WO2020098593A1 - Polyphenylene sulfide composite material, preparation method therefor and application thereof - Google Patents

Abstract

A polyphenylene sulfide composite material, a preparation method therefor and an application thereof. The polyphenylene sulfide composite material comprises the following components in percentage by weight: 30-60% of polyphenylene sulfide resin; 30-60% of glass fiber; 0.1-20% of a low-molecular-weight polymer plasticizer; 0.1-20% of a modifier; 0.1-10% of conductive filler; and 1-20% of polyamide. According to the polyphenylene sulfide composite material, by compounding the low-molecular-weight polymer plasticizer and the modifier, the fluidity of the polyphenylene sulfide composite material is improved, and the proof tracking performance of the material is also obviously improved; and moreover, by means of a small quantity of the conductive filler and polyamide resin, the proof tracking performance identical to that of a conventional polyphenylene sulfide composite material with high filling quantity is achieved.

Description

Polyphenylene sulfide composite material, and preparation method and application thereof Technical field

The invention relates to a high-contrast tracking index polyphenylene sulfide reinforced composite material and a preparation method thereof, which belong to the field of polymer material modification.

Background technique

Polyphenylene sulfide is a thermoplastic crystalline polymer with excellent comprehensive properties. It has good moldability, chemical resistance, flame retardancy, rigidity and modulus. It has high dimensional stability, excellent electrical properties, and fatigue resistance. High, good creep resistance, easy to form, and has the characteristics of aging resistance, radiation resistance, non-toxic and so on. It has a wide range of applications in the fields of electronics, automobiles, precision machinery, chemicals, home appliances, and aviation, aerospace, and national defense. In recent years, it has developed into the world's sixth-largest general-purpose engineering plastic.

With the development of high-voltage and ultra-high voltage power systems, transmission and distribution equipment tends to be light and small, and the harsh operating environment. The performance of insulating materials has a decisive impact on the reliability and service life of transmission and distribution equipment. In addition to the conventional evaluation items, how to evaluate the tolerance of insulating materials in harsh environments, especially under the combined action of polluted electrolytes and electric fields, is a matter of concern.

Tracking phenomenon of leakage of insulating materials. Polymer insulating materials are often contaminated by contaminants such as salt dew, moisture, dust, etc. when running outdoors and in harsh environments. An electrolyte is formed on the surface. Under the action of an electric field, a special type of polymer surface appears. Discharge destruction phenomenon --- leakage tracking damage phenomenon, forming incomplete conductive channels on the surface. The process of generating electrical leakage traces on the surface or close to the surface is called "electrical trace", and the corrosion damage caused by the insulating material under the effect of discharge is called "electrical corrosion". These situations are more serious for electrical equipment used in highways, coastal areas, plateaus and heavily polluted places, such as stator bars and outdoor insulators of hydroelectric generators.

In addition to the wetting state and pollution degree of the surface of the insulating material, the leakage traces on the surface of the insulating material also change with the strength of the electric field on the surface of the material, the magnitude of the surface current and the discharge condition caused by them. It is the surface current and spark discharge that cause the leakage trace. Therefore, the leakage traces are divided into two types: one occurs below the minimum atmospheric breakdown voltage of the solid surface, mainly caused by the conductance current caused by the dirt, and is generally not accompanied by gas discharge; the other is due to the conductive channel on the surface of the material Spark discharge caused by intermittent, and then form the accumulation and spread of carbides. The development of polymer insulation material leakage traces depends on the formation and accumulation of free carbon on the surface of the material. Spark discharge has the effect of removing free carbon, so the formation of leakage traces is actually a dynamic equilibrium process of carbon generation, aggregation and removal on the surface of the material. In addition to the strength of the electric field on the surface of the material, the magnitude of the current, the discharge status, the degree of surface pollution and the wetting state, more importantly, it is related to the composition of the polymer itself.

The weakest bond in the polymer insulating material breaks under the high temperature generated by the surface discharge, producing volatile by-products. The remaining residue contains unsaturated conjugated double bonds or forms a stable unsaturated or aromatic free radical. These free radicals will re-couple to form a conductive structure similar to graphite, making the material easier to develop traces of leakage. Polymer insulating materials with aromatic conjugated structures are not resistant to tracking due to leakage, because various aromatic compounds contain active electronic structures and are prone to generate free radicals, especially in the presence of oxygen. Conductive black residue of graphite structure. Therefore, the tracking resistance of polyphenylene sulfide is not ideal.

