CN110964322A - Polyphenylene sulfide composite material and preparation method and application thereof - Google Patents
Polyphenylene sulfide composite material and preparation method and application thereof Download PDFInfo
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- CN110964322A CN110964322A CN201911265522.3A CN201911265522A CN110964322A CN 110964322 A CN110964322 A CN 110964322A CN 201911265522 A CN201911265522 A CN 201911265522A CN 110964322 A CN110964322 A CN 110964322A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a polyphenylene sulfide composite material and a preparation method and application thereof, and belongs to the technical field of composite materials. The polyphenylene sulfide composite material provided by the invention comprises the following preparation raw materials in parts by weight: 100 parts of polyphenylene sulfide resin, 0.2-0.8 part of antioxidant, 0.1-2 parts of blending rheological agent, 0.5-8 parts of surface modifier, 3-15 parts of surface active filler, 3-10 parts of hot melt adhesive, 0.5-2 parts of carbon black and 85-165 parts of glass fiber; wherein the surface modifier is obtained by modifying organic silicon powder through a coupling agent; the surface active filler is obtained by modifying solid glass microspheres with a coupling agent. The polyphenylene sulfide composite material provided by the invention can meet the requirements of precision injection molding on stable appearance size, smooth surface, no floating fiber, high fluidity, easy molding and the like.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a polyphenylene sulfide composite material and a preparation method and application thereof.
Background
With the further development of material science, the application of 'replacing steel with plastic' is increasingly wide, and especially in the fields of confidential instruments, communication electronics, computers, aerospace and the like, the precision requirement of people on plastic products is higher and higher. The precision injection molding is mainly used for producing plastic products with good dimensional stability, high precision and low surface roughness, and gradually develops towards high speed, ultraprecision and micro-integration. Therefore, the material for precision injection molding must meet the conventional physical property requirements, be easy to mold and process and have good fluidity, and also require a smooth surface after molding and extremely high stability in terms of product size and shape.
Polyphenylene Sulfide (PPS), also known as polyphenylene sulfide, was first produced on a large scale in 1973 by Phillips oil Inc., USA, and is a crystalline thermoplastic special engineering plastic with excellent comprehensive properties. Due to the fact that the PPS molecular chain contains the thiophenyl, the PPS molecular chain has excellent heat resistance, flame retardance, high rigidity, high hardness, excellent dimensional stability and electrical performance, and can resist corrosion and radiation under extreme conditions. However, when the PPS is used alone, the PPS has the defects of low impact strength, unstable melt viscosity during molding and the like, and is improved by modification means such as toughening, inorganic filling, fiber reinforcement and the like at present. The modified PPS is widely applied to the fields of electronics, electrics, automobiles, rail traffic, aerospace, war industry and the like, and the yield and sales of the modified PPS become the first of special engineering plastics.
The PPS reinforcing and modifying method mainly adopts inorganic filler and/or glass fiber for filling, the reinforcing and modifying PPS has better rigidity, meanwhile, the wear resistance, the impact strength and the temperature resistance are also greatly improved, the application limit of pure PPS caused by the brittleness problem can be effectively removed, meanwhile, the inorganic filler and the glass fiber have more price advantages, and the cost of the modifying PPS can be reduced. However, when too much inorganic filler is used, the flowability and mechanical properties of the PPS composite material are easily greatly attenuated, and the surface is rough, so that the requirements of precision injection molding cannot be met; when the content of the glass fiber in the PPS composite material is high, the surface of a product is easy to have fiber floating, and meanwhile, the problem of warping is also caused, so that the surface and dimensional stability of the product is seriously influenced.
Disclosure of Invention
The polyphenylene sulfide composite material provided by the invention can meet the requirements of precision injection molding on stable appearance size, smooth surface, no floating fiber, high fluidity, easiness in molding and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyphenylene sulfide composite material which comprises the following preparation raw materials in parts by weight:
100 parts of polyphenylene sulfide resin, 0.2-0.8 part of antioxidant, 0.1-2 parts of blending rheological agent, 0.5-8 parts of surface modifier, 3-15 parts of surface active filler, 3-10 parts of hot melt adhesive, 0.5-2 parts of carbon black and 85-165 parts of glass fiber;
wherein the surface modifier is obtained by modifying organic silicon powder through a coupling agent;
the surface active filler is obtained by modifying solid glass microspheres with a coupling agent.
Preferably, the coupling agent for preparing the surface modifier is a silane coupling agent, the organic silicon powder is ultra-high molecular weight organic silicon powder and comprises silicon dioxide and polydimethylsiloxane loaded on the silicon dioxide, and the molecular weight of the polydimethylsiloxane is more than or equal to 200000; the mass ratio of the organic silicon powder to the coupling agent is 1: (0.05-0.1).
