CN116355410A - A kind of polyphenylene sulfide polyamide composite material and its preparation and application - Google Patents

Abstract

The invention belongs to the field of composite materials, and discloses a polyphenylene sulfide polyamide composite material and its preparation and application. The polyphenylene sulfide polyamide composite material comprises the following components in parts by mass: 35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolymerized polyamide; 0-50 parts of glass fiber; coupling agent 0-2.0 parts, nucleating agent 0-1.0 parts; lubricant 0-1.0 parts; antioxidant 0-1.0 parts, the copolyamide is a copolyamide with a melting point of 50°C-200°C. The polyphenylene sulfide polyamide composite material prepared by the present invention, with respect to conventionally used polyamide resin such as PPA, PA66, PA6 etc., the tensile strength of the obtained polyphenylene sulfide polyamide composite material, notched impact strength, CTI , Adhesive strength, etc. have been significantly improved. It has good applications in the fields of electronics, electrical appliances, automobiles, nano-injection molding, precision instruments, 5G communications, chemicals, and aerospace.

Description

A kind of polyphenylene sulfide polyamide composite material and its preparation and application

technical field

The invention belongs to the field of composite materials, in particular to a polyphenylene sulfide polyamide composite material and its preparation and application.

Background technique

PPS is one of the varieties with the best heat resistance in engineering plastics. After modified by glass fiber, its heat distortion temperature is greater than 260 degrees, and its chemical resistance is second only to polytetrafluoroethylene. In addition, it also has the advantages of small molding shrinkage, low water absorption, good fire resistance, good fatigue resistance, high breakdown voltage, etc., especially in high temperature and high humidity environments, it still has excellent electrical insulation, but PPS The disadvantages of poor toughness, low impact strength, low CTI (relative tracking index), and weak mutual adhesion also limit its application field. Therefore, it needs to be modified to solve the above shortcomings, so as to obtain excellent comprehensive performance.

Contents of the invention

In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a polyphenylene sulfide polyamide composite material.

Another object of the present invention is to provide a method for preparing the above polyphenylene sulfide polyamide composite material.

Another object of the present invention is to provide the application of the above-mentioned polyphenylene sulfide polyamide composite material in the fields of electronics, electrical appliances, automobiles, nano-injection molding, precision instruments, 5G communications, chemical industry, and aerospace.

The object of the present invention is achieved through the following solutions:

A polyphenylene sulfide polyamide composite material, which includes the following components in parts by mass:

35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolymerized polyamide; 0-50 parts of glass fiber; 0-2.0 parts of coupling agent, 0-1.0 parts of nucleating agent; 0-1.0 parts of lubricant; antioxidant Dose 0-1.0 part.

Preferably, the polyphenylene sulfide polyamide composite material includes the following components in parts by mass:

40-70 parts of polyphenylene sulfide resin; 3-20 parts of copolymerized polyamide; 30-40 parts of glass fiber; 0.1-0.5 parts of coupling agent, 0.1-0.5 parts of nucleating agent; 0.1-0.5 parts of lubricant; antioxidant Dose 0.1-0.5 part.

The polyphenylene sulfide resin is selected from a resin whose melt index range is 250-700g/10min measured under the condition of 316°C/5kg.

The copolyamide is preferably a copolyamide with a melting point of 50°C-200°C, more preferably at least one of the copolyamides with a melting point of 95-170°C. A further preferred copolyamide is synthesized from caprolactam, hexamethylenediamine, decanediamine, sebacic acid, and dodecanedibasic acid at a certain mass molar ratio, wherein caprolactam, hexamethylenediamine, and decanedidiamine , sebacic acid, the molar ratio of dodecane dibasic acid is 8:(2-10):(2:10):(3-6):(6-9).