At present, the method of increasing the tracking index of polyphenylene sulfide compared to the leakage tracking index is mainly to add an inorganic filler, but due to the higher proportion of the filler, the fluidity of the material is reduced, which is not conducive to injection molding.

The patent (CN106928710A) discloses a polyphenylene sulfide composite material, the composite material is added with a modifier, and the structure of the modifier is

By adding the modifier, the problem of poor fluidity of polyphenylene sulfide compound at processing temperature can be improved, but the patent does not address the problem of tracking.

The patent (CN 102924921A) discloses a polyphenylene sulfide reinforced composite material with a high comparative tracking index and its preparation method, and proposes a compound technology of mixing chopped glass fibers and ultra-fine filler minerals to improve polyphenylene sulfide Ether composites have a tracking index compared to the tracking index (CTI) of more than 225V, and the corresponding polyphenylene sulfide reinforced composite melt flow rate in this patent is less than 100g / 10min.

Summary of the invention

Problems to be solved by the invention

In order to solve the above-mentioned problems in the prior art, the present invention provides a high-contrast tracking index polyphenylene sulfide reinforced composite material and a preparation method thereof. The invention improves the tracking index of the polyphenylene sulfide composite material through the combination of long glass fiber and a small amount of conductive filler and supplemented with a certain amount of polyamide, while adding a certain amount of high flow modifier and low molecular weight Polymer plasticizer to improve the fluidity of polyphenylene sulfide reinforced composites and further improve its tracking index.

The polyphenylene sulfide reinforced composite material prepared by the invention has a high comparative tracking index, and the processing performance of the polyphenylene sulfide is significantly improved due to the low filler addition ratio and the addition of additives to improve the fluidity of the polyphenylene sulfide.

Solutions for solving problems

The invention provides a polyphenylene sulfide composite material, which includes the following components by weight percentage:

Preferably, the following components are included by weight percentage:

Preferably, the polyphenylene sulfide resin is linear polyphenylene sulfide, and the melt flow rate is 100-400 g / 10 min.

Preferably, the glass fiber is an alkali-free long fiber, the diameter of the monofilament is 10-20 μm, and optionally its surface is treated with a coupling agent, and the coupling agent is a silane coupling agent.

Preferably, the low molecular weight polymer plasticizer is selected from one or more of polyester, polyolefin and polyether; more preferably, the low molecular weight polyester is an unsaturated polyester, low molecular weight polymer The olefin is one or more of low molecular weight polypropylene, low molecular weight polyethylene or low molecular weight polystyrene, and the low molecular weight polyether is polyethylene glycol ether, polypropylene glycol ether, polyethylene glycol monomethyl ether or polyethylene One or more of glycol dimethyl ether.

Preferably, the isotacticity of the low molecular weight polymer plasticizer is 30% -60%, the weight average molecular weight of the low molecular weight polymer plasticizer is 1000-80000, and the molecular weight distribution is 1-10.

Preferably, the structural formula of the modifier is:

Wherein, n is an integer of 1-10; R _{1 is} selected from H, C ₁ -C ₆ alkyl substituted with at least one hydroxyl group, or C ₁ -C ₆ alkoxy substituted with at least one hydroxyl group; R _{2 is} selected from H, or at least one hydroxy-substituted C ₃ -C ₁₀ cycloalkyl group; R ₃ is selected from H, at least one hydroxy-substituted C ₆ -C ₂₀ aryl group, or at least one hydroxy-substituted C ₆ -C ₂₀ aryloxy group; preferably When any one of R ₁ , R ₂ or R ₃ is selected from H, then the remaining two functional groups have at least one selected from at least one hydroxy substituted C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group Group or C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ aryloxy group.

Preferably, the conductive filler is one or more of metal powder, carbon black powder, conductive graphite or carbon fiber. Preferably, the conductive filler is one or two of conductive graphite or carbon fiber. The particle diameter of the conductive graphite is 10-150 μm, preferably 30-100 μm, the carbon fiber is chopped carbon fiber, the length is 1-10 cm, preferably 3-5 cm, and the monofilament diameter is 5-20 μm, preferably 10-15 μm.