Preferably, the coupling agent for preparing the surface active filler is a silane coupling agent, and the solid glass microspheres are ultrafine solid glass microspheres with the particle size of 5-50 nm; the mass ratio of the solid glass microspheres to the coupling agent is 1: (0.05-0.1).
Preferably, the melt flow rate of the polyphenylene sulfide resin at 316 ℃ and 5kg is 450-1800 g/10 min.
Preferably, the antioxidant is a mixture of a phosphite antioxidant and a hindered phenol antioxidant, and the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1-2): 1.
preferably, the blending rheological agent is a hydroxyl-terminated polyester with a highly branched structure.
Preferably, the hot-melt adhesive is ethylene-acrylic acid copolymer resin, the melt flow rate of the hot-melt adhesive is 3-40 g/10min under the conditions of 190 ℃ and 2.16kg, the acrylic acid content is 6-20%, and the softening point is 60-80 ℃.
Preferably, the particle size of the carbon black is 10-20 nm; the diameter of the glass fiber is 9-14 μm.
The invention provides a preparation method of the polyphenylene sulfide composite material, which comprises the following steps:
mixing polyphenylene sulfide resin, an antioxidant, a blending rheological agent, a surface modifier, a surface active filler, a hot melt adhesive and carbon black to obtain a mixed material;
and carrying out melt blending granulation on the mixed material and the glass fiber to obtain the polyphenylene sulfide composite material.
The invention provides the application of the polyphenylene sulfide composite material in the technical scheme or the polyphenylene sulfide composite material prepared by the preparation method in the technical scheme in precision injection molding.
The invention provides a polyphenylene sulfide composite material which comprises the following preparation raw materials in parts by weight: 100 parts of polyphenylene sulfide resin, 0.2-0.8 part of antioxidant, 0.1-2 parts of blending rheological agent, 0.5-8 parts of surface modifier, 3-15 parts of surface active filler, 3-10 parts of hot melt adhesive, 0.5-2 parts of carbon black and 85-165 parts of glass fiber; wherein the surface modifier is obtained by modifying organic silicon powder through a coupling agent; the surface active filler is obtained by modifying solid glass microspheres with a coupling agent. The invention takes polyphenylene sulfide resin as a matrix, adopts a coupling agent to respectively carry out surface modification on organic silicon powder and solid glass microspheres to obtain a surface modifier and a surface active filler, and adds glass fiber to carry out reinforced modification under the action of a blending rheological agent and a hot melt adhesive, so that the obtained polyphenylene sulfide composite material has the advantages of higher mechanical property, good fluidity, easy processing and forming and the like, and can ensure that a formed product has low surface roughness, no floating fiber, stable product size and shape, low each shrinkage rate, uniform shrinkage and low warping degree, can meet various requirements of precise injection molding on materials, and can be widely used for producing precise products with various structures and shapes.
Detailed Description
The invention provides a polyphenylene sulfide composite material which comprises the following preparation raw materials in parts by weight:
100 parts of polyphenylene sulfide resin, 0.2-0.8 part of antioxidant, 0.1-2 parts of blending rheological agent, 0.5-8 parts of surface modifier, 3-15 parts of surface active filler, 3-10 parts of hot melt adhesive, 0.5-2 parts of carbon black and 85-165 parts of glass fiber;
wherein the surface modifier is obtained by modifying organic silicon powder through a coupling agent;
the surface active filler is obtained by modifying solid glass microspheres with a coupling agent.
In the invention, the preparation raw material of the polyphenylene sulfide composite material comprises 100 parts by weight of polyphenylene sulfide resin. In the invention, the melt flow rate of the polyphenylene sulfide resin at 316 ℃ and 5kg is preferably 450-1800 g/10min (test standard: ISO 1133). The polyphenylene sulfide resin is not particularly limited in source, and can be obtained from commercially available products meeting the above requirements; in the embodiment of the invention, polyphenylene sulfide Resin of Zhejiang New synthetic specialty materials, Inc., model number NHU-PPS Resin1130C, 1150C or 1190C, is specifically adopted.
Based on the parts by weight of the polyphenylene sulfide resin, the preparation raw material of the polyphenylene sulfide composite material comprises 0.2-0.8 part of antioxidant, preferably 0.4-0.6 part. In the invention, the antioxidant is preferably a mixture of phosphite antioxidant and hindered phenol antioxidant, and the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is preferably (1-2): 1. the present invention is not particularly limited with respect to the specific types of the phosphite antioxidant and hindered phenol antioxidant, and any antioxidant known to those skilled in the art may be used, and specifically, the phosphite antioxidant is preferably tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), and the hindered phenol antioxidant is preferably N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098); in the examples of the present invention, antioxidants 168 and 1098 from saint leikott fine chemicals (shanghai) ltd were specifically used.
