CN104974525B - Vinal enhancing polyphenyl thioether composite material and preparation method thereof - Google Patents

Vinal enhancing polyphenyl thioether composite material and preparation method thereof Download PDF

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Publication number
CN104974525B
CN104974525B CN201510439315.0A CN201510439315A CN104974525B CN 104974525 B CN104974525 B CN 104974525B CN 201510439315 A CN201510439315 A CN 201510439315A CN 104974525 B CN104974525 B CN 104974525B
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vinal
composite material
polyphenyl thioether
thioether composite
strengthens
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CN104974525A (en
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林良云
梁波
林显达
李绍男
周家鋆
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Pengyun Engineering Plastics Co., Ltd., Guangzhou
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GUANGZHOU GAOBAER PLASTIC Co Ltd
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Priority to PCT/CN2016/090833 priority patent/WO2017012563A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04Ingredients characterised by their shape and organic or inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/544Silicon-containing compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/548Silicon-containing compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions 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
    • C08L81/02Polythioethers; Polythioether-ethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils

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  • Chemical Kinetics & Catalysis (AREA)
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  • Reinforced Plastic Materials (AREA)

Abstract

The present invention discloses a kind of vinal enhancing polyphenyl thioether composite material, and containing polyphenylene sulfide, vinal, glass fibre and auxiliary agent, auxiliary agent contains compatilizer, antioxidant, coupling agent, lubricant.A kind of method for preparing vinal polyphenyl thioether composite material is also disclosed, comprises the following steps:(1) by polyphenylene sulfide, vinal and glass fibre, and the dispersion of compatilizer, antioxidant, coupling agent, mix lubricant, obtain compound;(2) compound is added into extruder, extrudes strip composite, then micelle is made through pelleter pelletizing.Vinal of the invention enhancing polyphenyl thioether composite material have existing high intensity, low compacted degree, good fluidity, it is easy to process the features such as, and the features such as with high tenacity, high-modulus.

