1. The polyphenylene sulfide composite material with high CTI is characterized by comprising the following raw materials in percentage by weight:

2. the polyphenylene sulfide composite material with high CTI as claimed in claim 1, wherein the polyphenylene sulfide resin is linear polyphenylene sulfide.

3. The polyphenylene sulfide composite material with high CTI as claimed in claim 2, wherein the melt flow rate of the polyphenylene sulfide resin is 400-1200 g/10 min.

4. The polyphenylene sulfide composite material with high CTI as claimed in claim 1, wherein the glass fiber is flat glass fiber with an oval cross section.

5. The polyphenylene sulfide composite material with high CTI as claimed in claim 4, wherein the flat glass fiber has a length of 3-6 mm and a cross-sectional flatness ratio of 3-12.

6. The polyphenylene sulfide composite material with high CTI as claimed in claim 1, wherein the purity of the magnesium hydroxide is more than 97%.

7. The polyphenylene sulfide composite material with high CTI as claimed in claim 5, wherein the magnesium hydroxide has an average particle size of 1 μm or less.

8. The polyphenylene sulfide composite material with high CTI as claimed in claim 1, wherein the metal deactivator is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate or N, N' -bis [ β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.

9. The polyphenylene sulfide composite material with high CTI as claimed in claim 1, wherein the sum of the weight percentages of the magnesium hydroxide and the glass fiber is 50-80%.

Background

Polyphenylene Sulfide (PPS) has excellent thermal stability, chemical stability, dimensional stability, corrosion resistance, excellent physical and mechanical properties of electrical property, good adhesive property, excellent flame retardance, good electrical property and can be blended and modified. The method has wide application in automobile manufacturing, electronics and electrics, chemical industry, instrument and aerospace industry and the like.

However, due to the existence of a large number of benzene rings on the PPS main chain, when the material is subjected to surface discharge while the rigidity of the material is increased, a large number of radicals are generated due to the breakage of the benzene ring structure, and a conductive carbon layer is formed on the surface, so that the tracking index of the material is relatively low, generally less than 150V, and in order to expand the application range, the electrical property of the material needs to be improved.

The Chinese patent CN112457670A is to add a coupling agent to improve the compatibility of polyphenylene sulfide resin and glass fiber, and to add fluorosilicone oil to improve the tracking index of the material. The Chinese invention patent CN109679345B improves the fluidity of the polyphenylene sulfide composite material by compounding the low molecular weight polymer plasticizer and the modifier, and obviously improves the tracking resistance of the material. Meanwhile, the same tracking resistance of the traditional high-filling-quantity polyphenylene sulfide composite material is achieved by matching a small amount of conductive filler with polyamide resin.

However, the tracking index of these resin composites is less than 300V, and with the increasing use of polyphenylene sulfide materials, especially in the application of electronic and electrical devices, the products require materials with higher fluidity and higher relative tracking index, and the resin composites proposed so far cannot meet higher requirements, so that the development of composites that can simultaneously meet higher molding processability, impact resistance and higher comparative tracking index is required.

Disclosure of Invention

In view of the above, the invention provides a polyphenylene sulfide composite material with high CTI by preparing specific raw materials, and the polyphenylene sulfide composite material has high rigidity, high fluidity, low creep deformation and high electric leakage tracking index, overcomes the defects in the prior art, and is a composite material suitable for popularization and application.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a polyphenylene sulfide composite material with high CTI, which comprises the following raw materials in percentage by weight:

preferably, the polyphenylene sulfide resin is linear polyphenylene sulfide; the melt flow rate of the polyphenylene sulfide resin is 400-1200 g/10 min;

specifically, the polyphenylene sulfide resin was tested at 316 ℃ and 5kg for melt flow rate.

Preferably, the glass fiber is a flat glass fiber with an oval cross section; the length of the flat glass fiber is 3-6 mm, and the flat ratio of the cross section is 3-12.

Preferably, the purity of the magnesium hydroxide is 97% or more; the average particle diameter of the magnesium hydroxide is less than 1 mu m;

specifically, the magnesium hydroxide is commercially available magnesium hydroxide, wherein the content of calcium oxide as an impurity is 1% or less, and the content of chlorine as an impurity is 0.5% or less.

Preferably, the metal deactivator is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate or N, N' -bis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine;

specifically, the addition of 1-3% of a metal passivator can improve the tracking index (CTI) of the material.

Preferably, the sum of the weight percentages of the magnesium hydroxide and the glass fiber is 50-80%;

specifically, when the sum of the weight percentages of the magnesium hydroxide and the glass fiber is less than 50%, the electrical leakage tracking index of the composite material cannot meet the requirement, and when the sum of the weight percentages of the magnesium hydroxide and the glass fiber is more than 80%, the composite material is difficult to process and has poor mechanical properties.

Preferably, one or more auxiliary agents selected from plasticizers, stabilizers, mold release agents, dyes, pigments and fillers can be added into the polyphenylene sulfide composite material as additives; the dosage of the additive is determined according to the actual production condition.

Preferably, the mixing sequence of the components in the preparation process of the polyphenylene sulfide composite material is not limited and is determined according to the actual production condition; the preparation method of the polyphenylene sulfide composite material is not limited, and the polyphenylene sulfide composite material can be prepared by kneading with an extruder (single-screw or twin-screw extruder), a hot roll, a kneader, a mixing roll or the like; the preparation temperature is 270-340 ℃.