Based on the parts by weight of the polyphenylene sulfide resin, the preparation raw material of the polyphenylene sulfide composite material comprises 0.1-2 parts of blending rheological agent, preferably 0.2-1 part, and specifically can be 0.2 part, 0.5 part or 1 part. In the present invention, the blending rheology agent is preferably a hydroxyl-terminated polyester having a highly branched structure; in the embodiment of the invention, a blending rheological agent of Beijing Huayu Rui Limited is specifically adopted, and the model is HY-D100. The blending rheological agent is hydroxyl-terminated polyester with a highly branched structure, has strong wetting ability, good compatibility with polyphenylene sulfide resin, filler and glass fiber, and small influence on the mechanical properties of a base material, and can effectively improve the processing fluidity, improve the filling amount and promote the reduction of the melt viscosity.
Based on the parts by weight of the polyphenylene sulfide resin, the preparation raw material of the polyphenylene sulfide composite material comprises 0.5-8 parts of the surface modifier, preferably 1-5 parts, and specifically 1 part, 2 parts, 3 parts, 4 parts or 5 parts. In the invention, the surface modifier is preferably obtained by modifying organosilicon powder by using a coupling agent, the coupling agent for preparing the surface modifier is preferably a silane coupling agent, more preferably a mixture of gamma-aminopropyl triethoxysilane (a silane coupling agent KH-550) and gamma-glycidoxypropyl trimethoxysilane (a silane coupling agent KH-560), and the mass ratio of the silane coupling agent KH-550 to the silane coupling agent KH-560 is preferably 1: (0.8-1.2), more preferably 1: 1; the organic silicon powder is preferably ultra-high molecular weight organic silicon powder, and comprises silicon dioxide and polydimethylsiloxane loaded on the silicon dioxide, wherein the molecular weight of the polydimethylsiloxane is preferably more than or equal to 20 ten thousand, and more preferably 20-200 ten thousand; the mass ratio of the organic silicon powder to the coupling agent is preferably 1: (0.05-0.1). In the embodiment of the invention, silane coupling agents KH-550 and KH-560 of Jiangsu morning light coupling agent GmbH are specifically adopted, and the ultrahigh molecular weight organosilicon powder is purchased from Beijing Huayutong Rui GmbH and has the model number of HY-SP 70.
In the present invention, the preparation method of the surface modifier preferably comprises the following steps:
and mixing the coupling agent and ethanol, spraying the mixture on the surface of the organic silicon powder, drying, and crushing to obtain the surface modifier.
In the present invention, the mass ratio of the coupling agent to ethanol is preferably 4: (0.8-1.2), more preferably 4: 1; the ethanol is used for diluting the coupling agent so as to better disperse the coupling agent on the surface of the organic silicon powder. In the invention, after spraying, the obtained mixed material is preferably placed in a high-speed stirrer for stirring and mixing treatment, wherein the temperature of the stirring and mixing treatment is preferably 30-40 ℃, and more preferably 35 ℃; the time for stirring and mixing treatment is preferably 10-20 min, and more preferably 15 min; the stirring speed is preferably 100 to 200r/min, and more preferably 150 r/min.
In the invention, the obtained material is dried after the stirring and mixing treatment is finished; the drying temperature is preferably 75-85 ℃, and more preferably 80 ℃; the drying time is preferably 2-4 h, and more preferably 3 h. The dried material is preferably placed in a high-speed stirrer to be crushed, and the crushed dried material is crushed under the stirring action of the high-speed stirrer, wherein the crushing temperature is preferably 30-40 ℃, and more preferably 35 ℃; the crushing time is preferably 10-20 min, and more preferably 15 min; the stirring speed in the crushing process is preferably 200-300 r/min, and more preferably 250 r/min. The invention has no special limit on the granularity of the crushed material, and the crushing can meet the requirement under the above conditions.
In the invention, the organosilicon powder is modified by using the coupling agent, and the obtained surface modifier has the characteristics of high surface activity, strong dispersing ability, high temperature resistance and the like, can effectively improve the processing performance of the material, reduce the viscosity difference in a melt, enhance the binding power of the glass fiber and PPS resin, and enhance the coating of the glass fiber, thereby being beneficial to improving the surface roughness of a product and eliminating floating fibers on the surface of the product.