Wherein the melting point and the density of the copolymerized polyamide resin are specifically shown in Table 1 below:

Table 1 Melting point and density of different grades of polyamide resin

Preferably, the molar ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid, and dodecanedibasic acid in the copolyamide 1# is 8:6:6:6:6; The molar ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedibasic acid in polyamide 2# is 8:6:6:3:9; in described copolyamide 3#, caprolactam, The molar ratio of hexamethylenediamine, hexamethylenediamine, sebacic acid, and dodecanedibasic acid is 8:2:10:3:9; , sebacic acid, and the molar ratio of dodecanedioic acid are 8:10:2:3:9.

The glass fiber is preferably a round glass fiber with a diameter of 9-13 μm and a chopped length of 3.0-5.0 mm or a flat glass fiber with a flatness ratio of 2-5.

Described coupling agent is at least one in amino silane coupling agent, acyloxy silane coupling agent, alkoxy silane coupling agent and epoxy silane coupling agent, preferably N-( 2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltris(methoxyethoxy)silane, vinyltrimethoxysilane, 3( At least one of 2,3-glycidoxy)propyltrimethoxysilane, more preferably commercially available N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, 3-aminopropyl At least one of the models of triethoxysilane and 3(2,3-glycidoxy)propyltrimethoxysilane;

The nucleating agent is at least one of talcum powder, calcium carbonate, glass microspheres, silicon dioxide, calcium oxide, magnesium oxide, carbon black, mica, and molybdenum disulfide, more preferably talc powder.

The lubricant is at least one of stearic acid metal salts, pentaerythritol stearate, ethylene bisstearamide, erucamide, oleic acid amide, silicones, polyolefin wax, etc., preferably pentaerythritol stearate.

The antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants, o-hydroxyphenyl triazine antioxidants, phosphite antioxidants, and thioester antioxidants. A sort of.

A kind of preparation method of above-mentioned polyphenylene sulfide polyamide composite material, comprises the following steps:

First premix the rest of the raw materials except glass fiber to obtain the premixed material, then feed the premixed material from the main feed port of the twin-screw extruder, and feed the glass fiber from the side feed port of the twin-screw extruder. Mixing materials + glass fibers are melted and extruded by a twin-screw extruder at 250-330°C, cooled and pelletized to obtain polyphenylene sulfide polyamide composite materials.

Or, first premix the rest of the raw materials except glass fiber and coupling agent to obtain a premix, then feed the premix from the main feeding port of the twin-screw extruder, and feed the glass fiber from the side of the twin-screw extruder The material is fed into the feed port, and the coupling agent is metered into the liquid injection port of the extruder according to the set ratio. The premix + glass fiber + coupling agent are melted and extruded at 250-330°C through the twin-screw extruder, and cooled , Pelletizing to obtain polyphenylene sulfide polyamide composite material.

The nucleating agent, lubricant and antioxidant are preferably firstly mixed uniformly to form a compound package, and then premixed with other raw materials to obtain a premix.

An application of the above-mentioned polyphenylene sulfide polyamide composite material in the fields of electronics, electrical appliances, automobiles, nano-injection molding, precision instruments, 5G communications, chemical industry, and aerospace.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

The invention provides a scheme for preparing polyphenylene sulfide polyamide composite material, and the obtained polyphenylene sulfide polyamide composite material has significantly improved tensile strength, notched impact strength, CTI, bonding strength and the like.

Detailed ways

The present invention will be described in further detail below in conjunction with comparative examples and examples, but the embodiments of the present invention are not limited thereto. Those who do not indicate specific conditions in the comparative examples and examples carry out according to conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

For the preparation methods of copolyamides in Comparative Examples and Examples, please refer to the description of the preparation methods, and the rest of the raw materials can be obtained commercially, as follows: polyphenylene sulfide is Xinhecheng 1150C, PA66 is BASF Ultramid A3L, and PA6 is Yuehua YH-800, PPA is Xinhecheng NH600, glass fiber is Chongqing International ECS10-03-584, coupling agent is Shin-Etsu KBE-903, antioxidant is Tianjin Lianlong 1010, nucleating agent is Xufeng BHS-503, The lubricant is LOXIOL P861/3.5 from Corning Company.