According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:

1. the polyphenylene sulfide composite material has excellent mechanical properties, high rigidity, high fluidity, low creep deformation and the like, has higher Comparative Tracking Index (CTI), and is suitable for manufacturing electronic and electric products, mechanical products, automobile parts and other heat-resistant and corrosion-resistant products.

2. The preparation process of the polyphenylene sulfide composite material is simple and easy to operate, the preparation method and the mixing sequence of the components are not limited, and the polyphenylene sulfide composite material with different characteristics can be obtained by matching with other additives (such as a plasticizer, a stabilizer, a release agent, a dye, a pigment, a filler and the like).

Detailed Description

The invention provides a polyphenylene sulfide composite material with high CTI, which comprises the following raw materials in percentage by weight:

in the present invention, the polyphenylene sulfide resin is preferably linear polyphenylene sulfide; the melt flow rate of the polyphenylene sulfide resin is preferably 400-1200 g/10min, and more preferably 400-800g/10 min;

specifically, the polyphenylene sulfide resin was tested at 316 ℃ and 5kg for melt flow rate.

In the present invention, the glass fiber is preferably a flat glass fiber having an elliptical cross section; the length of the flat glass fiber is preferably 3-6 mm, and the cross-section flatness ratio is preferably 3-12.

In the present invention, the purity of the magnesium hydroxide is preferably 97% or more, and more preferably 99%; the average particle diameter of the magnesium hydroxide is preferably 1 μm or less, and more preferably 0.84 μm; the magnesium hydroxide is preferably magnesium hydroxide subjected to surface treatment by a silane coupling agent;

specifically, the magnesium hydroxide is commercially available magnesium hydroxide, wherein the content of calcium oxide as an impurity is 1% or less, and the content of chlorine as an impurity is 0.5% or less.

In the invention, the metal deactivator is 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester or N, N' -bis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, and is further preferably 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester;

specifically, the Creepage Tracking Index (CTI) of the material can be improved by adding 1-3% of metal passivator.

In the invention, the sum of the weight percentages of the magnesium hydroxide and the glass fiber is preferably 50-80%;

specifically, when the sum of the weight percentages of the magnesium hydroxide and the glass fiber is less than 50%, the electrical leakage tracking index of the composite material cannot meet the requirement, and when the sum of the weight percentages of the magnesium hydroxide and the glass fiber is more than 80%, the composite material is difficult to process and has poor mechanical properties.

In the invention, one or more additives of a plasticizer, a stabilizer, a release agent, a dye, a pigment and a filler can be added into the polyphenylene sulfide composite material as an additive; the dosage of the additive is determined according to the actual production condition.

In the invention, the mixing sequence of the components in the preparation process of the polyphenylene sulfide composite material is not limited and is determined according to the actual production condition; the preparation method of the polyphenylene sulfide composite material is not limited, and the polyphenylene sulfide composite material is preferably prepared by kneading with an extruder (single-screw or twin-screw extruder), a hot roll, a kneader, a mixer, or the like, and more preferably with a single-screw or twin-screw extruder; the preparation temperature is preferably 270-340 ℃, and more preferably 280-300 ℃.

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The polyphenylene sulfide composite materials prepared in each example and comparative example were injection-molded into test standard bars in standard sizes, and the physical properties in each example were respectively tested in accordance with international standards.

Melt flow rate test conditions: 316 ℃ and 5 kg.

Comparative Tracking Index (CTI) test conditions were tested according to GB/T4207-.

The invention is verified by the following examples and comparative examples, with the following detailed data:

polyphenylene sulfide: PPS, melt flow rate of 400-.

Flat glass fibers: ECS309A-M4, manufactured by Chongqing International composite materials, Inc.;

ordinary glass fiber: ECS11-03-540, manufactured by Megaku corporation of China;

metal passivator: 3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid isooctyl ester, NAUGARD XL-1;

magnesium hydroxide-1: the magnesium hydroxide content is 95%, the average particle size is 0.83 μm, and the magnesium hydroxide is commercially available;

magnesium hydroxide-2: the content of magnesium hydroxide is 99%, the average grain diameter is 1.5 μm, and the magnesium hydroxide is sold in the market;

magnesium hydroxide-3: the magnesium hydroxide has a content of 99%, and has an average particle size of 0.84 μm, and is commercially available;

magnesium hydroxide-4: the content of magnesium hydroxide is 99 percent, the average grain diameter is 0.84 mu m, and the surface is treated by a silane coupling agent and is sold in the market;

calcium carbonate: manufactured by the Shanghai Kindi trade company, Inc.

The formulation tables and the performance test results of examples 1 to 5 and comparative examples 1 to 7 are shown in tables 1 and 2:

TABLE 1 formulation tables and performance test results for examples 1-2 and comparative examples 1-4

TABLE 2 formulation tables and results of the Performance test for examples 3-5 and comparative examples 5-7

As can be seen from Table 1, the higher the purity of magnesium hydroxide is, the higher the mechanical properties and the relative tracking index (CTI) of the polyphenylene sulfide composite material are; as can be seen from table 2, the relative tracking index (CTI) of the polyphenylene sulfide composite material using the flat glass fiber is significantly higher than that of the polyphenylene sulfide composite material using the common glass fiber, and the relative tracking index (CTI) of the polyphenylene sulfide composite material prepared using magnesium hydroxide is significantly higher than that of the polyphenylene sulfide composite material prepared using calcium carbonate. As can be seen from tables 1 and 2, the polyphenylene sulfide composite material of the invention not only has excellent mechanical properties, but also has a Comparative Tracking Index (CTI) of more than 400V, which is superior to the CTI of the existing material.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.