A carbon fiber reinforced acid and alkali resistant PPS material and its preparation method

Abstract

The present invention provides a kind of carbon fiber reinforced acid and alkali resistant PPS material, the carbon fiber reinforced acid and alkali resistant PPS material includes the following components by mass fraction: 40 80 parts of PPS, 5 10 parts of modified carbon fibers, 1 5 parts of modified glass fibers, 1 5 parts of coupling agents, 1 5 parts of antioxidants, 1 10 parts of lubricants. The modified carbon fibers of the present invention have phenylene sulfide structure and star-shaped structure, have good compatibility with other components, can form more regular, tight three-dimensional network structure with other components, strengthen the stability of product, realize the lifting of the multiple performances such as mechanical property, acid and alkali resistance. Meanwhile, the present invention, by introducing phenylene sulfide structure and benzyl alcohol structure in modified glass fibers, effectively improves interfacial compatibility and bonding strength, enhances the compatibility with other components, makes the combination between components tighter, thus further enhancing the dispersibility and stability of system, improves the performance of PPS material.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a carbon fiber reinforced acid and alkali resistant PPS material and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS), a high-performance engineering plastic, plays an important role in a variety of fields, including aerospace, electronics, and the automotive industry, due to its outstanding properties such as high temperature resistance, corrosion resistance, insulation, and low moisture absorption. However, with the advancement of science and technology and industrial development, the performance requirements for PPS materials are increasing. Although PPS itself possesses a series of excellent properties, its inherent performance limitations still exist, which to a certain extent restricts its application potential in a wider range of fields. Therefore, modifying and enhancing PPS materials to meet the demand for higher performance has become an important research direction in the field of materials science.

[0003] Modifying PPS to enhance its performance has become a common practice in the existing technology. Among these, the use of carbon fiber reinforced PPS materials is particularly popular. This composite material demonstrates significant performance improvements in several key areas, including mechanical strength, thermal stability, corrosion resistance, aging resistance, and flame retardancy. The addition of carbon fiber significantly enhances the toughness and strength of PPS, making it a preferred composite material for high-end applications such as aerospace. Furthermore, the addition of carbon fiber significantly improves the impact resistance of PPS composites, effectively absorbing external impact energy and thus increasing the material's load-bearing capacity.

[0004] However, despite the progress made in the performance of carbon fiber reinforced PPS materials, they still face some challenges, such as further improvement in mechanical properties and acid and alkali resistance to meet the application requirements of high performance and extreme chemical environments. Therefore, the development of a carbon fiber reinforced PPS material with both excellent mechanical properties and excellent acid and alkali resistance is of great significance for expanding its application range and enhancing its market competitiveness.

[0005] In summary, it is necessary to develop a new technical solution to solve the problems existing in the existing technology. Summary of the Invention

[0006] The present invention provides a carbon fiber reinforced acid and alkali resistant PPS material, which is prepared from PPS, modified glass fiber, a star-shaped phenylene sulfide compound, modified carbon fiber, and the like. The present invention combines oxidized carbon fiber and a star-shaped phenylene sulfide compound to obtain a modified carbon fiber, which is added to a PPS material to effectively improve the performance of the PPS material. On the one hand, the modified carbon fiber has a phenylene sulfide structure, which has good compatibility with components with similar structures such as PPS and modified glass fiber, and can effectively improve the dispersibility of the components; on the other hand, the modified carbon fiber has a star-shaped structure, which gives the modified carbon fiber a larger specific surface area and multiple side chains radiating from the central core, which can enhance the contact area between the modified carbon fiber and other components. At the same time, it has multiple active sites and can form a more regular and compact three-dimensional network structure with other components, thereby enhancing the stability of the product and achieving improvements in various properties such as mechanical properties and acid and alkali resistance. At the same time, the present invention effectively improves the interface compatibility and bonding strength by introducing phenylene sulfide structure and benzyl alcohol structure into the modified glass fiber, enhances the compatibility with other components, and makes the combination between the components tighter, thereby further enhancing the dispersibility and stability of the system and improving the performance of the PPS material.

[0007] One object of the present invention is to provide a carbon fiber reinforced acid and alkali resistant PPS material, wherein the carbon fiber reinforced acid and alkali resistant PPS material comprises the following components in parts by mass:

[0008]

[0009] in,

[0010] The modified carbon fiber is a star-shaped phenylene sulfide compound modified carbon fiber;

[0011] The modified glass fiber is a hydroxylated glass fiber, which is partially grafted with 3,3'-dicarboxyl diphenyl disulfide and partially grafted with p-hydroxybenzoic acid.