Preferably, the polyamide is one or more of polycondensates of diamines and dibasic acids, caprolactam ring-opening polymers, and aromatic polyamides.

The invention also provides a method for preparing the polyphenylene sulfide composite material according to any one of the above, the method includes the following steps:

(1) Weigh polyphenylene sulfide resin, low-molecular-weight polymer plasticizer, modifier, and conductive filler in proportion by weight to obtain a premix 1;

(2) Add the premix 1 to the twin-screw extruder, and then add glass fiber. After the extrusion is stabilized, turn on the vacuum exhaust pump. The molten strip is drawn into the water tank from the die of the extruder to cool and solidify. 1. Pelletize to obtain granular composite material 1;

(3) Dry the granular composite material 1 obtained in step (2);

(4) Weigh the dried granular composite material 1 and polyamide uniformly according to the weight ratio to obtain premix 2;

(5) Add the premix 2 obtained in step (4) to the twin-screw extruder. After the extrusion is stabilized, start the vacuum exhaust pump, the molten strip is extruded from the extruder, cooled and solidified, and pelletized The polyphenylene sulfide composite material.

Finally, the present invention also provides an injection-molded product, the injection-molded product includes any of the polyphenylene sulfide composite materials described above, the injection-molded product is selected from a laptop computer case, an automobile part, or a precision electronic appliance Structure.

Effect of invention

The advantage of the present invention is that it improves the disadvantage that the traditional preparation of high-tracking index polyphenylene sulfide reinforced composite materials requires a high filling amount, resulting in poor fluidity of the material, and is improved by the combination of low molecular weight plasticizers and modifiers. The fluidity of polyphenylene sulfide composite material and the tracking resistance of the material have also been significantly improved. At the same time, a small amount of conductive filler and polyamide resin are used to achieve the same tracking resistance of the traditional high-fill polyphenylene sulfide composite material. This kind of compounding method is unique to the present invention and has not been reported in relevant documents or patents.

detailed description

First, the present invention provides a polyphenylene sulfide composite material, which includes the following components by weight percentage:

In a preferred embodiment, the following components are included by weight percent:

In a preferred embodiment, the polyphenylene sulfide resin may be any polyphenylene sulfide resin common in the art, preferably linear polyphenylene sulfide, and its melt mass flow rate is 100-400g / 10min, It is preferably 200-350 g / 10min, and the molecular weight range of the above polyphenylene sulfide is 20000-40000, preferably 25000-30000.

In a more preferred embodiment, the polyphenylene sulfide resin mass percentage is 30-50%, further preferably 35-50%.

In a preferred embodiment, the glass fiber may be any glass fiber commonly known in the art, preferably an alkali-free long fiber, whose monofilament diameter is 10-20 μm, and its surface is optionally treated with a coupling agent, The coupling agent may be a silane coupling agent. Preferably, the diameter of the alkali-free long glass fiber monofilament is 14 μm.

In a more preferred embodiment, the mass percentage of the glass fiber is 30-50%, further preferably 35-50%.

In a preferred embodiment, the low molecular weight polymer plasticizer is one or more of low molecular weight esters, low molecular weight polyolefins, and low molecular weight polyethers. Preferably, the low molecular weight polymer plasticizer Ester is unsaturated polyester, low molecular weight polyolefin is one or more of low molecular weight polypropylene, low molecular weight polyethylene or low molecular weight polystyrene, low molecular weight polyether is polyethylene glycol ether, polypropylene glycol ether, One or more of polyethylene glycol monomethyl ether or polyethylene glycol dimethyl ether, more preferably, the low molecular weight plasticizer is low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene One or more of them.

In a more preferred embodiment, the low molecular weight polymer plasticizer has a weight average molecular weight of 10,000-80,000, a molecular weight distribution of 1-10, and an isotacticity of 30% -60%. Preferably, the The low molecular weight polymer plasticizer has a weight average molecular weight of 10,000 to 80,000, a molecular weight distribution of 1-5, and an isotacticity of 30% to 50%. More preferably, the low molecular weight polymer plasticizer has a weight average molecular weight of 10000-50000, molecular weight distribution is 1-2, isotacticity is 35% -45%.

In a more preferred embodiment, the mass percentage of the low molecular weight polymer plasticizer is 0.1-10%, further preferably 0.5-10%, and more preferably 1-8%.