Based on the parts by weight of the polyphenylene sulfide resin, the preparation raw material of the polyphenylene sulfide composite material comprises 3-15 parts of surface active filler, preferably 5-12 parts, and specifically can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts. In the invention, the coupling agent for preparing the surface active filler is preferably a silane coupling agent, and more preferably is consistent with the optional range of the coupling agent for preparing the surface modifier, and is not described again; the solid glass microspheres are preferably ultrafine solid glass microspheres, more preferably ultrafine soda lime type solid glass microspheres, and the granularity is preferably 5-50 nm; the mass ratio of the solid glass microspheres to the coupling agent is preferably 1: (0.05-0.1). In the embodiment of the invention, silane coupling agents KH-550 and KH-560 of the silane coupling agents of Jiangsu morning light coupling agent GmbH are specifically adopted, and ultrafine soda lime type solid glass microspheres are specifically purchased from Beijing Huayutong Rui GmbH, and have the model number of HY-GB 2500.
In the present invention, the preparation method of the surface active filler preferably comprises the following steps:
and mixing the coupling agent with ethanol, spraying the mixture on the surface of the solid glass microsphere, drying, and crushing to obtain the surface active filler.
In the present invention, the mass ratio of the coupling agent to ethanol is preferably 4: (0.8-1.2), more preferably 4: 1; the ethanol is used for diluting the coupling agent so as to better disperse the coupling agent on the surface of the solid glass microsphere. In the present invention, the preparation method of the surface active filler preferably refers to the preparation method of the surface modifier, and is not described in detail herein.
In the invention, the coupling agent is used for modifying the solid glass microspheres, the obtained surface active filler has the advantages of small anisotropy, high surface activity, good compatibility with matrix resin, large specific surface area, good dispersibility and the like, the shrinkage rate of the material can be reduced, the dimensional stability is improved, the appearance and warpage of a workpiece are obviously improved, and the problem of warpage deformation caused by uneven shrinkage generated by orientation and crystallization of each component in the composite material is solved.
Based on the parts by weight of the polyphenylene sulfide resin, the polyphenylene sulfide composite material provided by the invention comprises 3-10 parts of hot melt adhesive, preferably 4-8 parts, and specifically 4, 6 or 8 parts. In the invention, the hot melt adhesive is preferably ethylene-acrylic acid copolymer resin, the melt flow rate of the hot melt adhesive at 190 ℃ under the condition of 2.16kg is preferably 3-40 g/10min (test standard: GB/T3682-. The source of the hot-melt adhesive is not specially limited, and the hot-melt adhesive can be made of a commercially available commodity meeting the requirements; in the examples of the invention, use is made in particular of a hot-melt adhesive from DuPont, USA, type EAA20E482, or of an Exxon Mobil, type EAA5020 or 5200. The hot-melt adhesive is ethylene-acrylic acid copolymer (EAA) resin, has good cohesiveness to metal and nonmetal materials, better improves the low-temperature hot-melt property of the obtained composite material, has better coating effect on glass fiber and filler, and can reduce the fiber floating of a workpiece and improve the surface effect.
Based on the parts by weight of the polyphenylene sulfide resin, the preparation raw material of the polyphenylene sulfide composite material comprises 0.5-2 parts of carbon black, preferably 1.5-2 parts. In the invention, the particle size of the carbon black is preferably 10-20 nm. The carbon black of the present invention is not particularly limited in its source, and commercially available products well known to those skilled in the art may be used; in the examples of the present invention, M800 pigment carbon black, which is American carbon black, is specifically used.
Based on the parts by weight of the polyphenylene sulfide resin, the polyphenylene sulfide composite material comprises 85-165 parts of glass fiber, preferably 90-150 parts; in the invention, the glass fiber preferably accounts for 45-55% of the total mass of the polyphenylene sulfide resin preparation raw materials, and specifically can be 45%, 50% or 55%. In the invention, the diameter of the glass fiber is preferably 9-14 μm; the glass fiber can be continuous long glass fiber and/or chopped glass fiber, wherein the length of the chopped glass fiber is preferably 3.0-4.5 mm. In the present invention, the glass fiber is preferably an alkali-free glass fiber. The source of the glass fiber is not specially limited, and the glass fiber can be a commercially available product meeting the requirements; in the embodiment of the invention, long glass fiber ERS200-11-T635B and chopped glass fiber T443R of Taishan glass fiber company Limited are specifically adopted.
The invention provides a preparation method of the polyphenylene sulfide composite material, which comprises the following steps:
mixing polyphenylene sulfide resin, an antioxidant, a blending rheological agent, a surface modifier, a surface active filler, a hot melt adhesive and carbon black to obtain a mixed material;
and carrying out melt blending granulation on the mixed material and the glass fiber to obtain the polyphenylene sulfide composite material.
