Conductive Wear-Resistant Polyphenylene Sulfide / Polyketone Composite Material and Preparation Method Thereof

Abstract

The present invention relates to a conductive wear-resistant polyphenylene sulfide / polyketone composite material and a preparation method thereof, and belongs to the technical field of polyphenylene sulfide composite material preparation. The composite material comprises the following raw materials in parts by weight: 30-70 parts of polyphenylene sulfide resin, 13-33 parts of polyketone resin, 8-15 parts of conductive agent, 35-100 parts of glass fiber, and 1-5 parts of auxiliary agent. The present invention imparts conductive properties to the final composite material by introducing a conductive agent into a PPS and POK mixed material system, and the conductive agent in the present invention is a binary copolymer of ethylene-quaternary ammonium salt monomer; the quaternary ammonium salt monomer is generated by quaternization reaction of 4-vinyl pyridine; it is known that the conductive agent is a quaternary ammonium salt polymer, which is an organic conductive agent with the characteristics of permanence and good miscibility, and imparts stable conductive properties to the obtained composite material.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of polyphenylene sulfide composite materials, and in particular relates to a conductive and wear-resistant polyphenylene sulfide / polyketone composite material and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS), short for polyphenylene sulfide, is a thermoplastic resin with phenylthio groups in its main chain. It exhibits crystalline properties and boasts high mechanical strength, high-temperature and chemical resistance, flame retardancy, good thermal stability, and excellent electrical properties. It is widely used in the electronics, automotive, machinery, and chemical industries. However, its poor toughness and brittleness limit its use in components requiring toughness.

[0003] Polyketone (POK) is a linear crystalline polymer obtained by alternating copolymerization of carbon monoxide and ethylene. It has excellent self-lubrication and impact resistance. Taking advantage of its impact resistance, it can be used as a filling resin material for polyphenylene sulfide to enhance the toughness of polyphenylene sulfide.

[0004] With the widespread application of polyphenylene sulfide materials, such as electronic shielding layers and electronic accessories, there are certain requirements for the conductivity of polyphenylene sulfide materials.

[0005] Therefore, in order to solve the above problems, the present invention provides a conductive and wear-resistant polyphenylene sulfide / polyketone composite material and a preparation method thereof. Summary of the Invention

[0006] The purpose of the present invention is to provide a conductive and wear-resistant polyphenylene sulfide / polyketone composite material and a preparation method thereof, so as to solve the following technical problems: improving the conductivity of the PPS / POK composite material.

[0007] The first object of the present invention can be achieved by the following technical solutions:

[0008] The conductive and wear-resistant polyphenylene sulfide / polyketone composite material comprises the following raw materials in parts by weight: 30-70 parts of polyphenylene sulfide resin, 13-33 parts of polyketone resin, 8-15 parts of conductive agent, 35-100 parts of glass fiber, and 1-5 parts of auxiliary agent.

[0009] Furthermore, the conductive agent is a binary copolymer of ethylene and quaternary ammonium salt monomers;

[0010] The quaternary ammonium salt monomer is generated by quaternization reaction of 4-vinylpyridine.

[0011] Furthermore, the binary copolymer of ethylene-quaternary ammonium salt monomer is obtained by:

[0012] The quaternary ammonium salt monomer, water and tert-butyl alcohol are uniformly mixed to obtain a first mixed solution;

[0013] The first mixed liquid is placed in a reactor, degassed by displacement with ethylene, pressurized with ethylene to a first target pressure, stirred and heated to a target temperature, an initiator solution is pumped into the reactor, stirred and reacted for a first period of time, and then pressurized with ethylene to a second target pressure, and the initiator solution is added. The second target pressure is maintained and stirred and reacted for a second period of time. The reaction is stopped, cooled, emptied, and post-treated to obtain a binary copolymer of ethylene and quaternary ammonium salt monomer.

[0014] Furthermore, the first target pressure is 4-6 MPa, the first time period is 1-2 hours, the second target pressure is 15-18 MPa, and the second time period is 5-10 hours.

[0015] Furthermore, the mass ratio of the quaternary ammonium salt monomer, water, and tert-butanol is 1:40-55:8-10; and the mass concentration of the initiator solution is 4-6%.

[0016] Furthermore, the initiator is one of potassium persulfate and ammonium persulfate, or a mixture of the two.

[0017] Furthermore, the quaternizing agent in the quaternization reaction is γ-chloropropyltriethoxysilane, and the molar ratio of the γ-chloropropyltriethoxysilane to the 4-vinylpyridine is 1-1.5:1.

[0018] Furthermore, in the quaternization reaction, the reaction temperature is 60-80° C. and the reaction time is 12-24 h in an organic solvent.

