WO2019024224A1 - Glass fiber reinforced polyphenyl sulfide composite material and preparation method thereof - Google Patents

Abstract

Disclosed are a glass fiber-reinforced polyphenylene sulfide composite material and a preparation method therefor. A trace amount of gold potassium citrate and sodium tungstate effectively improve the creep resistance of glass fiber, thereby effectively improving the structural stability of the glass fiber, and avoiding dimensional instability and deformation of products caused by creep of the glass fiber. Due to the improvement of the creep resistance, the glass fiber can be applied to the manufacturing and production of automobile parts, electronic elements, instrument components, and aerospace equipment components with high precision requirements.

Description

 Glass fiber reinforced polyphenylene sulfide composite material and preparation method thereof

 [0001] The present invention relates to the technical field of polymer materials, and in particular to a glass fiber reinforced polyphenylene sulfide composite material and a preparation method thereof.

 Background technique

 [0002] Polyphenylene sulfide is a high-density polymer, which has higher impact resistance than ordinary plastic materials, and has the advantages of heat resistance and corrosion resistance. The glass fiber reinforced polyphenylene sulfide material is a kind of "strong and tough" material with high strength, high impact resistance and good dimensional stability. After adding glass fiber reinforced, it greatly improves its mechanical properties and heat resistance. Dimensional stability. In practical applications, it can replace plastics with plastics and replace engineering plastics to meet the requirements of light weapons packaging, automotive, and home appliances. However, the existing glass fiber materials have low intermolecular force, and the fibers are prone to large creep under the action of long intertwisting force, resulting in dimensional and morphological instability, which severely limits the glass fiber reinforced polyphenylene sulfide material. Many aspects are particularly applicable to automotive components, electronic components, instrumentation components, and aerospace components.

 [0003] In addition, the glass-filled polyphenylene sulfide composite material easily forms floating fibers during the injection molding process, resulting in a decrease in the strength of the composite material itself.

 technical problem

 [0004] A glass-filled polyphenylene sulfide composite material easily forms a floating fiber during an injection molding process, resulting in a decrease in the strength of the composite material itself.

 Problem solution

 Technical solution

 [0005] The object of the present invention is achieved by the following technical solutions: A glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0006] polyphenylene sulfide 80-100 parts;

 [0007] glass fiber 15-20 parts;

[0008] potassium citrate 0.005-0.007 parts; [0009] sodium tungstate 0.006-0.012 parts;

 [0010] 0.1-0.5 parts of hypophosphorous acid.

[0011] In the present invention, the polyphenylene sulfide and the glass fiber can be selected by any of the prior art. Gold Potassium Citrate is a chemical substance with a molecular formula of KAu ₂ N ₄ C1 ₂ H „ 0 ₈ . White crystalline powder, soluble in water, slightly soluble in alcohol, insoluble in ether. A prior art realization. Sodium tungstate, colorless crystal or white crystalline powder. Weathered in dry air, lost crystal water at 100 ° C. Soluble in water, insoluble in ethanol. Relative density 3.23~ 3.25. Melting point 698 °C (anhydrous). Used in mordants, analytical reagents, catalysts, water treatment agents, manufacture of fireproof, waterproof materials, and phosphotungstate, boron tungstate, etc. Hypophosphorous acid is a colorless oily liquid or deliquescent Crystalline. Density 1.493g/cm3. Melting point 26.5°C. Soluble in hot water, ethanol, ether. Soluble in cold water. When heated to 130°C, it will be decomposed into orthophosphoric acid and phosphine. It is a strong reducing agent. Sodium phosphate is treated by ion exchange resin, adsorbed, desorbed, filtered, and concentrated by evaporation. It can be used as a fungicide, a nervous system strongener, a metal surface treatment agent, and a catalyst and hypophosphite. The inventors found in the study that trace amounts of potassium citrate and sodium tungstate effectively improve the creep resistance of glass fiber, thereby effectively improving the structural stability of the glass fiber, and avoiding product size instability and deformation due to creep. Due to the increased creep resistance of glass fiber, it can be used in the manufacture of high-precision automotive parts, electronic components, instrumentation components, and aerospace components. In addition, the inventors found trace amounts of citric acid. The presence of bismuth in potassium and hypophosphorous acid can greatly improve the compatibility of glass fiber and polyphenylene sulfide material, so that the glass fiber can be uniformly mixed in the polyphenylene sulfide material, and the obtained polyphenylene sulfide composite material can be effectively improved. Mechanical properties.

 [0012] Further, the glass fiber is an anti-floating fiberglass fiber, and the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A. Adding 2 times the amount of ethylene glycol to the solution A, stirring to obtain the solution B; pouring the solution B into the hydrothermal reaction kettle, the filling degree is controlled at 70~80%; then sealing the hydrothermal reaction kettle , placed in an electric heating constant temperature blast oven, at a temperature of 140 ° C, reaction for 30h, after the end of the reaction, naturally cooled to room temperature; smash the hydrothermal reaction kettle, the product is washed with distilled water, anhydrous ethanol 1~ Three times, it was dried in an electric thermostatic blast drying oven at 96 ° C for 2 h to obtain the anti-floating fiberglass.