The invention mixes polyphenylene sulfide resin, antioxidant, blending rheological agent, surface modifier, surface active filler, hot melt adhesive and carbon black to obtain a mixed material. The mixing mode of the preparation raw materials is not particularly limited, and the preparation raw materials can be uniformly mixed, for example, the mixture is mixed for 10-20 min at room temperature.
After the mixed material is obtained, the mixed material and the glass fiber are subjected to melt blending granulation to obtain the polyphenylene sulfide composite material. In the present invention, the melt blending granulation is preferably performed in a twin-screw extruder, which preferably has a length-to-diameter ratio of 44: 1; in the examples of the present invention, a twin screw extruder TSE-30PLUS, Nanjing, Reya, was specifically used. In the embodiment of the invention, the mixed material is added from a main feeding port of a double-screw extruder, and simultaneously, the glass fiber is added from a glass fiber feeding port, and the mixture is subjected to melt blending granulation by the double-screw extruder to obtain the polyphenylene sulfide composite material; the processing technology of melt blending granulation is preferably as follows: the rotating speed of the main machine is 220 rpm; the temperature of each section of the extruder is sequentially one-section-six-section from the feed opening to the machine head, wherein the temperature of the first section is 240-260 ℃, the temperature of the second section is 280-290 ℃, the temperature of the third section is 290-3000 ℃, the temperature of the fourth section is 290-300 ℃, the temperature of the fifth section is 280-290 ℃, and the temperature of the sixth section is 280-290 ℃; the feeding speed is 20kg/h, and the cooling water temperature is 70 ℃.
The invention provides the application of the polyphenylene sulfide composite material in the technical scheme or the polyphenylene sulfide composite material prepared by the preparation method in the technical scheme in precision injection molding.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
In the following examples and comparative examples, the starting materials used for the preparation were:
PPS resin: purchased from new synthetic specialty materials, Zhejiang, model NHU-PPS Resin1130C, 1150C, or 1190C;
phosphite ester antioxidant: antioxidant 168 from saint leikote fine chemicals (shanghai) ltd;
hindered phenol antioxidant: antioxidant 1098 from saint leikote fine chemicals (shanghai) ltd;
blending rheological agent: purchased from Beijing Huayutong Rui Limited, model number HY-D100;
coupling agent: KH-550 and KH-560, silane coupling agents of Chinesu morning light coupling agent Co., Ltd;
ultra-high molecular weight organosilicon powder: purchased from Beijing Huayutong Rui Limited, model number HY-SP 70;
ultra-fine soda lime type solid glass microspheres: purchased from Beijing Huayutong Rui Limited and having a model number of HY-GB 2500;
hot melt adhesive: purchased from dupont, usa under model EAA20E 482; or from exxonmobil corporation, model number EAA5020 or 5200;
carbon black: american cabot black M800 pigment carbon black;
glass fiber: long glass fiber ERS200-11-T635B and chopped glass fiber T443R from Taishan glass fiber company Limited.
Example 1
Preparation of surface modifier: mixing silane coupling agents KH-550 and KH-560 with absolute ethyl alcohol according to a mass ratio of 2: 2: 1, spraying the mixture on the surface of ultrahigh molecular weight organosilicon powder HY-SP70 (the mass ratio of the total mass of silane coupling agents KH-550 and KH-560 to the mass of ultrahigh molecular weight organosilicon powder HY-SP70 is 0.07: 1), placing the obtained mixture in a high-speed stirrer, stirring for 15min at the temperature of 150r/min and 35 ℃, then placing the obtained material in an oven to dry for 4h at the temperature of 80 ℃, then placing the obtained dried material in the high-speed stirrer, and stirring for 15min at the temperature of 250r/min and 35 ℃ to obtain the surface modifier.
Preparation of surface active filler: mixing silane coupling agents KH-550 and KH-560 with absolute ethyl alcohol according to a mass ratio of 2: 2: 1, uniformly mixing, spraying the mixture on the surface of superfine soda lime type solid glass microsphere HY-GB2500 (the mass ratio of the total mass of silane coupling agents KH-550 and KH-560 to the mass of the superfine soda lime type solid glass microsphere HY-GB2500 is 0.07: 1), placing the obtained mixed material in a high-speed stirrer, stirring for 15min at the temperature of 150r/min and 35 ℃, then placing the obtained material in an oven for drying at the temperature of 80 ℃ for 4h, then placing the obtained dried material in the high-speed stirrer, and stirring for 15min at the temperature of 250r/min and 35 ℃ to obtain the surface active filler.
