CN102888039A - Preparation method of nano modified ultra-high molecular weight polyethylene (UHMWPE) antistatic composite material - Google Patents

Preparation method of nano modified ultra-high molecular weight polyethylene (UHMWPE) antistatic composite material Download PDF

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CN102888039A
CN102888039A CN2012103962004A CN201210396200A CN102888039A CN 102888039 A CN102888039 A CN 102888039A CN 2012103962004 A CN2012103962004 A CN 2012103962004A CN 201210396200 A CN201210396200 A CN 201210396200A CN 102888039 A CN102888039 A CN 102888039A
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uhmwpe
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molecular weight
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weight polyethylene
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CN102888039B (en
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张炜
李志�
洪尉
许振华
赵春保
李建龙
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Shanghai Research Institute of Chemical Industry SRICI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention relates to a preparation method of a nano modified ultra-high molecular weight polyethylene (UHMWPE) antistatic composite material, which comprises the following steps: putting 2-20 parts by weight of coating agent into a reaction kettle, melting at 150-180 DEG C, adding 1-10 parts by weight of nano conducting material and 1-5 parts by weight of dispersant, stirring for dispersion at high speed for 10-30 minutes, adding 10-50 parts by weight of solvent, cooling, filtering, and drying to obtain an organic layer coated nano conducting material; and mixing the organic layer coated nano conducting material with 100 parts by weight of UHMWPE at high speed, and granulating by extruding the mixture with a double screw extruder, thereby obtaining the product, wherein the extruded melt temperature is controlled at 200-230 DEG C. Compared with the prior art, the nano modified UHMWPE antistatic composite material forms a nano continuous three-dimensional net structure conducting network, and such three-dimensional interpenetrating nano dimensions are uniformly distributed, and make contributions to the formation of stable conducting path under the condition of low content of the conducting material.