[0013] 3-Pyridinesulfonic acid can be selected using any of the prior art techniques. It can effectively inhibit the aggregation and floating of glass fiber in polyphenylene sulfide, avoiding the formation of protruding points on the surface of the product, and is beneficial for injection molding. The surface finish of the product. The uniform filling of the glass fiber in the polyphenylene sulfide material also contributes to the improvement of the notched impact strength of the polyphenylene sulfide material.

 [0014] The present invention also provides a method for preparing the glass fiber reinforced polyphenylene sulfide composite material, which comprises the following steps

[0015] According to the set weight parts, polyphenylene sulfide, glass fiber, potassium citrate, sodium tungstate, hypophosphorous acid is added to a high-speed mixer and uniformly mixed, and then heated to 190 to 200 ° C by a twin-screw extruder to obtain a plastic. The polyphenylene sulfide mixture, and then the plasticized polyphenylene sulfide mixture is extruded by a twin-screw extruder, and subjected to traction, cooling forming, and cutting to prepare a glass fiber reinforced polyphenylene sulfide composite having a length of 10-15 mm. material.

 [0016] The above preparation method can further increase the strength of the obtained composite material.

 Advantageous effects of the invention

 Beneficial effect

 [0017] The strength of the resulting composite material can be further increased.

 BEST MODE FOR CARRYING OUT THE INVENTION

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0018] This embodiment provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0019] 95 parts;

[0020] 18 parts of glass fiber;

[0021] potassium citrate 0.006 parts;

[0022] sodium tungstate 0.009 parts;

[0023] Hypophosphorous acid

[0024] Further, the glass fiber is an anti-floating fiberglass fiber, and the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A. Adding 2 times the amount of ethylene glycol to the solution A, stirring to obtain the solution B; pouring the solution B into the hydrothermal reaction kettle, the filling degree is controlled at 70~80%; then sealing the hydrothermal reaction kettle , placed in an electric heating constant temperature blast oven, at a temperature of 140 ° C, reaction for 30h, after the end of the reaction, naturally cooled to room temperature; smash the hydrothermal reaction kettle, the product is washed with distilled water, anhydrous ethanol 1~ Three times, it was dried in an electric thermostatic blast drying oven at 96 ° C for 2 h to obtain the anti-floating fiberglass. This embodiment is prepared using the prior art. Embodiments of the invention

 Embodiment 1

[0026] The embodiment provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0027] 95 parts;

[0028] 18 parts of glass fiber;

[0029] potassium citrate 0.006 parts;

[0030] sodium tungstate 0.009 parts;

[0031] Hypophosphorous acid

[0032] Further, the glass fiber is an anti-floating fiberglass fiber, and the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A. Adding 2 times the amount of ethylene glycol to the solution A, stirring to obtain the solution B; pouring the solution B into the hydrothermal reaction kettle, the filling degree is controlled at 70~80%; then sealing the hydrothermal reaction kettle , placed in an electric heating constant temperature blast oven, at a temperature of 140 ° C, reaction for 30h, after the end of the reaction, naturally cooled to room temperature; smash the hydrothermal reaction kettle, the product is washed with distilled water, anhydrous ethanol 1~ Three times, it was dried in an electric thermostatic blast drying oven at 96 ° C for 2 h to obtain the anti-floating fiberglass.

 Example 2

[0034] This embodiment provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0035] 80 parts;

[0036] 20 parts of glass fiber;

[0037] potassium citrate 0.005 parts;

[0038] sodium tungstate 0.012 parts;

[0040] Further, the glass fiber is a commercially available product. This embodiment is prepared using the prior art.

Embodiment 3

[0042] This embodiment provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0043] 100 parts of polyphenylene sulfide;

[0044] 15 parts of glass fiber; [0045] 0.007 parts of potassium citrate;

[0046] sodium tungstate 0.006 parts;

[0047] 0.5 parts '.

[0048] Further, the glass fiber is an anti-floating fiberglass fiber, and the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A. Adding 2 times the amount of ethylene glycol to the solution A, stirring to obtain the solution B; pouring the solution B into the hydrothermal reaction kettle, the filling degree is controlled at 70~80%; then sealing the hydrothermal reaction kettle , placed in an electric heating constant temperature blast oven, at a temperature of 140 ° C, reaction for 30h, after the end of the reaction, naturally cooled to room temperature; smash the hydrothermal reaction kettle, the product is washed with distilled water, anhydrous ethanol 1~ Three times, it was dried in an electric thermostatic blast drying oven at 96 ° C for 2 h to obtain the anti-floating fiberglass.

 [0049] This embodiment was prepared using the prior art.

Embodiment 4

[0051] This embodiment provides a glass fiber reinforced polyphenylene sulfide composite material, which is consistent with the first embodiment.