According to the weight parts, 100 parts of PPS resin (the specific model is 1130C), 0.2 part of hindered phenol antioxidant (the specific model is 1098), 0.4 part of phosphite antioxidant (the specific model is 168), 1 part of blending rheological agent (the specific model is HY-D100), 5 parts of surface modifier, 5 parts of surface active filler, 6 parts of hot melt adhesive (the specific model is EAA5200) and 1.4 parts of carbon black (the specific model is M800 pigment carbon black) are mixed for 15min at room temperature, the obtained mixed material is added from a main feeding port of a double-screw extruder (TSE-30 PLUS double-screw extruder with the length-diameter ratio of 44: 1), and 97.4 parts of glass fiber (the specific part is chopped glass fiber T443R, namely the glass fiber accounts for 45 percent of the total preparation raw materials of the polyphenylene sulfide composite material) is added from the feeding port and is melted and blended and granulated by the extruder, obtaining the polyphenylene sulfide composite material; wherein the processing technology comprises the following steps: the rotating speed of the main machine is 220rpm, the first-stage temperature is 240 ℃, the second-stage temperature is 280 ℃, the third-stage temperature is 290 ℃, the fourth-stage temperature is 300 ℃, the fifth-stage temperature is 300 ℃, the sixth-stage temperature is 290 ℃, the feeding speed is 20kg/h, and the cooling water temperature is 70 ℃.
Example 2
A polyphenylene sulfide composite was prepared according to the method of example 1, except that: the amount of surface-active filler added is 8 parts.
Example 3
A polyphenylene sulfide composite was prepared according to the method of example 1, except that: the addition amount of the blending rheological agent is 0.5 part, the addition amount of the surface active filler is 8 parts, and the glass fiber adopts long glass fiber ERS 200-11-T635B.
Example 4
According to the weight parts, 100 parts of PPS resin (the specific model is 1150C), 0.2 part of hindered phenol antioxidant (the specific model is antioxidant 1098), 0.4 part of phosphite antioxidant (the specific model is antioxidant 168), 0.5 part of blending rheological agent (the specific model is HY-D100), 1 part of surface modifier (prepared in example 1), 9 parts of surface active filler (prepared in example 1), 8 parts of hot melt adhesive (the specific model is EAA5020) and 1.4 parts of carbon black (the specific model is M800 pigment carbon black) are mixed for 15min at room temperature, the obtained mixed material is added from a main feeding port of a Nanjing Ruiya TSE-30 twin screw PLUS extruder with the length-diameter ratio of 44: 1), and simultaneously 120.5 parts of glass fiber (the specific part is chopped glass fiber T443R, namely the glass fiber accounts for 50% of the total preparation raw materials of the polyphenylene sulfide composite material) from a glass fiber feeding port 443, melting, blending and granulating by an extruder to obtain the polyphenylene sulfide composite material; wherein the processing technology comprises the following steps: the rotating speed of the main machine is 220rpm, the first-stage temperature is 240 ℃, the second-stage temperature is 290 ℃, the third-stage temperature is 300 ℃, the fourth-stage temperature is 300 ℃, the fifth-stage temperature is 300 ℃, the sixth-stage temperature is 290 ℃, the feeding speed is 20kg/h, and the cooling water temperature is 70 ℃.
Example 5
A polyphenylene sulfide composite was prepared according to the method of example 4, except that: the addition amount of the surface modifier was 3 parts.
Example 6
A polyphenylene sulfide composite was prepared according to the method of example 4, except that: the addition amount of the surface modifier is 3 parts, the addition amount of the hot-melt adhesive is 4 parts, and the glass fiber adopts long glass fiber ERS 200-11-T635B.
Example 7
According to the weight parts, 100 parts of PPS resin (the specific model is 1190C), 0.2 parts of hindered phenol antioxidant (the specific model is 1098), 0.4 parts of phosphite antioxidant (the specific model is 168), 0.2 parts of blending rheological agent (the specific model is HY-D100), 1 part of surface modifier (prepared in example 1), 5 parts of surface active filler (prepared in example 1), 8 parts of hot melt adhesive (the specific model is EAA20E482) and 1.4 parts of carbon black (the specific model is M800 carbon black pigment) are mixed for 15min at room temperature, the obtained mixed material is added from a main feeding port of a Nanjing Ruiya twin-screw extruder (TSE-30 PLUS extruder, the length-diameter ratio is 44: 1), and 142 parts of glass fiber (the specific part is chopped glass fiber T443R, namely, the glass fiber accounts for 55 percent of the total preparation raw materials of the polyphenylene sulfide composite material) from a glass fiber feeding port, melting, blending and granulating by an extruder to obtain the polyphenylene sulfide composite material; wherein the processing technology comprises the following steps: the rotation speed of the main machine is 220rpm, the first-stage temperature is 260 ℃, the second-stage temperature is 290 ℃, the third-stage temperature is 300 ℃, the fourth-stage temperature is 300 ℃, the fifth-stage temperature is 300 ℃, the sixth-stage temperature is 290 ℃, the feeding speed is 20kg/h, and the cooling water temperature is 70 ℃.