Copolyamide 1# in embodiment 1-11 and comparative example 6, copolyamide 2#, copolyamide 3#, copolyamide 4# are made of caprolactam, hexamethylenediamine, sebacic acid, decanediamine and decane Two-carbon dibasic acid is used as raw material, and polyamide # resin is prepared by monomer melt polymerization method. The specific raw material consumption and synthesis process are shown in Table 2 below:

Table 2 Copolyamide 1#, Copolyamide 2#, Copolyamide 3#, Copolyamide 4# Raw material types and molar quantities

The preparation method of composite material in comparative example 1-5 and embodiment 1-8 comprises the following steps:

(1) Weigh each raw material according to the ratio of each raw material component, premix the resin + additive compound package in the mixer for 3 minutes, and then feed the obtained premixed material through the main feeding port of the twin-screw extruder ;

(2) The glass fiber is fed from the side feeding port of the twin-screw extruder;

(3) The coupling agent is added at the liquid filling port of the extruder;

(4) The premix + glass fiber + coupling agent are melted and extruded at 250-330° C. through a twin-screw extruder, cooled, and pelletized to prepare a polyphenylene sulfide polyamide composite material.

Then, according to the ISO294-1-2018 standard, thermoplastic material injection molding samples were made, wherein the processing mold temperature: 135°C; injection molding processing temperature: 295-330°C. The obtained samples were subjected to corresponding tensile strength, notched impact, flame retardancy, CTI test, and bond strength test. The tensile strength test adopts the ISO 527 standard, the impact strength test adopts the ISO 180 standard, the flame retardant test adopts the IEC60695-11-10 standard, and the CTI index adopts the IEC 60112 standard method for testing. The adhesive performance test simulates the ISO 527-2 standard test. The middle position of the injection molded 1A dumbbell-shaped spline is cut and then glued. The bonding area between the two splines is 40mm ² , and the thickness of the glue layer is 0.2mm. Erbang 5354 (glue heating temperature 125°C), after curing for 24 hours in an environment with a temperature of 23°C and a relative humidity of 55%, conduct a tensile strength test.

Comparative Examples 1-5 and Examples 1-8

The formula of composite material and material test item result in comparative examples 1-5 and embodiment 1-8 are specifically shown in table 3 below:

The formula of composite material and material test item result in table 3 comparative example 1-5 and embodiment 1-8

The amounts of the above-mentioned resins, glass fibers, coupling agents, and auxiliary agents all refer to their weight percentages, and the unit is %.

It can be seen from Table 3 that when the copolyamide and polyphenylene sulfide are selected for compounding, compared with the commonly used PPA, PA66, PA6, etc., the tensile strength, notched impact strength, CTI, viscosity, etc. The bonding strength has been significantly improved, and more excellent performance can be obtained. In Example 8, when the ratio of copolyamide and polyphenylene sulfide resin in the compound is 20:39, the flame retardant performance of the material is V1 level, and the ratio of copolyamide and polyphenylene sulfide in Examples 1-7 is lower than In Example 8, the flame retardant performance of the composite is V0.

Comparative Examples 6-8 and Examples 9-11

The formula of composite material and material test item result in comparative example 6-8 and embodiment 9-11 are specifically shown in table 4 below:

The formula of composite material and material test item result in table 4 comparative example 6-8 and embodiment 9-11

The preparation method of the composite material in Comparative Examples 6-8 and Examples 9-11 is basically the same as that of Examples 1-8, and the only difference is that the way of adding the coupling agent is different, specifically as follows:

(1) Weigh each raw material according to the ratio of each raw material component in Table 4, then premix the resin + coupling agent + auxiliary agent in a mixer for 3 minutes, and then extrude the obtained premixed material through twin-screw The main feeding port of the machine is used for feeding;

(2) The glass fiber is fed from the side feeding port of the twin-screw extruder;

(3) The premix + side material is melted and extruded by a twin-screw extruder at 250-330° C., cooled, and pelletized to prepare a polyphenylene sulfide polyamide composite material;

Then carry out sample preparation test according to the method identical with embodiment 1-8, and test result is as shown in table 4.