[0052] The method for preparing a glass fiber reinforced polyphenylene sulfide composite material according to the embodiment includes the following steps: [0053] polyphenylene sulfide, glass fiber, potassium gold citrate, tungsten according to a set weight Sodium and hypophosphorous acid are added to a high-speed mixer and uniformly mixed, and then heated to 190 to 200 ° C by a twin-screw extruder to obtain a plasticized polyphenylene sulfide mixture, and then the plasticized polyphenylene sulfide mixture is subjected to a twin-screw extruder. Extrusion, traction, cooling forming, cutting treatment to prepare a glass fiber reinforced polyphenylene sulfide composite material with a length of 10-15 mm.

 Comparative Example 1

[0055] The present comparative example provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0056] 95 copies;

[0057] 18 parts of glass fiber;

[0058] potassium citrate 0.006 parts;

[0059] sodium tungstate 0.009 parts;

[0060] Hypophosphorous acid

Comparative Example 2

[0062] The present comparative example provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

[0063] 95 parts; [0064] 18 parts of glass fiber;

 [0065] potassium citrate 0.006 parts;

 [0066] sodium phosphate, 0.009 parts;

 [0067] 0.2 parts of hypophosphorous acid.

 Comparative Example 3

 [0069] The present comparative example provides a glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:

 [0070] polyphenylene sulfide 95 parts;

 [0071] 18 parts of glass fiber;

 [0072] potassium citrate 0.006 parts;

 [0073] sodium tungstate 0.009 parts;

 [0074] 0.2 parts of orthophosphoric acid.

 [0075] The mechanical properties of the composite material are judged by the bending strength obtained by the test. The impact resistance of the material is characterized by two methods, one is characterized by the notched impact strength and the unnotched impact strength of the test material, and the other is by The material is made into a square plate of 150mm*150mm*3mm, and the square plate is supported by the support, with 0.

The 5KG ball hits the square plate from different heights and falls freely, observing how many heights of the square plate are cracked. In the case of the floating material of the composite material, the material is made into a square plate on a mold which is polished on the surface, and the surface is observed by a secondary phase detector.

The bending strength, impact properties and surface floatation of the examples and comparative examples were measured, and the test results are shown in Table 1.

[Table 1]

 [0077] Injection molding test.

[0078] The polyphenylene sulfide composite material was injection molded by the prior art, and formed into a 30 _C mx30 _C mx 30 cm square, and the surface floating fiber condition was observed. Cut the skin of 30 _C mx30cmx2 _C m on the 6 surfaces of the square, and obtain all the small squares to the epidermis; test the density difference between the epidermis and the small square. Density difference rate = (p skin-P small square) xl00<3⁄4

 [Table 2]

 [0079] Creep resistance test.

The polyphenylene sulfide composite materials of the examples and the comparative examples were formed into strips having a radius of 1 cm and a length of 20 cm. Long strip The tension of the B5000N is applied to both ends for 100 days. Test its length growth rate. The results are shown in Table 2.

[] [table 3]

 The above is a specific implementation of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It is to be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

 Industrial applicability

 [0082] Enter the paragraph of industrial applicability description here.

 Sequence table free content

 [0083] Type the sequence table free content description paragraph here.

Claims

Claim  [Claim 1] A glass fiber reinforced polyphenylene sulfide composite material, the raw materials of which include:  Polyphenylene sulfide 80-100 parts;  Glass fiber 15-20 parts;  Potassium citrate 0.005-0.007 parts;  Sodium tungstate 0.006-0.012 parts;  0.1-0.5 parts of hypophosphorous acid.  [Claim 2] The glass fiber reinforced polyphenylene sulfide composite material according to claim 1, wherein the glass fiber is an anti-floating fiberglass, and the preparation method is the method of immersing the glass fiber in deionized water. Adding 3-pyridine sulfonic acid with the mass of 5 times glass fiber to obtain solution A; adding ethylene glycol twice as much as glass fiber to solution A, stirring to obtain solution B; pouring solution B into water In the thermal reactor, the filling degree is controlled at 70~80%; then the hydrothermal reaction kettle is sealed, placed in an electric heating constant temperature blast oven, and reacted at a temperature of 140 ° C for 30 hours, and then naturally cooled to room temperature after the reaction is completed. The hydrothermal reaction kettle was blown, and the product was washed successively with distilled water and absolute ethanol for 1 to 3 times, and dried in an electric thermostatic blast drying oven at 96 ° C for 2 hours to obtain the anti-floating fiberglass.  [Claim 3] The method for producing a glass fiber reinforced polyphenylene sulfide composite material according to claim 1 or 2, which comprises the following steps:  Polyphenylene sulfide, glass fiber, potassium citrate, sodium tungstate, hypophosphorous acid are added to a high-speed mixer to be uniformly mixed according to the set weight, and then heated to 190 to 200 ° C by a twin-screw extruder to obtain a plasticized poly The phenyl sulfide mixture, and then the plasticized polyphenylene sulfide mixture is extruded by a twin-screw extruder, and is subjected to drawing, cooling forming, and cutting to prepare a glass fiber reinforced polymer having a length of 10-15 mm.