The above low molecular weight polymer plasticizer has the characteristics of low molecular weight, low isotacticity, and narrow molecular weight distribution. At high temperatures, the above low molecular weight polymer plasticizer penetrates between polyphenylene sulfide macromolecular chains, reducing polyphenylene The friction between the sulfide macromolecular chains delays the crystallization rate of polyphenylene sulfide, improves the fluidity of the polyphenylene sulfide melt, and enhances the infiltration effect of the polyphenylene sulfide resin matrix and glass fiber. The good compatibility between glass fiber and polyphenylene sulfide resin can reduce the defects of the structure of the polyphenylene sulfide reinforced composite material itself. Such defects often lead to a decrease in the tracking resistance of the material, so it can be said that the low molecular weight The addition of polymer amount of plasticizer not only improves the processing flow properties of the material but also enhances the tracking resistance of the material.

In a preferred embodiment, the structural formula of the modifier is:

Wherein, n is an integer of 1-10; R _{1 is} selected from H, C ₁ -C ₆ alkyl substituted with at least one hydroxyl group, or C ₁ -C ₆ alkoxy substituted with at least one hydroxyl group; R _{2 is} selected from H, or at least one hydroxy-substituted C ₃ -C ₁₀ cycloalkyl group; R ₃ is selected from H, at least one hydroxy-substituted C ₆ -C ₂₀ aryl group, or at least one hydroxy-substituted C ₆ -C ₂₀ aryloxy group.

The modifier in the above polyphenylene sulfide composite material has a large number of non-polar functional groups such as alkyl or aryl groups, and a large number of polar functional groups such as hydroxyl groups, so that the modifier and the polyphenylene sulfide resin and other components It has good compatibility; on the other hand, the modifier has a good lubricating effect, which can effectively reduce the viscosity of the polyphenylene sulfide melt system, thereby improving its infiltration effect with glass fiber. The modifier is similar to the above-mentioned low molecular weight plasticizer, which not only improves the processing fluidity of the material, but also reduces the structural defects of the material due to the improved wetting effect between the polyphenylene sulfide matrix resin and the glass fiber. Enhanced the tracking resistance of the material.

In a more preferred embodiment, the modifier has the following formula I structure:

In a more preferred embodiment, the modifier has a mass percentage of 0.2-5%, preferably 0.5-4%.

In a preferred embodiment, the conductive filler may be any conductive filler commonly known in the art, preferably one or more of metal powder, carbon black powder, conductive graphite or carbon fiber. The conductive filler has a certain conductivity, and can shunt a part of the current when a leakage current is generated on the surface of the polyphenylene sulfide composite material to avoid the local current intensity is too high and a large amount of heat generation causes local carbonization of the surface of the material to form a conductive path. More preferably, the conductive filler is one or two of conductive graphite or carbon fiber; wherein the particle size of the conductive graphite is 10-150 μm, preferably 30-100 μm, the carbon fiber is chopped carbon fiber, and its length is 1- 10cm, preferably 3-5cm, monofilament diameter 5-20μm, preferably 10-15μm.

In a more preferred embodiment, the conductive filler has a mass percentage of 0.2-5%, preferably 0.5-4%.

In a preferred embodiment, the polyamide is one or more of polycondensates of diamines and dibasic acids, caprolactam ring-opening polymers, and aromatic polyamides. The molecular weight of the polyamide ranges from 15,000 to 30,000, preferably from 17,000 to 23,000. Because the molecular structure of the polyamide is a long-chain structure, the carbon aggregation density in the molecular chain is small, and the residual carbon content after combustion is small; in the polyphenylene sulfide molecular chain, due to the presence of the benzene ring, the carbon aggregation density of the molecular chain Large, the large amount of carbon residue after combustion is easy to form a conductive path with poor tracking resistance. The polyphenylene sulfide reinforced composite material can effectively reduce the carbon aggregation density in the resin matrix after adding the above polyamide to improve the tracking resistance of the material. In addition, the aromatic polyamide although the carbon aggregation density in the molecular chain does not contain benzene ring The polyamide is low, but due to its excellent thermal barrier effect, it can delay the thermal aging caused by the Joule heat generated by the leakage current on the surface of the polyphenylene sulfide reinforced composite material.

