CN105802206B - A kind of high glass fiber content nylon66 fiber glass fiber compound material and preparation method thereof - Google Patents

A kind of high glass fiber content nylon66 fiber glass fiber compound material and preparation method thereof Download PDF

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Publication number
CN105802206B
CN105802206B CN201610240137.3A CN201610240137A CN105802206B CN 105802206 B CN105802206 B CN 105802206B CN 201610240137 A CN201610240137 A CN 201610240137A CN 105802206 B CN105802206 B CN 105802206B
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China
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glass
nylon
fiber
glass fiber
nylon66 fiber
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CN201610240137.3A
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CN105802206A (en
Inventor
唐颂超
李文振
施正堂
李�远
王石雄
王丽
王婷兰
潘泳康
张来胜
王论
董亮
刘竹霖
陈智
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East China University of Science and Technology
Zhejiang Asia Pacific Mechanical and Electronic Co Ltd
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East China University of Science and Technology
Zhejiang Asia Pacific Mechanical and Electronic Co Ltd
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a kind of high glass fiber content nylon66 fiber glass fiber compound materials and preparation method thereof.The composite material is reinforcing material by matrix, high-content glass fibre of nylon, and hollow glass micropearl is auxiliary filler, adds interface cohesion agent and other auxiliary agents；Wherein, auxiliary filler is ball shape, can improve composite fluidity, improves processing performance；Interface cohesion agent is that the one end that consists of two parts anchors and be adsorbed in fiberglass surfacing, and the other end can mutually be wound outward with nylon molecules chain, and has effective Steric stabilization.Present invention improves the interfacial bonding properties of glass fibre and nylon to improve its dispersibility in nylon matrix again, is more advantageous to glass fibre and is orientated in nylon matrix, improves the performance of composite material.