[0012] Furthermore, the coupling agent is selected from one or more of silane, titanate, phosphate, chromium complex or zirconium coupling agents.

[0013] Furthermore, the antioxidant is selected from one or more of antioxidant 245, antioxidant 1076 or antioxidant 168.

[0014] Furthermore, the lubricant is selected from one or more of zinc stearate and silicone powder.

[0015] Another object of the present invention is to provide a method for preparing the above-mentioned carbon fiber reinforced acid and alkali resistant PPS material, comprising the following steps:

[0016] S1, soaking carbon fiber in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, heating and stirring to react, to obtain oxidized carbon fiber;

[0017] S2, mixing p-aminothiophenol with acetic anhydride, heating and stirring to react, to obtain p-acetaminothiophenol; mixing the p-acetaminothiophenol with hexabromobenzene, adding N,N-dimethylformamide under inert gas and low temperature conditions, stirring, and then adding sodium hydride to react; after the reaction is completed, adding HCl solution under low temperature conditions, and then adding water to precipitate to obtain a star-shaped phenylene sulfide compound;

[0018] S3, blending the oxidized carbon fiber and the star-shaped phenylene sulfide compound, and reacting them by ultrasonic heating to obtain modified carbon fiber;

[0019] S4, soaking the glass fiber in hydrogen peroxide, heating and stirring to react, to obtain hydroxylated glass fiber; blending the hydroxylated glass fiber with 3,3'-dicarboxyl diphenyl disulfide, and ultrasonically heating to react, to obtain an intermediate product; blending the intermediate product with p-hydroxybenzoic acid, and ultrasonically heating to react, to obtain a modified glass fiber;

[0020] S5. Blend the modified PPS, coupling agent, lubricant and antioxidant, and feed them from the main feeding port of the extruder; feed the modified carbon fiber from the first side feeding port of the extruder barrel; feed the modified glass fiber from the second side feeding port of the extruder barrel; and blend and granulate them through the extruder to obtain the carbon fiber reinforced acid and alkali resistant PPS material.

[0021] Furthermore, in step S2, the mass ratio of p-aminothiophenol to acetic anhydride is 1:(1-3); the mass ratio of p-acetaminothiophenol, hexabromobenzene and sodium hydride is 1:(2-4):(0.1-0.5).

[0022] Furthermore, in step S4, the mass ratio of the hydroxylated glass fiber, 3,3'-dicarboxydiphenyl disulfide and p-hydroxybenzoic acid is 1:(0.5-2):(0.1-1).

[0023] Furthermore, in step S1, the heating temperature is 50-70°C.

[0024] Furthermore, in step S2, the heating temperature is 50-70°C.

[0025] Furthermore, in step S3, the heating temperature is 50-70°C.

[0026] Furthermore, in step S4, the heating temperature is 60-100°C.

[0027] The present invention has the following beneficial effects:

[0028] The present invention obtains modified carbon fiber by reacting oxidized carbon fiber and star-shaped phenylene sulfide compound whose terminal group is carboxyl, and adds to PPS material, can effectively improve the performance of PPS material. On the one hand, modified carbon fiber has phenylene sulfide structure, has good compatibility with components with similar structure such as PPS and modified glass fiber, can effectively improve the dispersibility of component; On the other hand, modified carbon fiber has star-shaped structure, and this structure makes modified carbon fiber have larger specific surface area, and multiple side chains radiating from central core, can enhance the contact area between modified carbon fiber and other components, has multiple active sites at the same time, can form more regular, tight three-dimensional network structure with other components, strengthen product stability, realize the improvement of multiple performances such as mechanical property, acid and alkali resistance. At the same time, the present invention effectively improves interfacial compatibility and bonding strength by introducing phenylene sulfide structure and benzyl alcohol structure in modified glass fiber, enhances compatibility with other components, makes the combination between components tighter, thereby further enhancing the dispersibility and stability of system, improves the performance of PPS material. DETAILED DESCRIPTION

[0029] In order to more clearly illustrate the technical solutions of the present invention, the following examples are given. Unless otherwise stated, the raw materials, reactions and post-processing methods mentioned in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0030] The terms "preferred," "preferably," "more preferred," and the like, used herein, refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0031] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

[0032] The following raw materials were used in the examples and comparative examples of the present invention:

[0033] PPS was purchased from Shanghai Yuanye Biotechnology Co., Ltd. with an average molecular weight of 10,000.

[0034] Glass fiber was purchased from Shanghai MacLean Biochemical Technology Co., Ltd. with the brand number F864783.

[0035] Carbon fiber was purchased from Toray New Materials (Guangdong) Co., Ltd. with the brand name T700.

[0036] The coupling agent is silane coupling agent KH550.