Description

Vinal enhancing polyphenyl thioether composite material and preparation method thereof
Technical field
The present invention relates to polymeric material field, more particularly to vinal enhancing polyphenyl thioether composite material and its Preparation method.
Background technology
Fiberglass enhanced polyphenyl thioether composite is the macromolecular material commonly used in current industrial production, but because of its material Material fragility is big, bending modulus is small, density is big, dielectric constant is big, in the application by a definite limitation.
The content of the invention
It is an object of the invention to provide a kind of vinal enhancing polyphenyl thioether composite material and preparation method thereof, can To solve one or more in above-mentioned prior art problem.
According to an aspect of the invention, there is provided a kind of vinal enhancing polyphenyl thioether composite material, contains Polyphenylene sulfide, vinal, glass fibre and auxiliary agent, auxiliary agent contain compatilizer, antioxidant, coupling agent, lubricant.
Vinal enhancing polyphenyl thioether composite material of the invention has existing high intensity, low compacted degree, mobility Good, easy to process the features such as, and the features such as with high tenacity, high-modulus.Vinal has good mechanical performance, its Intensity is high, modulus is high, degree of drawing is low.Can be carried vinal is added in fiberglass enhanced polyphenyl thioether composite The bending modulus of the high composite, bending modulus and impact strength, it is also possible to improve the mobility of the composite.
The bending modulus of fiberglass enhanced polyphenyl thioether composite common at present is 13000~18000, bent 10000 times or so;The bending modulus of this vinal enhancing polyphenyl thioether composite material can be more than 20000, bent 2 Ten thousand times or so, it is adaptable to make the product for needing high temperature resistant, bearing bending for a long time, such as flabellum, the automobile of high-temperature exhaust air fan Blast pipe etc..
In some embodiments, compatilizer is maleic anhydride stem grafting polyolefin or acrylic acid-grafted PP.Thus, it is possible to make Activated with the end group of polyphenylene sulfide and polyvinyl alcohol both macromolecular materials, do not produce repulsive interaction, formed one it is whole Body.
In some embodiments, antioxidant is hydroxy phenyl acrylate, hydroxyphenylmethyl acrylate, alkylidene pair Atmosphere or thiobis atmosphere.Thus, it is possible to hinder oxidation reaction of the macromolecular material in hot procedure, macromolecular material is prevented Degradation.
In some embodiments, coupling agent is γ-aminopropyl triethoxysilane, propanethiol trimethyl TMOS Or ethyoxyl triethoxysilane.Thus, it is possible to be surface-treated to glass fibre, vinal, increase it with height The cohesive force of molecular material.
In some embodiments, lubricant is stearic acid, Tissuemat E, fatty acid mono-amide, acetic acid or metallic soap.By This, can reduce the kinematic viscosity of melt polymer material state, be easy to processing.
In some embodiments, in terms of parts by weight, wherein polyphenylene sulfide 40~50, vinal 20~30, Glass fibre 20~40.The existing high intensity of material that advantage is formed into, low compacted degree, good fluidity, it is easy to process the features such as, have The features such as high tenacity, low-density, high-modulus.
In some embodiments, in terms of parts by weight, wherein compatilizer 1, antioxidant 0.3, coupling agent 0.3, lubricant 0.4.Advantage is to increase the adhesion of different materials, increase intensity, convenient processing.
It is including as follows present invention also offers the preparation method that a kind of vinal strengthens polyphenyl thioether composite material Step:(1) by polyphenylene sulfide, vinal and glass fibre, and compatilizer, antioxidant, coupling agent and lubricant are mixed Close, obtain compound;(2) extruder is added mixture into, strip composite is extruded.
In some embodiments, vinal strengthens the preparation method of polyphenyl thioether composite material, wherein also wrapping Include the strip composite cooling and dicing that step (3) will obtain in step (2) and be made plastic pellet.Thus, it is easy to material to store, with And process again.
Vinal strengthens the preparation method of polyphenyl thioether composite material in some embodiments, wherein in step (1) by polyphenylene sulfide, and auxiliary agent adds glass fibre and vinal passes through after high-speed stirred mixes dispersion Stirring at low speed obtains compound.By polyphenylene sulfide, and auxiliary agent can be with by (more than 3000 revs/min) stirring mixing dispersions at a high speed Make stirring efficiency higher, (less than 200 revs/min) stirrings of low speed can be avoided again to add glass fibre and vinal Glass fibre forms cotton wool and is difficult scattered situation in stirring.
Specific embodiment
The invention will be further described by the following examples, but protection domain is not restricted by the embodiments.
Embodiment 1:
First, polyphenylene sulfide and compatilizer, antioxidant, coupling agent, lubricant are passed through into high-speed stirred under normal temperature and pressure Mixing is uniformly dispersed, and mixing speed is about more than 3000 revs/min, and mixing time is about 3 minutes.Again by glass fibre and poly- second Enol fiber is added, and is uniformly dispersed by stirring at low speed, and mixing speed is about less than 200 revs/min, obtains compound.At this In embodiment, in terms of parts by weight, polyphenylene sulfide 40, vinal 30, glass fibre 40, auxiliary agent 2.With parts by weight Meter, compatilizer 1, antioxidant 0.3, coupling agent 0.3, lubricant 0.4.
Then, in adding mixture into double screw extruder, double screw extruder set process conditions as temperature 300~ 350 DEG C, 1100 revs/min of screw speed.
Finally, the discharging opening in double screw extruder sets cold rinse bank, and the strip composite that will be extruded is in cold rinse bank Tie rod pelletizing, is cut into 5~6mm vinal enhancing polyphenyl thioether composite material particles long, is easy to store and transports.It is cold Water temperature in tank is less than 40 DEG C.
After measured, the notch impact strength of vinal enhancing polyphenyl thioether composite material manufactured in the present embodiment is 9.8 kilojoules/square metre, melt index (MI) is 0.9 gram/10 seconds, and bending modulus is 23500, and tensile strength is 190 MPas, and bending is strong It is 200 MPas to spend, and heat distortion temperature is 260 degrees Celsius, and density is 1.72 grams/cc.
Mixing time can extend or shorten according to actual conditions.
In the present embodiment, compatilizer is maleic anhydride grafted polyethylene.In other embodiments, compatilizer can also be The maleic anhydride stem grafting polyolefin class material such as maleic anhydride inoculated polypropylene or maleic anhydride grafting polybutene, can also be propylene Sour graft polypropylene (acrylic acid-grafted PP) etc..
In the present embodiment, antioxidant is hydroxy phenyl acrylate.In other embodiments, antioxidant can also be hydroxyl Base benzyl acrylic ester, alkylidene bisphenols or thiobisphenol etc..
In the present embodiment, coupling agent is γ-aminopropyl triethoxysilane.In other embodiments, coupling agent also may be used Think propanethiol trimethyl TMOS or ethyoxyl triethoxysilane etc..
In the present embodiment, lubricant is stearic acid.In other embodiments, lubricant can also be Tissuemat E, fat Fat acid monoamides, acetic acid, metallic soap etc..
Table 1 is embodiment 1, and prepares vinal enhancing in other 15 methods same as Example 1 In the embodiment of polyphenyl thioether composite material, the parts by weight of polyphenylene sulfide, glass fibre, vinal and auxiliary agent, with And it is the notch impact strength of prepared vinal enhancing polyphenyl thioether composite material, bending modulus, tensile strength, curved Qu Qiangdu, heat distortion temperature and density.
In these embodiments, in terms of parts by weight, wherein polyphenylene sulfide 40~50, vinal 20~30, glass Glass fiber 20~40, auxiliary agent 1~3.
From data in table 1, the notch shock of vinal enhancing polyphenyl thioether composite material of the invention is strong Degree, bending modulus and bending strength are improved.
The bending modulus of fiberglass enhanced polyphenyl thioether composite common at present is 13000~18000, bent 10000 times or so;The bending modulus of this vinal enhancing polyphenyl thioether composite material can be more than 20000, bent 2 Ten thousand times or so, it is adaptable to make the product for needing high temperature resistant, bearing bending for a long time, such as flabellum, the automobile of high-temperature exhaust air fan Blast pipe etc..
Above-described is only some embodiments of the present invention.For the person of ordinary skill of the art, not On the premise of departing from the invention design, various modifications and improvements can be made, these belong to protection model of the invention Enclose.