Description

A kind of high glass fiber content nylon66 fiber glass fiber compound material and preparation method thereof
Technical field
The present invention relates to a kind of high glass fiber content nylon66 fiber glass fiber compound materials and preparation method thereof.
Background technique
Polyamide (PA is commonly called as nylon) is that Du Pont company, the U.S. develops the resin for being used for fiber at first, is had good Comprehensive performance, including mechanical property, heat resistance, wear resistance, chemical resistance and self-lubrication, and coefficient of friction is low, has Certain anti-flammability, it is easy to process.Wherein yield highest, it is most widely used be fatty polyamide, mainly have nylon 6 and nylon 66。
But pure nylon difference of hardness, water imbibition are high, tensile strength is low, and there are friction factor when dry friction is higher, easily The shortcomings that generating serious adhesive wear, being not particularly suitable for high load, high-speed friction environment, these disadvantages limit making for nylon66 fiber With, it is therefore necessary to enhancing modification is carried out to nylon.Enhancing modification is carried out to nylon and is to confer to its high performance effective ways, It is middle using it is most, most widely used be glass fiber reinforcement.
The research of glass fiber reinforcement PA66 widely and has been goed deep into, has realized industrialized production, but glass exists The dispersion in matrix PA66 resin will have a direct impact on the reinforcing effect of composite material, because the addition of glass, makes PA66 Original smooth surface becomes very coarse, and then influences the surface quality of product, simultaneously because the interface of glass and PA66 are tied Composition and division in a proportion is poor, so that the physical mechanics intensity of product is lower.Furthermore glass is also extremely serious to the abrasion of process equipment, very The wear and tear expense of machine context is increased in big degree, it is serious to limit its application.Therefore, glass fibre is modified Buddhist nun at present For the content of glass fibre substantially within 40%, performance is not able to satisfy the requirement of some parts in imperial composite system.
Summary of the invention
In order to solve the problems, such as background technique, it is an object of the invention to propose a kind of high glass fiber content nylon 66 glass fiber compound materials and preparation method thereof do lubricant using the auxiliary filler of ball shape, improve the processing of system Performance improves nylon/glass system interfacial bonding property using the interface cohesion agent with certain length solvent chain, makes glass Preferably dispersion, improves the mechanical property of the high glass fiber content compound system.
The technical solution adopted in the present invention is as follows:
One, a kind of high glass fiber content nylon66 fiber/glass fiber compound material:
It is the raw material for including following component and parts by weight: 36~46 parts of nylon；50~60 parts of glass fibre；Auxiliary filling 0~3 part of agent；0~2 part of interface cohesion agent；1 part of antioxidant, 1 part of lubricant.
The nylon can be nylon 6, nylon66 fiber, and group in the composite is divided into 36~46 parts.
The glass fibre can be short glass fiber, continuous glass fibre, woven glass roving fabric, Group in composite material is divided into 50~60 parts.
The auxiliary filler is the hollow glass micropearl of 100~800 mesh of partial size, in component in the composite It is 1~3 part.
The interface cohesion agent uses the interface cohesion agent of CH-1, CH-2 or CH-3 model, three kinds of interface cohesions Its anchoring group of agent is different, and polar solvent chain length is different, and molecular weight is different, and number-average molecular weight is 1500~2500 Daltons。
The antioxidant is the combination of main antioxidant 1010, auxiliary anti-oxidant 168, and addO-on therapy is 1 part.
The lubricant is the combination of EBS, calcium stearate, and addO-on therapy is 1 part.
The equipment of the synthetic composite material is the double screw extruder with lateral feeding.
Two, a kind of preparation method of high glass fiber content nylon66 fiber/glass fiber compound material:
1) nylon is 10 hours dry in 80 DEG C of vacuum drying oven, glass is 8 hours dry at 60 DEG C, assists filler It is 8 hours dry at 80 DEG C,
2) by addition to glass fibre other auxiliary agents and nylon according to above-mentioned and ingredient and proportion mix in a high speed mixer It closes 3~5min and obtains mixture, then mixture is added from the major ingredient mouth of double screw extruder, glass is added from side spout, so Extruding pelletization, barrel revolving speed are 15r/min after melt blending at 235~280 DEG C afterwards, and screw speed is 150~200r/min, It is finally that pellet is 10 hours dry in 80 DEG C of baking ovens, obtain the composite products.
To prepare high strength glass fiber modified nylon materials, the present invention selects the glass fibre that superelevation 50% is added, and The shortcomings that auxiliary filler and interface cohesion agent are to overcome glass fibre is added simultaneously.Filling the fillers such as hollow glass micropearl can It is floating fine exposed to improve, improve product surface finish, improve mobile performance, reduce contraction distortion rate, make it is easy to process, overcome Warping phenomenon after product, the heat resisting temperature and wear-resisting, scratch resistance for improving product, and assist the lower price of filler can be with Substantially reduce production cost.
Interface cohesion agent of the invention be consist of two parts one end be can with fiberglass surfacing occur physics, chemistry The group of effect anchors and is adsorbed in fiberglass surfacing, and one end is the long solvent chain of the polarity affinity with nylon, long Solvent chain can mutually be wound outward with nylon molecules chain, and make it steady with effective space with certain length It is set for using, the interfacial bonding property for improving glass fibre and nylon improves its dispersibility in nylon matrix again, more favorably It is orientated in nylon matrix in glass fibre, improves the performance of composite material.
The invention has the following advantages that
The content of glass fiber that the present invention obtains is higher, and every mechanical property is more excellent.
The present invention improves composite fluidity, improves the processing performance of system by the addition of auxiliary filler.
The present invention passes through the addition of interface cohesion agent, improves the dispersibility of glass fibre, is more advantageous to it in nylon base It is orientated in body, improves the performance of composite material.
Specific embodiment
The contents of the present invention are described in detail now in conjunction with specific embodiment.
Embodiment 1
It is formulated by following raw material ratio by weight:
Nylon is 10 hours dry in 80 DEG C of vacuum drying oven, and glass is 8 hours dry at 60 DEG C, and auxiliary filler exists It is 8 hours dry at 80 DEG C, other auxiliary agents in addition to glass fibre are mixed into 3min with nylon in a high speed mixer, and press respectively According to proportion, mixture is added in double screw extruder major ingredient mouth, glass is added in side spout, then the melt blending at 235 DEG C Extruding pelletization afterwards.Barrel revolving speed is 15r/min, screw speed 150r/min.Finally by pellet dry 10 in 80 DEG C of baking ovens Hour.
Embodiment 2
It is formulated by following raw material ratio by weight:
Nylon is 10 hours dry in 80 DEG C of vacuum drying oven, and glass is 8 hours dry at 60 DEG C, and auxiliary filler exists It is 8 hours dry at 80 DEG C, other auxiliary agents in addition to glass fibre are mixed into 5min with nylon in a high speed mixer, and press respectively According to proportion, mixture is added in double screw extruder major ingredient mouth, glass is added in side spout, then the melt blending at 280 DEG C Extruding pelletization afterwards.Barrel revolving speed is 15r/min, screw speed 200r/min.Finally by pellet dry 10 in 80 DEG C of baking ovens Hour.
The composite material that the present embodiment prepares is through detecting, tensile strength 187.4MPa, with 35% glass fibre 66 composite material of modification of nylon improves at 8.1%, but 275 DEG C compared to 20.6%, bending modulus 11.77GPa is improved Melt flow index (MVR) is 8.73ccm/10min, reduces 66.7%, illustrates the composite materials property compared with 35% glass Glass fibre modification nylon 66 composite material mechanical property increases, but mobile performance sharp fall, processing performance are poor.
Embodiment 3
It is formulated by following raw material ratio by weight:
Nylon66 fiber is 10 hours dry in 80 DEG C of vacuum drying oven, and glass is 8 hours dry at 60 DEG C, will remove glass fibers Other auxiliary agents outside dimension mix 4min with nylon in a high speed mixer, and respectively according to the proportion, in double screw extruder plus fibre Mouthful glass is added, mixture is added in major ingredient mouth, then the extruding pelletization after melt blending at 275 DEG C.Barrel revolving speed is 15r/ Min, screw speed 170r/min.It is finally that pellet is 10 hours dry in 80 DEG C of baking ovens.
The composite material that the present embodiment prepares is through detecting, tensile strength 215.1MPa, with 35% glass fibre 66 composite material of modification of nylon improves 13.8% compared to 38.7%, bending modulus 12.4GPa is improved, molten at 275 DEG C Body flow index (MVR) is 21.17ccm/10min, reduces 21.6%, illustrates the composite materials property compared with 35% glass Fibre modification nylon 66 composite material mechanical property is improved largely, and mobile performance fall is little, technical effect It is significant prominent.
Embodiment 4
It is formulated by following raw material ratio by weight:
Nylon is 10 hours dry in 80 DEG C of vacuum drying oven, and glass is 8 hours dry at 60 DEG C, and auxiliary filler exists It is 8 hours dry at 80 DEG C, other auxiliary agents in addition to glass fibre are mixed into 3.5min with nylon in a high speed mixer, and respectively According to the proportion, mixture is added in double screw extruder major ingredient mouth, glass is added in side spout, then melts altogether at 275 DEG C Extruding pelletization after mixed.Barrel revolving speed is 15r/min, screw speed 180r/min.It is finally that pellet is dry in 80 DEG C of baking ovens 10 hours.
The composite material that the present embodiment prepares is through detecting, tensile strength 212.8MPa, with 35% glass fibre 66 composite material of modification of nylon improves 12.8% compared to 37.3%, bending modulus 12.3GPa is improved, molten at 275 DEG C Body flow index (MVR) is 20.69ccm/10min, reduces 23.3%, illustrates the composite materials property compared with 35% glass Fibre modification nylon 66 composite material mechanical property is improved largely, and mobile performance fall is little, and size Stability has promotion, and obvious technical effects are prominent.