[0037] The lubricant is zinc stearate.

[0038] The antioxidant is antioxidant 245.

[0039] Example 1

[0040] A carbon fiber reinforced acid and alkali resistant PPS material, comprising the following components in parts by mass:

[0041]

[0042] The preparation method of the carbon fiber reinforced acid and alkali resistant PPS material comprises the following steps:

[0043] S1. Immerse the carbon fiber in a mixed solution of concentrated sulfuric acid and concentrated nitric acid (concentrated sulfuric acid: concentrated nitric acid = 3:1, v / v), stir and react at 60°C for 4 hours, filter, wash, and dry to obtain oxidized carbon fiber;

[0044] S2. Add 15.5g of p-aminothiophenol to 45mL of distilled water, heat to 60°C, then add 18g of acetic anhydride under stirring and react for 15min, cool, filter, wash, and dry to obtain p-acetaminothiophenol; add 1.2g of the p-acetaminothiophenol and 2.85g of hexabromobenzene to a reaction bottle equipped with a condenser and blend, evacuate and fill with nitrogen, place in an ice bath, and turn on the condensed water, then add 25mL of dried N, N-dimethylformamide, stir, add 0.35g of sodium hydride, turn off the condensed water after the reaction system temperature drops to room temperature, evacuate the ice bath, and stir at room temperature for 3 days. After the reaction is completed, cool it to 0°C, add 50mL of freshly prepared 1mol / L ice HCl aqueous solution, then pour it into 200mL of double distilled water, precipitate, filter the precipitate, wash, and dry it to obtain a star-shaped phenylene sulfide compound;

[0045] S3. Using ethanol as a solvent, the oxidized carbon fiber and the star-shaped phenylene sulfide compound (oxidized carbon fiber: star-shaped phenylene sulfide compound = 1:1, m / m) were blended, stirred at 70° C. for 8 h, filtered, washed, and dried to obtain a modified carbon fiber;

[0046] S4. Soak 1 g of glass fiber in 10 mL of hydrogen peroxide, stir evenly, reflux at 105° C. for 3 h, filter, wash, and dry to obtain hydroxylated glass fiber; using methanol as a solvent, blend 5 g of the hydroxylated glass fiber with 5 g of 3,3'-dicarboxydiphenyl disulfide, ultrasonically react at 80° C. for 10 h, filter, wash, and dry to obtain an intermediate product; using methanol as a solvent, blend the intermediate product with 3 g of p-hydroxybenzoic acid, ultrasonically react at 80° C. for 10 h, filter, wash, and dry to obtain a modified glass fiber;

[0047] S5. Blend PPS, a coupling agent, an antioxidant, and a lubricant in the above-mentioned proportions by mass, and feed them from the main feed port of the extruder; feed the modified carbon fiber from the first side feed port of the extruder barrel; feed the modified glass fiber from the second side feed port of the extruder barrel; melt extrude at 310°C, with a screw extruder speed of 500 rpm and a pressure of 2 MPa, and obtain the carbon fiber reinforced acid and alkali resistant PPS material through melt extrusion and granulation.

[0048] Example 2

[0049] A carbon fiber reinforced acid and alkali resistant PPS material, comprising the following components in parts by mass:

[0050]

[0051] The preparation method of the above carbon fiber reinforced acid and alkali resistant PPS material is the same as that in Example 1.

[0052] Example 3

[0053] A carbon fiber reinforced acid and alkali resistant PPS material, comprising the following components in parts by mass:

[0054]

[0055] The preparation method of the above carbon fiber reinforced acid and alkali resistant PPS material is the same as that in Example 1.

[0056] Comparative Example 1

[0057] A carbon fiber reinforced acid- and alkali-resistant PPS material. The difference between this comparative example and Example 1 is that in step S5, the mass of the modified carbon fiber is replaced by a mixture of carbon fiber and a star-shaped phenylene sulfide compound (carbon fiber: star-shaped phenylene sulfide compound = 1:1, m / m), and the amounts of the remaining components and the preparation method are the same as those in Example 1.

[0058] Comparative Example 2

[0059] A carbon fiber reinforced acid and alkali resistant PPS material. The difference between this comparative example and Example 1 is that in step S5, the modified glass fiber and other qualities are replaced by the intermediate product, and the amounts of the remaining components and the preparation method are the same as those in Example 1.

[0060] Comparative Example 3

[0061] A carbon fiber reinforced acid and alkali resistant PPS material. The difference between this comparative example and Example 1 is that in step S4, the reaction between hydroxylated glass fiber and 3,3'-dicarboxydiphenyl disulfide is not carried out, and the amounts of other components and the preparation method are the same as those in Example 1.