In a more preferred embodiment, the mass percentage of the polyamide is 2-15%, preferably 5-15%.

In addition, the invention also provides a method for preparing the above polyphenylene sulfide composite material. The method includes the following steps:

(1) Weigh polyphenylene sulfide resin, low-molecular-weight plasticizer, modifier, and conductive filler according to weight ratio to obtain a premix 1;

(2) Add the premix 1 to the twin-screw extruder, and then add glass fiber. After the extrusion is stabilized, turn on the vacuum exhaust pump. The molten strip is drawn into the water tank from the die of the extruder to cool and solidify. 1. Pelletize to obtain granular composite material 1;

(3) Dry the granular composite material 1 obtained in step (2);

(4) Weigh the dried granular composite material 1 and polyamide according to the weight ratio and mix them uniformly to obtain a premix 2;

(5) Add the premix 2 obtained in step (4) to the twin-screw extruder. After the extrusion is stabilized, turn on the vacuum exhaust pump. The molten strip is drawn from the extruder die into the water tank to cool and solidify. Cut the pellets to obtain the polyphenylene sulfide composite material.

In a preferred embodiment, step (2) is to add the premix 1 from the main feed port to the pre-heated twin screw extruder, and the long glass fiber is added from the side feed port; to be extruded Turn on the vacuum exhaust pump after being stable; the molten strip is drawn into the water tank from the die of the extruder to cool and solidify, and then enters the pelletizing device to be cut into granular composite material 1;

In a preferred embodiment, step (3) is to place the granular composite material 1 in a blast drying oven at 90-110 ° C for 1-2 hours;

In a preferred embodiment, step (5) is to add the premix 2 from the main feed port to the pre-heated twin screw extruder; after the extrusion is stabilized, the vacuum exhaust pump is turned on; the molten state The material bar is drawn into the water tank from the die of the extruder to cool and solidify, and then enters the pelletizing device to be cut into granular composite material 2 which is a polyphenylene sulfide reinforced composite material with high tracking index.

Finally, the present invention also provides an injection molded product of a notebook computer case, automobile parts, and precision electronic and electrical structural parts, which contains any one of the above polyphenylene sulfide composite materials.

In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terminology used in the description of the present invention herein is for the purpose of describing specific embodiments, and is not intended to limit the present invention.

Sources and specifications of the raw materials of the examples and comparative examples: the polyphenylene sulfide resins used in the examples of the present invention were provided by Xinhecheng Special Material Company, with a molecular weight of 25,000-30000, and the low molecular weight polymer plasticizer was supplied by ExxonMobil Provided by the company, the modifier: phenolic resin (preparation refer to patent CN201710272718.X), glass fiber is provided by Jushi Glass Fiber Company, the specification is continuous direct alkali-free yarn; polyamide resin is provided by Taiwan Jisheng Company, molecular weight is 17000- 23000.

Example 1

(1) Weigh the polyphenylene sulfide resin, low molecular weight plasticizer, modifier, and conductive filler according to the weight ratio of Table 1 to obtain a premix 1;

(2) Add premix 1 from the main feed port to the pre-heated twin-screw extruder, and add long glass fiber from the side feed port; after the extrusion is stable, turn on the vacuum exhaust pump; molten material The strip is drawn from the die of the extruder into the water tank to cool and solidify, and then enters the pelletizing device to be cut into granular composite material 1;

(3) Place the granular composite material 1 in a blast drying oven at 90-110 ℃ for 1-2 hours;

(4) Weigh the dried granular composite material 1 and polyamide according to the weight ratio in Table 1 and mix them uniformly to obtain premix 2;

(5) Add the premix 2 from the main feed port to the pre-heated twin screw extruder; after the extrusion is stabilized, turn on the vacuum exhaust pump; the molten strip is drawn into the extruder die After cooling and solidifying, the water tank enters the pelletizing device and is cut into granular composite material 2 which is a polyphenylene sulfide reinforced composite material with high tracking index.

A high-contrast tracking index polyphenylene sulfide reinforced composite material, according to the weight ratio, includes the following raw materials in Table 1:

Table I

Component	weight(%)
Polyphenylene sulfide resin	40
Low molecular weight polymer plasticizer (low molecular weight polyethylene)	6
Modifier (compound of formula I)	2
glass fiber	40
Conductive filler (carbon fiber)	2
Polyamide resin (polycaprolactam)	10

The low molecular weight polyethylene in Table 1 has a weight average molecular weight of 40,000-50,000.