It can be seen from Table 4 that the performance of the scheme of metering the coupling agent at the liquid filling port of the extruder is significantly better than the traditional process of adding the coupling agent through the premix in the main feed. Because the traditional process requires a mechanical mixer to operate for 3-10 minutes to mix evenly when the main feed is mixed in, because the silane coupling agent will hang on the arm during the mixing process, volatilize and lose, and the coupling agent is very easy to react with air moisture or The surface of the material reacts with moisture, and the substrate will also agglomerate after the reaction, resulting in difficult and uneven processing, and the actual addition amount will reduce its efficacy. By directly injecting the liquid into the filling port of the extruder, the timeliness and accuracy are higher than the traditional main feed mixing performance.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

1. The polyphenylene sulfide polyamide composite material is characterized by comprising the following components in parts by weight:

35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolyamide; 0-50 parts of glass fiber; 0-2.0 parts of coupling agent and 0-1.0 parts of nucleating agent; 0-1.0 parts of lubricant; 0-1.0 part of antioxidant;

the copolyamide is a copolyamide with a melting point of 50-200 ℃.

2. The polyphenylene sulfide polyamide composite material according to claim 1, which is characterized by comprising the following components in parts by mass:

40-70 parts of polyphenylene sulfide resin; 3-20 parts of copolyamide; 30-40 parts of glass fiber; 0.1-0.5 part of coupling agent and 0.1-0.5 part of nucleating agent; 0.1-0.5 part of lubricant; 0.1-0.5 part of antioxidant.

3. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the polyphenylene sulfide resin is selected from the resins with the melt index range of 250-700g/10min measured under the condition of 316 ℃/5 kg.

4. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the copolyamide is a copolyamide with a melting point of 95-170 ℃; further preferred are copolyamides having a melting point of 115 to 160 ℃.

5. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the copolyamide is synthesized by taking caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid as raw materials.

6. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the glass fiber is round glass fiber with diameter of 9-13 μm and short cutting length of 3.0-5.0mm or flat glass fiber with flat rate of 2-5.

7. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the coupling agent is at least one of amino silane coupling agent, acyloxy silane coupling agent, alkoxy silane coupling agent and epoxy silane coupling agent, preferably at least one of N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, vinyl tri (methoxyethoxy) silane, vinyl trimethoxy silane and 3 (2, 3-epoxypropoxy) propyl trimethoxy silane.

8. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:

the nucleating agent is at least one of talcum powder, calcium carbonate, glass beads, silicon dioxide, calcium oxide, magnesium oxide, carbon black, mica and molybdenum disulfide;

the lubricant is at least one of metal stearate, pentaerythritol stearate, ethylene bis-stearamide, erucamide, oleamide, silicone and polyolefin wax;

the antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants, o-hydroxy phenyl triazine antioxidants, phosphite antioxidants and thioester antioxidants.

9. A method for preparing the polyphenylene sulfide polyamide composite material according to any one of claims 1 to 8, characterized by comprising the steps of:

premixing the rest raw materials except glass fibers to obtain a premix, then discharging the premix from a main position feed opening of a double-screw extruder, discharging glass fibers from a side position feed opening of the double-screw extruder, melting and extruding the premix and the glass fibers at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material;

or premixing the rest raw materials except the glass fiber and the coupling agent to obtain a premix, then discharging the premix from a main feeding port of the double-screw extruder, discharging the glass fiber from a side feeding port of the double-screw extruder, adding the coupling agent into a liquid filling port of the extruder, melting and extruding the premix, the glass fiber and the coupling agent at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material.

10. Use of the polyphenylene sulfide polyamide composite material according to any one of claims 1-8 in electronics, electrical appliances, automobiles, laser welding, precision instruments, 5G applications, chemical and aerospace applications.