Description

The preparation method of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material
Technical field
The invention belongs to technical field of polymer, relate to a kind of preparation method of continuous stereo reticulated structure nano modification UHMWPE anti-static composite material.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is viscosity-average molecular weight greater than 1,500,000 polyethylene (PE), is a kind of novel thermoplastic engineering plastics, and its high molecular weight, the segmented structure of highly twining are given its excellent mechanical property.The shock resistance of UHMWPE occupies first of the plastics, and is low temperature resistant, still can keep toughness at-80 ℃, corrosion-resistant, wear-resistant and self-lubricating property is excellent, is the ideal material of moulding Dai Gang.This material is studied and is used at high-technology fields such as petrochemical complex, technics of metallurgy mineral dressing, biomedicine, microelectron-mechanical, oceanographic engineerings.But the shortcomings such as UHMWPE exists, and heat resistance is poor, hardness is low, poor fluidity, tensile strength is low and flame retardant properties is poor.Utilize the distinctive surface effects of nanoparticle, small-size effect, quantum effect and macro quanta tunnel effect, exploitation Novel series nano-catalytic prepares UHMWPE resin and novel nano Complex Function UHMWPE material, is to improve the UHMWPE performance and make it obtain the effective way of broader applications.
Nano modification UHMWPE has the scholar to do certain research both at home and abroad.Krasnor etc. make the UHMWPE/Fe matrix material, and iron particle in the high-speed friction process chemical reaction occurs, and can play the active centre effect.Matrix material has low frictional coefficient, and good stability.Some scholar has released layered silicate fusion intercalation modified UHMWPE, research is found, layered silicate is peeled off and is dispersed in the UHMWPE matrix, the flow processability of material can be made moderate progress, but this method of modifying to as if the UHMWPE of viscosity-average molecular weight about 1,500,000, for the higher UHMWPE of viscosity-average molecular weight, layered silicate just can't be peeled off and be dispersed in the UHMWPE matrix.
Nanometer particle-modified UHMWPE, if do not resolve the compatible of nanoparticle and UHMWPE and dispersion, the interface of nanoparticle and UHMWPE has the hole, slit or nanoparticle is reunited in the UHMWPE matrix, the mechanical property of material especially wear resistance and shock-resistance significantly descends, and has lost as the UHMWPE tubing of slurry body, powder medium the most key wear-resisting, voltage endurance.So nano-material surface is processed and efficient dispersion technology is the effectively essential condition of performance of its function.
Because the melt viscosity of UHMWPE own is high, can't use conventional extrusion equipment machine-shaping tubing, and the adding of nanoparticle, so that the melt viscosity of system further strengthens.Dispersion and the microstructure control techniques of nanoparticle in the matrix of high melt viscosity is to realize the key of high-performance UHMWPE matrix material industryization production and application.
Summary of the invention
Purpose of the present invention is exactly the preparation method that the cancellated nano modification ultrahigh molecular weight polyethylene(UHMWPE) of a kind of continuous stereo anti-static composite material is provided for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material, it is characterized in that, the method is put into reactor with 2-20 part coating by weight, in 150-180 ℃ of melting, put into 1-10 part nanometer conductive material, 1-5 part dispersion agent, high-speed stirring was disperseed 10-30 minute, add 10-50 part solvent, cooling down, filtering drying obtains organic layer clad nano electro-conductive material; Then with above-mentioned organic layer clad nano electro-conductive material and 100 parts of ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 200-230 ℃, namely gets product.
Described coating is one or more in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, the ethylene-methacrylic acid copolymer.
Described nanometer conductive material is selected from one or more in nano carbon black, nano-graphite, carbon fiber, the copper nanoparticle.
Described dispersion agent is one or more in polyethylene wax, the paraffin.
Described solvent is one or more in distilled water, acetone, the ethanol.
Described ultrahigh molecular weight polyethylene(UHMWPE) is the polyethylene of viscosity-average molecular weight 1,500,000-7,000,000.
Compared with prior art, the present invention is directed to the adding of nanoparticle, so that the melt viscosity of UHMWPE matrix material further strengthens, be difficult to the technological difficulties such as extrusion moulding, with organic layer clad nano electro-conductive material, the UHMWPE matrix of itself and high melt viscosity is combined closely, improved consistency; Utilize simultaneously the organic coating agent have better flowability and UHMWPE matrix more than fusing point also without mobile feature difference, the dispersion microstructure of design organic layer clad nano electro-conductive material in the UHMWPE matrix, the modified UHMWPE anti-static composite material of realization twin-screw extrusion nano level continuous stereo reticulated structure conductive network.The interspersed nanoscale of this solid evenly distributes, to making contributions with regard to forming stable conductive path in low electro-conductive material content situation.
Description of drawings
Fig. 1 is the Electronic Speculum figure of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material of the present invention.
Embodiment
Embodiment 1
By weight 5 parts of ethylene-vinyl acetate copolymers are put into reactor, in 160 ℃ of meltings, put into 3 parts of nano carbon blacks, 2 parts of polyethylene waxs, 1 part of paraffin, high-speed stirring was disperseed 15 minutes, added 10 parts of acetone, cooling down, filtering drying obtains organic layer clad nano graphitized carbon black.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 3,500,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 210 ℃.The property indices of tubing sees Table 1.
Embodiment 2
By weight 2 parts of ethylene-methacrylic acid copolymers are put into reactor, in 150 ℃ of meltings, put into 1 part of carbon fiber, 4 parts of polyethylene waxs, high-speed stirring was disperseed 10 minutes, added 15 parts of distilled water, cooling down, filtering drying obtains organic layer coated with conductive carbon fiber.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 1,500,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 200 ℃.The property indices of tubing sees Table 1.
Embodiment 3
By weight 20 parts of ethylene-acrylic acid copolymers are put into reactor, in 180 ℃ of meltings, put into 6 parts of nano-graphites, 4 parts of copper nanoparticles, 5 parts of paraffin, high-speed stirring was disperseed 30 minutes, added 45 parts of ethanol, cooling down, filtering drying obtains organic layer clad nano electro-conductive material.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 5,000,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 230 ℃.The property indices of tubing sees Table 1.
Embodiment 4
By weight 8 parts of ethylene-vinyl acetate copolymers are put into reactor, in 155 ℃ of meltings, put into 5 parts of nano carbon blacks, 3 parts of polyethylene waxs, 2 parts of paraffin, high-speed stirring was disperseed 20 minutes, added 30 parts of distilled water, cooling down, filtering drying obtains organic layer clad nano graphitized carbon black.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 7,000,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 230 ℃.The property indices of tubing sees Table 1.
Embodiment 5
By weight 15 parts of ethylene-vinyl acetate copolymers are put into reactor, in 170 ℃ of meltings, put into 8 parts of nano-graphites, 5 parts of polyethylene waxs, high-speed stirring was disperseed 25 minutes, added 50 parts of distilled water, cooling down, filtering drying obtains organic layer clad nano electrically conductive graphite.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 4,500,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 220 ℃.The property indices of tubing sees Table 1.
Embodiment 6
By weight 2 parts of ethylene-vinyl acetate copolymers, 3 parts of ethylene-acrylic acid copolymers are put into reactor, in 160 ℃ of meltings, put into 1 part of nano carbon black, 1 part of carbon fiber, 2 parts of polyethylene waxs, 1 part of paraffin, high-speed stirring was disperseed 20 minutes, add 30 parts of acetone, cooling down, filtering drying obtains organic layer clad nano electro-conductive material.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 2,500,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 225 ℃.The property indices of tubing sees Table 1.
Embodiment 7
By weight 10 parts of ethylene-vinyl acetate copolymers are put into reactor, in 150 ℃ of meltings, put into 2 parts of nano carbon blacks, 2 parts of copper nanoparticles, 3 parts of polyethylene waxs, high-speed stirring was disperseed 15 minutes, add 20 parts of acetone, cooling down, filtering drying obtains organic layer clad nano electro-conductive material.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 6,000,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 230 ℃.The property indices of tubing sees Table 1.
Embodiment 8
By weight 20 parts of ethylene-vinyl acetate copolymers are put into reactor, in 160 ℃ of meltings, put into 2 parts of nano carbon blacks, 1 part of polyethylene wax, high-speed stirring was disperseed 20 minutes, added 30 parts of acetone, cooling down, filtering drying obtains organic layer clad nano electro-conductive material.Then with above-mentioned materials and 100 parts of viscosity-average molecular weight 2,500,000 ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 225 ℃.
Table 1 embodiment performance
Figure BDA00002267647000041
Figure BDA00002267647000051