Comparative Example 1

A polyphenylene sulfide reinforced composite material is prepared in the same manner as in Example 1, and is prepared according to the weight ratio including the raw materials in Table 2 below:

Table II

Component	weight(%)
Polyphenylene sulfide resin	48
Low molecular weight polymer plasticizer	-
Modifier	-
glass fiber	40
Conductive filler (carbon fiber)	2
Polyamide resin (polycaprolactam)	10

Comparative Example 2

A polyphenylene sulfide reinforced composite material is prepared in the same way as in Example 1, and is prepared according to the weight ratio including the raw materials in Table 3 below:

Table 3

Component	weight(%)
Polyphenylene sulfide resin	42
Low molecular weight polymer plasticizer (low molecular weight polyethylene)	6
Modifier	-
glass fiber	40
Conductive filler (carbon fiber)	2
Polyamide resin (polycaprolactam)	10

The weight average molecular weight of the low molecular weight polyethylene in Table 3 is 40,000-50000.

Comparative Example 3

A polyphenylene sulfide reinforced composite material is prepared in the same way as in Example 1, and is prepared according to the weight ratio including the raw materials in Table 4 below:

Table 4

Component	weight(%)
Polyphenylene sulfide resin	46
Low molecular weight polymer plasticizer	-
Modifier (compound of formula I)	2
glass fiber	40
Conductive filler (carbon fiber)	2
Polyamide resin (polycaprolactam)	10

Example 2

A polyphenylene sulfide reinforced composite material is prepared in the same way as in Example 1, and is prepared according to the weight ratio including the raw materials in Table 5 below:

Table 5

Component	weight(%)
Polyphenylene sulfide resin	45
Low molecular weight plasticizer (low molecular weight polystyrene)	7
Modifier (compound of formula I)	2
glass fiber	30
Conductive filler (conductive graphite)	1
Polyamide resin (polyadipyltoluene dimethylamine)	15

The low molecular weight polystyrene in Table 5 has a weight average molecular weight of 60,000 to 70,000.

Comparative Example 4

A polyphenylene sulfide reinforced composite material is prepared according to the scheme of Example 2 of CN10292421A, and is prepared according to the weight ratio including the raw materials in Table 6 below:

Table 6

Component	weight(%)
Polyphenylene sulfide resin	35
glass fiber	35
Filler (calcium carbonate)	14
Filler (barium sulfate)	15
A silane coupling agent	0.4
Antioxidant 1076	0.3

Lubricant silicone

0.3

The composites prepared in the examples and comparative examples were injection-molded according to standard sizes into standard splines for testing. The size of the standard splines was 80 mm in length, 50 mm in width, and 3 mm in thickness. Relevant properties were tested with reference to the following standards.

The melt flow rate is tested according to GB / T3682 standard;

Compared with the tracking index of leakage, it is tested according to the GB / T4207 standard.

The test results of the above embodiments and comparative examples are shown in Table 7 below:

Table 7

In summary, it can be seen from Table 7 that compared with Comparative Example 1, in the absence of low molecular weight polymer plasticizers and modifiers, the polyphenylene sulfide reinforced composite material regardless of the melt flow rate Compared with the tracking tracking index, the melt flow rate and the tracking tracking index respectively represent the processing flow performance and tracking resistance of the material, indicating that the low molecular weight polymer plasticizer and modifier The polyphenylene sulfide reinforced composite material has obvious gain effect in processing flowability and tracking resistance.

Through the comparison of Example 1 with Comparative Examples 2 and 3, it can be found that the polyphenylene sulfide reinforced composite material with low molecular weight plasticizer or modifier added alone has lower melt flow rate and comparative tracking index than low molecular weight. The polyphenylene sulfide reinforced composite material corresponding to the compound of the polymer plasticizer and the modifier shows that the low molecular weight polymer plasticizer and the modifier have a certain synergistic effect, and the combination of the two can achieve the ideal Effect.