Example 8
A polyphenylene sulfide composite was prepared as in example 7, except that: the addition amount of the surface modifier is 2 parts, and the addition amount of the surface active filler is 10 parts.
Example 9
A polyphenylene sulfide composite was prepared as in example 7, except that: the addition amount of the surface modifier is 3 parts, the addition amount of the surface active filler is 12 parts, and the glass fiber adopts long glass fiber ERS 200-11-T635B.
Comparative example 1
A polyphenylene sulfide composite was prepared according to the method of example 1, except that: no surface active filler is added.
Comparative example 2
A polyphenylene sulfide composite was prepared according to the method of example 4, except that: no surface modifier was added.
Comparative example 3
A polyphenylene sulfide composite was prepared as in example 7, except that: the addition amount of the blending rheological agent is 0.5 part, and a surface modifier, a surface active filler and a hot melt adhesive are not added.
The performance of the polyphenylene sulfide composite materials prepared in examples 1 to 9 and comparative examples 1 to 3 was measured, and the test standards were as follows:
(1) the tensile strength test sample is in a dumbbell shape with the size of 155mm multiplied by 10mm multiplied by 4mm, and is tested according to the GB/T1040-2008 standard, and the test equipment is a universal tester of the Meitess Industrial System (China) Co.Ltd;
(2) the size of the bending strength sample is 80mm multiplied by 10mm multiplied by 4mm, the test is carried out according to the GB/T9341-2008 standard, and the test equipment is a universal tester of the Meitess Industrial System (China) Co.Ltd;
(3) the size of a simple beam impact strength sample is 80mm multiplied by 10mm multiplied by 4mm, the strength is tested according to GB/T1043-2008 standard, and the testing equipment is an impact testing machine of Meitess Industrial systems (China) Co;
(4) the melt index is tested according to the specification of GB/T3682-2000, the test temperature is 316 ℃, the load is 2.16kg, and the test equipment is a melt flow rate tester of Beijing crown test instrument Limited;
(5) warp test specimen size of
The thickness of the wafer is 3.2mm, and the warping degree value is the maximum warping height of the wafer;
(6) the appearance shape condition is visual inspection;
(7) the condition of fiber floating on the surface is visual inspection.
The performance test results of the polyphenylene sulfide composite materials in examples 1 to 9 and comparative examples 1 to 3 are shown in tables 1 to 3.
TABLE 1 Performance test results of polyphenylene sulfide composite materials in examples 1 to 3 and comparative example 1
| Test items | Unit of | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Tensile strength | MPa | 187 | 185 | 187 | 185 |
| Bending strength | MPa | 270 | 270 | 277 | 263 |
| Non-notched impact strength of simply supported beam | kJ/m2 | 43 | 44 | 43 | 41 |
| Melt index | g/10min | 47 | 40 | 42 | 41 |
| Degree of warp | mm | 0.14 | 0.08 | 0.08 | 0.20 |
| Appearance shape | - | Slight warping | Leveling | Leveling | Warp of |
| Surface floating fiber | - | Bright non-floating fibre | Bright non-floating fibre | Is brighter without floating fiber | Bright non-floating fibre |
TABLE 2 Performance test results of polyphenylene sulfide composite materials in examples 4-6 and comparative example 2
| Test items | Unit of | Example 4 | Example 5 | Example 6 | Comparative example 2 |
| Tensile strength | MPa | 220 | 215 | 217 | 220 |
| Bending strength | MPa | 305 | 301 | 296 | 308 |
| Simply supported beamNotched impact strength | kJ/m2 | 47 | 45 | 36 | 50 |
| Melt index | g/10min | 42 | 52 | 57 | 35 |
| Degree of warp | mm | 0.07 | 0.07 | 0.07 | 0.07 |
| Appearance shape | - | Leveling | Leveling | Leveling | Leveling |
| Surface floating fiber | - | Light micro-floating fiber | Bright non-floating fibre | Bright non-floating fibre | Severe whitish and loose fibers |
TABLE 3 Performance test results of polyphenylene sulfide composite materials in examples 7 to 9 and comparative example 3
| Test items | Unit of | Example 7 | Example 8 | Example 9 | Comparative example 3 |
| Tensile strength | MPa | 200 | 196 | 180 | 201 |
| Bending strength | MPa | 287 | 282 | 270 | 290 |
| Non-notched impact strength of simply supported beam | kJ/m2 | 52 | 45 | 40 | 42 |
| Melt index | g/10min | 61 | 64 | 70 | 53 |
| Degree of warp | mm | 0.21 | 0.10 | 0.07 | 0.28 |
| Appearance shape | - | Slight warping | Leveling | Leveling | Warp of |
| Surface floating fiber | - | Light micro-floating fiber | Light micro-floating fiber | Bright non-floating fibre | Severe whitish and loose fibers |
As can be seen from tables 1-3, the addition of the blending rheological agent effectively improves the melt flowability of the polyphenylene sulfide composite material, has a certain surface improvement function, and can reduce the roughness of the surface of a workpiece; the hot melt adhesive is added, so that the toughness of the polyphenylene sulfide composite material can be effectively improved, the filler and the glass fiber are well coated, and the influence of the filler and the glass fiber on the surface of the polyphenylene sulfide composite material can be reduced.