[0019] Furthermore, the organic solvent is one of benzene, toluene, dichloromethane, and N,N-dimethylformamide.

[0020] Furthermore, the auxiliary agent is an antioxidant and / or a lubricant.

[0021] The first object of the present invention can be achieved by the following technical solutions:

[0022] A method for preparing a conductive and wear-resistant polyphenylene sulfide / polyketone composite material, comprising:

[0023] The polyphenylene sulfide resin, polyketone resin, conductive agent, glass fiber and auxiliary agent are mixed, melt-blended and extruded, and granulated to obtain a composite material.

[0024] Beneficial effects of the present invention:

[0025] The conductive and wear-resistant polyphenylene sulfide / polyketone composite material of the present invention is endowed with conductive properties by introducing a conductive agent into a PPS and POK mixed material system. The conductive agent in the present invention is a binary copolymer of ethylene and a quaternary ammonium salt monomer; the quaternary ammonium salt monomer is produced by a quaternization reaction of 4-vinylpyridine. It can be seen that the conductive agent is a quaternary ammonium salt polymer, which is an organic conductive agent with the characteristics of permanence and good miscibility, and endows the resulting composite material with stable conductive properties.

[0026] Surprisingly, the quaternary ammonium salt unit in the molecular chain of the conductive agent in the present invention is a pyridinium nitrogen quaternary ammonium salt, wherein the pyridine ring has a π-π stacking effect with the benzene ring in PPS, and the polyethylene unit in its molecular chain has good compatibility with the ethylene chain in the POK molecular chain, and thus the conductive agent can also serve as a compatibilizer between PPS and POK molecules (PPS is a non-polar polymer, and POK is a polar polymer with poor compatibility);

[0027] Even more unexpectedly, the quaternary ammonium salt unit in the conductive agent of the present invention contains a siloxane chain, which acts as a coupling agent and has good wetting properties for glass fibers, allowing the glass fibers to be evenly dispersed in the blending system and improving the mechanical properties of the resulting composite material. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0029] Example 1

[0030] Preparation of conductive agent:

[0031] A1. Mix 0.1 mol of 4-vinylpyridine, 0.1 mol of γ-chloropropyltriethoxysilane, and 100 mL of benzene, stir and heat to 60°C, and keep stirring for 24 hours. Stop the reaction, rotary evaporate, wash, and dry to obtain a quaternary ammonium salt monomer;

[0032] A2, after quaternary ammonium salt monomer 20g, 800g water and 160g tributyl carbinol are mixed, obtain the first mixed solution; With the first mixed solution as in reactor, degas with ethylene replacement, and be pressurized to 4MPa with ethylene, be heated with stirring to 90 ℃, in reactor, pump into mass concentration and be 5% potassium persulfate solution (quality 2g of potassium persulfate), after stirring 1h, be pressurized to 16MPa with ethylene again, and supplement mass concentration and be 5% potassium persulfate solution (1g), in the reaction process, mend ethylene to remain under 16MPa, stirring reaction 10h, stopped reaction, cooling, emptying, add into the water and stir, then add 0.1M hydrochloric acid, stir at 40 ℃, cooling and ageing, filter, washing, drying, obtain the binary copolymer (being conductive agent) of ethylene-quaternary ammonium salt monomer.

[0033] Example 2

[0034] Preparation of conductive agent:

[0035] A1. Mix 0.1 mol of 4-vinylpyridine, 0.15 mol of γ-chloropropyltriethoxysilane, and 100 mL of benzene, stir and heat to 80°C, and keep stirring for 12 hours. Stop the reaction, rotary evaporate, wash, and dry to obtain a quaternary ammonium salt monomer;

[0036] A2, after quaternary ammonium salt monomer 20g, 1100g water and the 200g tributyl carbinol are mixed, obtain the first mixed solution; With the first mixed solution as in reactor, degas with ethylene replacement, and be pressurized to 6MPa with ethylene, be heated with stirring to 80 ℃, in reactor, pump into mass concentration and be 5% potassium persulfate solution (the quality 2g that contains potassium persulfate), after stirring 1h, be pressurized to 18MPa with ethylene again, and supplement mass concentration and be 5% potassium persulfate solution (the quality that contains 1g potassium persulfate), in the reaction process, mend ethylene to remain under 18MPa, stirring reaction 5h, stopped reaction, cooling, emptying, add into the water and stir, then add 0.1M hydrochloric acid, stir at 40 ℃, cooling and ageing, filter, washing, drying, obtain the binary copolymer (being conductive agent) of ethylene-quaternary ammonium salt monomer.