Claims (9)

1. vinal enhancing polyphenyl thioether composite material, it is characterised in that containing polyphenylene sulfide, vinal, Glass fibre and auxiliary agent, the auxiliary agent contain compatilizer, antioxidant, coupling agent and lubricant;
In terms of parts by weight, wherein polyphenylene sulfide 40~50, vinal 20~30, glass fibre 20~40.
2. vinal according to claim 1 strengthens polyphenyl thioether composite material, wherein the compatilizer is horse Maleic anhydride grafted polyolefin or acrylic acid-grafted PP.
3. vinal according to claim 1 strengthens polyphenyl thioether composite material, wherein the antioxidant is hydroxyl Base phenyl acrylate, hydroxyphenylmethyl acrylate, alkylidene bisphenols or thiobisphenol.
4. vinal according to claim 1 enhancing polyphenyl thioether composite material, wherein the coupling agent be γ- Aminopropyl triethoxysilane, propanethiol trimethyl TMOS or ethyoxyl triethoxysilane.
5. vinal according to claim 1 strengthens polyphenyl thioether composite material, wherein the lubricant is hard Ester acid, Tissuemat E, fatty acid mono-amide, acetic acid, metallic soap.
6. the vinal according to any one of Claims 1 to 5 strengthens polyphenyl thioether composite material, with parts by weight Meter, wherein compatilizer 1, antioxidant 0.3, coupling agent 0.3, lubricant 0.4.
7. preparing vinal as claimed in claim 1 strengthens the preparation method of polyphenyl thioether composite material, including such as Lower step:
(1) by polyphenylene sulfide, vinal and glass fibre, and compatilizer, antioxidant, coupling agent and mix lubricant Dispersion, obtains compound;
(2) compound is added into extruder, extrudes strip composite.
8. vinal according to claim 7 strengthens the preparation method of polyphenyl thioether composite material, wherein also wrapping Include the strip composite cooling and dicing that step (3) will obtain in the step (2) and be made plastic pellet.
9. the vinal according to claim 7 or 8 strengthens the preparation method of polyphenyl thioether composite material, wherein Polyphenylene sulfide and vinal, and auxiliary agent are added glass by the step (1) after high-speed stirred mixes dispersion Fiber obtains compound by stirring at low speed.
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PCT/CN2016/090833 WO2017012563A1 (en) 2015-07-22 2016-07-21 Polyvinyl alcohol fiber reinforced polyphenylene sulfide composite and preparation method therefor

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CN104974525B (en) * 2015-07-22 2017-07-04 广州高八二塑料有限公司 Vinal enhancing polyphenyl thioether composite material and preparation method thereof
CN105504812A (en) * 2015-12-21 2016-04-20 佛山市中科院环境与安全检测认证中心有限公司 Anti-impact engineering plastic
CN106928710B (en) * 2017-04-24 2019-05-07 苏州纳磐新材料科技有限公司 Polyphenyl thioether composite material and preparation method thereof
CN109517307A (en) * 2018-10-30 2019-03-26 南京聚隆科技股份有限公司 A kind of long glass fibres enhancing polyvinyl alcohol material and preparation method thereof
CN113174134A (en) * 2021-04-29 2021-07-27 怀化学院 High-impact-resistance flame-retardant polyphenylene sulfide composite material for optical fiber connector and preparation method thereof

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CN101397405A (en) * 2007-09-27 2009-04-01 四川得阳化学有限公司 Method for manufacturing high toughness polyphenyl thioether composite pellets
CN103289405A (en) * 2013-06-24 2013-09-11 苏州新区佳合塑胶有限公司 Polyurethane elastomer toughened polyphenylene sulfide resin plastic and preparation method thereof
CN103305003A (en) * 2013-07-11 2013-09-18 常熟市慧丰塑料制品有限公司 Formula of modified polyphenylene sulfide plastic

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