[0062] Test Case

[0063] The carbon fiber reinforced acid and alkali resistant PPS materials prepared in Examples 1-3 and Comparative Examples 1-3 were dried in an oven at 140°C for 4 hours and then injection molded. The injection molded specimens were ASTM specimens, and the injection molding temperature was as follows: blanking section: 280-290°C; second section: 300-310°C; third section: 310-320°C; nozzle: 310-315°C; and mold temperature of the injection molded specimens: 120°C.

[0064] The above injection molded specimens were taken for the following performance tests.

[0065] Test method:

[0066] Tensile strength: tested in accordance with ISO527 standard;

[0067] Impact strength: tested in accordance with ISO179 standard;

[0068] Strength retention: The retention of tensile strength after the injection molded strips are immersed in acid / alkali at 93°C for 15 days.

[0069] The test results are shown in Table 1.

[0070] Table 1 Performance test results

[0071]

[0072] It can be seen from the above test results that the carbon fiber reinforced acid and alkali resistant PPS materials of Examples 1-3 of the present invention have good mechanical properties, and have excellent tensile strength retention under various acid and alkali conditions. All capabilities are significantly better than those of Comparative Examples 1-3 with replaced components, proving that in the technical scheme of the present invention, modified carbon fibers, modified glass fibers and components such as star-shaped phenylene sulfide compounds can interact with each other, enhance the dispersibility and stability of the system, and achieve improvements in various properties of the product, such as mechanical properties and acid and alkali resistance.

[0073] 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 embodied 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 illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0074] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A carbon fiber reinforced acid and alkali resistant PPS material, characterized in that: The carbon fiber reinforced acid and alkali resistant PPS material includes the following components in parts by mass: in, The modified carbon fiber is a star-shaped phenylene sulfide compound modified carbon fiber; The modified glass fiber is a hydroxylated glass fiber, which is partially grafted with 3,3'-dicarboxyl diphenyl disulfide and partially grafted with p-hydroxybenzoic acid.

2. The carbon fiber reinforced acid and alkali resistant PPS material according to claim 1, characterized in that: The coupling agent is selected from one or more of silane, titanate, phosphate, chromium complex or zirconium coupling agents.

3. The carbon fiber reinforced acid and alkali resistant PPS material according to claim 1, characterized in that: The antioxidant is selected from one or more of antioxidant 245, antioxidant 1076 or antioxidant 168.

4. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to any one of claims 1 to 3, characterized in that: The steps include: S1, soaking carbon fiber in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, heating and stirring to react, to obtain oxidized carbon fiber; S2, mixing p-aminothiophenol with acetic anhydride, heating and stirring to react, to obtain p-acetaminothiophenol; mixing the p-acetaminothiophenol with hexabromobenzene, adding N,N-dimethylformamide under inert gas and low temperature conditions, stirring, and then adding sodium hydride to react; after the reaction is completed, adding HCl solution under low temperature conditions, and then adding water to precipitate to obtain a star-shaped phenylene sulfide compound; S3, blending the oxidized carbon fiber and the star-shaped phenylene sulfide compound, and reacting them by ultrasonic heating to obtain modified carbon fiber; S4, soaking the glass fiber in hydrogen peroxide, heating and stirring to react, to obtain hydroxylated glass fiber; blending the hydroxylated glass fiber with 3,3'-dicarboxyl diphenyl disulfide, and ultrasonically heating to react, to obtain an intermediate product; blending the intermediate product with p-hydroxybenzoic acid, and ultrasonically heating to react, to obtain a modified glass fiber; S5. Blend the PPS, coupling agent, lubricant and antioxidant, and feed them from the main feeding port of the extruder; feed the modified carbon fiber from the first side feeding port of the extruder barrel; feed the modified glass fiber from the second side feeding port of the extruder barrel; and blend and granulate them through the extruder to obtain the carbon fiber reinforced acid and alkali resistant PPS material.

5. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S2, the mass ratio of p-aminothiophenol to acetic anhydride is 1:(1-3); the mass ratio of p-acetaminothiophenol, hexabromobenzene and sodium hydride is 1:(2-4):(0.1-0.5).

6. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S4, the mass ratio of the hydroxylated glass fiber, 3,3'-dicarboxydiphenyl disulfide and p-hydroxybenzoic acid is 1:(0.5-2):(0.1-1).

7. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S1, the heating temperature is 50-70°C.

8. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S2, the heating temperature is 50-70°C.

9. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S3, the heating temperature is 50-70°C.

10. The method for preparing the carbon fiber reinforced acid and alkali resistant PPS material according to claim 4, characterized in that: In step S4, the heating temperature is 60-100°C.

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