Comparing Example 2 and Comparative Example 4 can be found that the present invention relates to a high-contrast tracking index polyphenylene sulfide reinforced composite material without adding a large amount of filler in the case of a small amount of conductive filler and polyamide resin The compounding and the compounding of the low molecular weight polymer and the modifier achieve the equivalent tracking mark index of the traditional high-fill polyphenylene sulfide composite materials, and at the same time, it involves a high tracking mark index polyphenylene sulfide The melt flow rate of reinforced composites is significantly higher than that of traditional high-fill polyphenylene sulfide composites.

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the present invention. Within the scope of protection.

Claims (11)

1. A polyphenylene sulfide composite material, characterized in that it comprises the following components in weight percent:

   
2. The polyphenylene sulfide composite material according to claim 1, characterized in that it comprises the following components in weight percentage:

   
3. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the polyphenylene sulfide resin is linear polyphenylene sulfide, and the melt flow rate is 100-400 g / 10 min.
4. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the glass fiber is an alkali-free long fiber with a monofilament diameter of 10-20 μm, and its surface is optionally treated with a coupling agent, The coupling agent is a silane coupling agent.
5. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the low molecular weight polymer plasticizer is selected from one or more of polyester, polyolefin and polyether; preferably The low molecular weight polyester is unsaturated polyester, the low molecular weight polyolefin is one or more of low molecular weight polypropylene, low molecular weight polyethylene or low molecular weight polystyrene, and the low molecular weight polyether is polyethylene One or more of glycol ether, polypropylene glycol ether, polyethylene glycol monomethyl ether or polyethylene glycol dimethyl ether.
6. The polyphenylene sulfide composite material according to claim 5, wherein the isotacticity of the low molecular weight polymer plasticizer is 30% -60%, and the low molecular weight polymer plasticizer The weight average molecular weight is 1000-80000, and the molecular weight distribution is 1-10.
7. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the structural formula of the modifier is:

   

   Wherein, n is an integer of 1-10; R _{1 is} selected from H, C ₁ -C ₆ alkyl substituted with at least one hydroxyl group, or C ₁ -C ₆ alkoxy substituted with at least one hydroxyl group; R _{2 is} selected from H, or at least one hydroxy-substituted C ₃ -C ₁₀ cycloalkyl group; R ₃ is selected from H, at least one hydroxy-substituted C ₆ -C ₂₀ aryl group, or at least one hydroxy-substituted C ₆ -C ₂₀ aryloxy group; preferably When any one of R ₁ , R ₂ or R ₃ is selected from H, then the remaining two functional groups have at least one selected from at least one hydroxy substituted C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group Group or C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ aryloxy group.
8. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the conductive filler is one or more of metal powder, carbon black powder, conductive graphite or carbon fiber, preferably, The conductive filler is one or two of conductive graphite or carbon fiber, the particle size of the conductive graphite is 10-150 μm, preferably 30-100 μm, the carbon fiber is chopped carbon fiber, and the length is 1-10 cm, preferably 3-5cm, monofilament diameter is 5-20μm, preferably 10-15μm.
9. The polyphenylene sulfide composite material according to claim 1 or 2, wherein the polyamide is a polycondensate of diamine and dibasic acid, caprolactam ring-opening polymer, aromatic polyamide One or more.
10. A method for preparing a polyphenylene sulfide composite material according to any one of claims 1-9, characterized in that the method comprises the following steps:

    (1) Weigh polyphenylene sulfide resin, low-molecular-weight polymer plasticizer, modifier, and conductive filler in proportion by weight to obtain a premix 1;

    (2) Add the premix 1 to the twin-screw extruder, and then add glass fiber. After the extrusion is stabilized, turn on the vacuum exhaust pump. The molten strip is drawn into the water tank from the die of the extruder to cool and solidify. 1. Pelletize to obtain granular composite material 1;

    (3) Dry the granular composite material 1 obtained in step (2);

    (4) Weigh the dried granular composite material 1 and polyamide uniformly according to the weight ratio to obtain premix 2;

    (5) Add the premix 2 obtained in step (4) to the twin-screw extruder. After the extrusion is stabilized, start the vacuum exhaust pump, the molten strip is extruded from the extruder, cooled and solidified, and pelletized The polyphenylene sulfide composite material.
11. An injection-molded product, characterized in that the injection-molded product contains the polyphenylene sulfide composite material according to any one of claims 1-9, and the injection-molded product is selected from a notebook computer case, an automobile part, or a precision electronics Electrical structural parts.