Meanwhile, as can be seen from tables 1 to 3, the surface modifier can effectively improve the floating fiber of a product, can improve the luster and the fluidity of the product, and has small influence on the mechanical property of the product; the surface active filler improves the mechanical property of the polyphenylene sulfide composite material, can effectively improve the dimensional accuracy of a workpiece, reduces shrinkage and reduces the warping degree of the workpiece.
In conclusion, the polyphenylene sulfide composite material prepared by the invention has good comprehensive performance, can meet the requirements of precision injection molding on the mechanical property, the fluidity, the surface, the dimensional stability, the buckling deformation and the like of the material under the conditions of different filling and reinforcing ratios of glass fibers, and has wide prospects in the application fields of light weight, precision and micro-integration.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The polyphenylene sulfide composite material is characterized by comprising the following preparation raw materials in parts by weight:
100 parts of polyphenylene sulfide resin, 0.2-0.8 part of antioxidant, 0.1-2 parts of blending rheological agent, 0.5-8 parts of surface modifier, 3-15 parts of surface active filler, 3-10 parts of hot melt adhesive, 0.5-2 parts of carbon black and 85-165 parts of glass fiber;
wherein the surface modifier is obtained by modifying organic silicon powder through a coupling agent;
the surface active filler is obtained by modifying solid glass microspheres with a coupling agent.
2. The polyphenylene sulfide composite material as claimed in claim 1, wherein the coupling agent for preparing the surface modifier is a silane coupling agent, the silicone powder is ultra-high molecular weight silicone powder comprising silica and polydimethylsiloxane loaded on the silica, and the molecular weight of the polydimethylsiloxane is not less than 200000; the mass ratio of the organic silicon powder to the coupling agent is 1: (0.05-0.1).
3. The polyphenylene sulfide composite material according to claim 1, wherein the coupling agent for preparing the surface active filler is a silane coupling agent, and the solid glass microspheres are ultrafine solid glass microspheres with a particle size of 5-50 nm; the mass ratio of the solid glass microspheres to the coupling agent is 1: (0.05-0.1).
4. The polyphenylene sulfide composite material according to claim 1, wherein the polyphenylene sulfide resin has a melt flow rate of 450 to 1800g/10min at 316 ℃ and 5 kg.
5. The polyphenylene sulfide composite material as claimed in claim 1, wherein the antioxidant is a mixture of phosphite antioxidant and hindered phenol antioxidant, and the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1-2): 1.
6. the polyphenylene sulfide composite of claim 1, wherein the blending rheology agent is a hydroxyl terminated polyester with a highly branched structure.
7. The polyphenylene sulfide composite material as claimed in claim 1, wherein the hot melt adhesive is an ethylene-acrylic acid copolymer resin, the melt flow rate of the hot melt adhesive at 190 ℃ under 2.16kg is 3-40 g/10min, the acrylic acid content is 6-20%, and the softening point is 60-80 ℃.
8. The polyphenylene sulfide composite material according to claim 1, wherein the particle size of the carbon black is 10 to 20 nm; the diameter of the glass fiber is 9-14 μm.
9. The method for preparing the polyphenylene sulfide composite material as recited in any one of claims 1 to 8, characterized by comprising the steps of:
mixing polyphenylene sulfide resin, an antioxidant, a blending rheological agent, a surface modifier, a surface active filler, a hot melt adhesive and carbon black to obtain a mixed material;
and carrying out melt blending granulation on the mixed material and the glass fiber to obtain the polyphenylene sulfide composite material.
10. The polyphenylene sulfide composite material as defined in any one of claims 1-8 or the polyphenylene sulfide composite material prepared by the preparation method as defined in claim 9, and the application thereof in precision injection molding.
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