Glass fibers were treated at 450℃ for 1 hour, washed and dried, and then added to a 5 mol / L hydrochloric acid solution at 100℃ for 8 hours to obtain hydroxylated glass fibers.

[0057] S2. Using cyclohexane as a solvent, 6 parts of hydroxylated glass fiber and 3 parts of hydroxylated inorganic particles were placed in 10 parts of polyacrylic acid, and 0.2 parts of 4-dimethylaminopyridine were added. The mixture was heated to 80°C under ultrasonic conditions and reacted for 4 hours. After filtration and drying, the modified compatibilizer was obtained.

[0058] (2) Preparation of green novel nylon materials

[0059] S3. Mix the modified compatibilizer with nylon 6, polypropylene, glass fiber, inorganic particles, toughening agent, antioxidant, and anti-aging agent in the above-mentioned mass proportions, add the mixture to a twin-screw extruder, and melt-extrude at 240°C to obtain the product.

[0060] Example 3

[0061] A novel green nylon material comprises the following components in parts by weight:

[0062]

[0063] The preparation method of the green novel nylon material includes the following steps:

[0064] (1) Preparation of modified compatibilizer

[0065] S1. The inorganic particles were calcined at 500℃ for 1 hour, then added to a 2 mol / L sodium hydroxide solution and ultrasonically treated for 8 hours to obtain hydroxylated inorganic particles.

[0066] Glass fibers were treated at 450℃ for 1 hour, washed and dried, and then added to a 5 mol / L hydrochloric acid solution at 100℃ for 8 hours to obtain hydroxylated glass fibers.

[0067] S2. Using cyclohexane as a solvent, 6 parts of hydroxylated glass fiber and 3 parts of hydroxylated inorganic particles were placed in 10 parts of polyacrylic acid, and 0.2 parts of 4-dimethylaminopyridine were added. The mixture was heated to 80°C under ultrasonic conditions and reacted for 4 hours. After filtration and drying, the modified compatibilizer was obtained.

[0068] (2) Preparation of green novel nylon materials

[0069] S3. Mix the modified compatibilizer with nylon 6, polypropylene, glass fiber, inorganic particles, toughening agent, antioxidant, and anti-aging agent in the above-mentioned mass proportions, add the mixture to a twin-screw extruder, and melt-extrude at 240°C to obtain the product.

[0070] Comparative Examples 1-2 are set up based on Example 1, and the difference from Example 1 is that:

[0071] In Comparative Example 1, the hydroxylated glass fibers in step S2 were replaced with hydroxylated inorganic particles, and the other components and preparation methods were the same as in Example 1.

[0072] In Comparative Example 2, the hydroxylated inorganic particles in step S2 were replaced with hydroxylated glass fibers, while the other components and preparation methods were the same as in Example 1.

[0073] Test case

[0074] The performance of the novel green nylon materials prepared in Examples 1-3 and Comparative Examples 1-2 was tested.

[0075] Test methods: Tensile strength, flexural strength, notched impact strength and water absorption were tested according to ASTM D638, ASTM D790, ASTM D256 and ASTM D570 standards respectively.

[0076] The sample was placed in an 80℃ oven for 30 days, and the tensile strength was tested again.

[0077] The test results are shown in Table 1.

[0078] Table 1 Performance Test Results

[0079]

[0080] Table 1 shows that the low water absorption glass fiber reinforced nylon material prepared in the examples has good mechanical properties, with excellent tensile strength, flexural strength, and notched impact strength. It also has lower water absorption and better thermal stability. Many of its properties are improved compared to comparative examples 1-2, which proves that in the technical solution of the present invention, the modified compatibilizer enhances the compatibility between inorganic particles, glass fibers, and PA6, thereby optimizing the various properties of the composite material. Furthermore, the material has significantly improved rigidity while also exhibiting good toughness.

[0081] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0082] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A green nylon material, characterized in that, The green nylon material comprises the following components in parts by weight: Nylon 6 40-60 parts 20-40 parts of polypropylene 30-50 parts glass fiber 5-15 parts of inorganic particles 4-8 parts toughening agent Antioxidant 1-5 parts Anti-aging agent 0.5-2 parts 5-10 parts of modified compatibilizer; The modified compatibilizer is a product obtained by blending polyacrylic acid and hydroxylated glass fiber with hydroxylated inorganic particles and then ultrasonically heating it. The inorganic particles are nano-titanium dioxide.

2. The green nylon material according to claim 1, characterized in that, The polyacrylic acid is selected from polyacrylic acid with a molecular weight of 2000-6000.

3. The green nylon material according to claim 1, characterized in that, The polypropylene is selected from polypropylene with a molecular weight of 80,000-150,000.

4. The green nylon material according to claim 1, characterized in that, The toughening agent is obtained by reacting ethylene-1-octene copolymer, polypropylene, ethylene-acrylic acid copolymer and maleic anhydride.

5. A method for preparing the green nylon material according to any one of claims 1-4, characterized in that, The preparation method of the green nylon material includes the following steps: S1. Hydroxylating glass fiber and inorganic particles to obtain hydroxylated glass fiber and hydroxylated inorganic particles; S2. Blend hydroxylated glass fiber, hydroxylated inorganic particles and polyacrylic acid, add catalyst, and heat and react under ultrasonic conditions to obtain modified compatibilizer; S3. Mix the modified compatibilizer with the remaining components, melt-extrude, and obtain green nylon material.

6. The method for preparing the green nylon material according to claim 5, characterized in that, In step S2, the mass ratio of the polyacrylic acid, hydroxylated glass fiber and hydroxylated inorganic particles is (10-25):(5-7):(2-4).

7. The method for preparing the green nylon material according to claim 5, characterized in that, In step S2, the temperature of the heating reaction is 60-100 °C.

8. The method for preparing the green nylon material according to claim 5, characterized in that, In step S3, the temperature of the melt extrusion is 220-250 ℃.

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