[0037] Example 3

[0038] Preparation of composite materials:

[0039] The first step includes the following raw materials in parts by weight: 30 parts of polyphenylene sulfide resin, 33 parts of polyketone resin, 8 parts of conductive agent, 40 parts of glass fiber, 1.5 parts of antioxidant 1010, and 1.5 parts of polyethylene wax;

[0040] In the second step, the polyphenylene sulfide resin, polyketone resin, conductive agent, glass fiber and auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material at an extrusion temperature of 245-280°C.

[0041] Example 4

[0042] Preparation of composite materials:

[0043] The first step includes the following raw materials in parts by weight: 60 parts of polyphenylene sulfide resin, 23 parts of polyketone resin, 10 parts of conductive agent, 50 parts of glass fiber, 1 part of antioxidant 1010, and 0.5 parts of polyethylene wax;

[0044] In the second step, the polyphenylene sulfide resin, polyketone resin, conductive agent, glass fiber and auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material at an extrusion temperature of 245-280°C.

[0045] Example 5

[0046] Preparation of composite materials:

[0047] The first step includes the following raw materials in parts by weight: 70 parts of polyphenylene sulfide resin, 13 parts of polyketone resin, 15 parts of conductive agent, 60 parts of glass fiber, 1 part of antioxidant 1010, and 1 part of polyethylene wax;

[0048] In the second step, the polyphenylene sulfide resin, polyketone resin, conductive agent, glass fiber and auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material at an extrusion temperature of 245-280°C.

[0049] Comparative Example 1

[0050] Preparation of composite materials:

[0051] Compared with Example 3, the conductive agent in the raw materials is deleted, and the rest is the same.

[0052] Comparative Example 2

[0053] Preparation of composite materials:

[0054] Compared with Example 3, an equal amount of the conductive agent in the raw materials is replaced with conductive carbon black, and the rest are the same.

[0055] Comparative Example 3

[0056] Compared with Example 3, an equal amount of the conductive agent in the raw materials was replaced with a compatibilizer (ethylene-acrylate-glycidyl methacrylate terpolymer), and the rest were the same.

[0057] The physical properties of the composite materials obtained in Examples 3-5 and Comparative Examples 1-2 were tested, and the results are shown in Table 1.

[0058] Table 1

[0059]

[0060] From the data in Table 1, it can be seen that the composite materials obtained in Examples 3-5 of the present invention have good toughness and electrical conductivity.

[0061] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0062] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. Conductive and wear-resistant polyphenylene sulfide / polyketone composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 30-70 parts of polyphenylene sulfide resin, 13-33 parts of polyketone resin, 8-15 parts of conductive agent, 35-100 parts of glass fiber, and 1-5 parts of auxiliary agent; The conductive agent is a binary copolymer of ethylene and quaternary ammonium salt monomers; The quaternary ammonium salt monomer is generated by quaternization reaction of 4-vinylpyridine.

2. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 1, characterized in that: The binary copolymer of ethylene-quaternary ammonium salt monomer is obtained, comprising: The quaternary ammonium salt monomer, water and tert-butyl alcohol are uniformly mixed to obtain a first mixed solution; The first mixed liquid is placed in a reactor, degassed with ethylene, pressurized with ethylene to a first target pressure, stirred and heated to a target temperature, an initiator solution is pumped into the reactor, stirred and reacted for a first period of time, and then pressurized with ethylene to a second target pressure, and the initiator solution is added. The second target pressure is maintained and stirred and reacted for a second period of time. The reaction is stopped, cooled, emptied, and post-treated to obtain a binary copolymer of ethylene and quaternary ammonium salt monomer.

3. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 2, characterized in that: The first target pressure is 4-6 MPa, the first time period is 1-2 hours, the second target pressure is 15-18 MPa, and the second time period is 5-10 hours.

4. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 2, characterized in that: The mass ratio of the quaternary ammonium salt monomer, water, and tert-butanol is 1:40-55:8-10; and the mass concentration of the initiator solution is 4-6%.

5. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 2, characterized in that: The initiator is one of potassium persulfate and ammonium persulfate or a mixture of the two.

6. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 1, characterized in that: The quaternizing agent in the quaternization reaction is γ-chloropropyltriethoxysilane, and the molar ratio of the γ-chloropropyltriethoxysilane to the 4-vinylpyridine is 1-1.5:

1.

7. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 1, characterized in that: In the quaternization reaction, the reaction temperature is 60-80° C. in an organic solvent, and the reaction time is 12-24 h.

8. The conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to claim 1, characterized in that: The auxiliary agent is an antioxidant and / or a lubricant.

9. The method for preparing the conductive and wear-resistant polyphenylene sulfide / polyketone composite material according to any one of claims 1 to 8, characterized in that: include: The polyphenylene sulfide resin, polyketone resin, conductive agent, glass fiber and auxiliary agent are mixed, melt-blended and extruded, and granulated to obtain a composite material.

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