Claims (1)

1. a kind of high glass fiber content nylon66 fiber glass fiber compound material, it is characterised in that:
The glass fiber compound material matches one of corresponding method preparation process using following two and is prepared:
The first matches corresponding method preparation process, by weight are as follows:
42 parts of nylon66 fiber
55 parts of woven glass roving fabric
1 part of CH-2 interface cohesion agent
Antioxidant 1010 and 1 part of mixing of 168,1010 and 168 be 3:2 mass ratio
1 part of mixing of EBS and calcium stearate, EBS and calcium stearate are 1:1 mass ratio
Nylon66 fiber is 10 hours dry in 80 DEG C of vacuum drying oven, and woven glass roving fabric is 8 hours dry at 60 DEG C, will Other auxiliary agents in addition to woven glass roving fabric mix 4min with nylon66 fiber in a high speed mixer, and respectively according to the proportion, Woven glass roving fabric is added in double screw extruder plus fine mouth, mixture is added in major ingredient mouth, then melts altogether at 275 DEG C Extruding pelletization after mixed；Barrel revolving speed is 15r/min, screw speed 170r/min；It is finally that pellet is dry in 80 DEG C of baking ovens 10 hours；
The corresponding method preparation process of second of proportion, by weight are as follows:
43 parts of nylon66 fiber
53 parts of woven glass roving fabric
Partial size is 2 parts of hollow glass micropearl of 300 mesh
Antioxidant 1010 and 1 part of mixing of 168,1010 and 168 be 3:2 mass ratio
1 part of mixing of EBS and calcium stearate, EBS and calcium stearate are 1:1 mass ratio
Nylon66 fiber is 10 hours dry in 80 DEG C of vacuum drying oven, and woven glass roving fabric is 8 hours dry at 60 DEG C, empty Heart glass microballoon dry 8 hours at 80 DEG C, by addition to woven glass roving fabric other auxiliary agents and nylon66 fiber it is mixed in high speed 3.5min is mixed in conjunction machine, and respectively according to the proportion, mixture is added in double screw extruder major ingredient mouth, glass is added in side spout The fibre untwisted rove of glass, the then extruding pelletization after melt blending at 275 DEG C；Barrel revolving speed is 15r/min, and screw speed is 180r/min；It is finally that pellet is 10 hours dry in 80 DEG C of baking ovens.
CN201610240137.3A 2016-04-15 2016-04-15 A kind of high glass fiber content nylon66 fiber glass fiber compound material and preparation method thereof Active CN105802206B (en)

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CN110256841B (en) * 2019-05-27 2021-10-15 中广核俊尔(浙江)新材料有限公司 High-performance high-fluidity polyamide composite material and preparation method thereof

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CN105153662B (en) * 2015-07-23 2017-10-17 深圳华力兴新材料股份有限公司 A kind of polycarbonate composite material of glass fiber reinforcement and preparation method thereof

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