Claims (6)

1. the preparation method of a nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material, it is characterized in that, the method is put into reactor with 2-20 part coating by weight, in 150-180 ℃ of melting, put into 1-10 part nanometer conductive material, 1-5 part dispersion agent, high-speed stirring was disperseed 10-30 minute, add 10-50 part solvent, cooling down, filtering drying obtains organic layer clad nano electro-conductive material; Then with above-mentioned organic layer clad nano electro-conductive material and 100 parts of ultrahigh molecular weight polyethylene(UHMWPE) high-speed mixing, with mixture twin screw extruder extruding pelletization, the melt extrusion temperature is controlled at 200-230 ℃, namely gets product.
2. the preparation method of a kind of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material according to claim 1, it is characterized in that, described coating is one or more in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, the ethylene-methacrylic acid copolymer.
3. the preparation method of a kind of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material according to claim 1 is characterized in that, described nanometer conductive material is selected from one or more in nano carbon black, nano-graphite, carbon fiber, the copper nanoparticle.
4. the preparation method of a kind of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material according to claim 1 is characterized in that, described dispersion agent is one or more in polyethylene wax, the paraffin.
5. the preparation method of a kind of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material according to claim 1 is characterized in that, described solvent is one or more in distilled water, acetone, the ethanol.
6. the preparation method of a kind of nano modification ultrahigh molecular weight polyethylene(UHMWPE) anti-static composite material according to claim 1 is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) is the polyethylene of viscosity-average molecular weight 1,500,000-7,000,000.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435904A (en) * 2013-09-18 2013-12-11 中国石油化工股份有限公司 Antistatic high-rigidity rotational-moulded polyethylene composition and preparation method thereof
CN104530527A (en) * 2014-12-24 2015-04-22 陈程 High-strength PE (polyethylene) conducting composite material and preparation method thereof
CN105693937A (en) * 2016-02-24 2016-06-22 湖南琦琳高分子导电材料有限公司 Conducting composite material with ultrahigh molecular weights and method for manufacturing conducting composite material
CN107602984A (en) * 2017-09-27 2018-01-19 江苏瑞腾涂装科技有限公司 A kind of ultra-high molecular weight polyethylene composite material
CN107663328A (en) * 2017-10-13 2018-02-06 扬州大学 The preparation method of carbon fiber and the ultrahigh molecular weight polyethylene abrasion-proof material of silica nanosphere collaboration filling
CN107746497A (en) * 2017-11-21 2018-03-02 广东工业大学 A kind of anti-static composite material and preparation method thereof
CN110471134A (en) * 2018-05-11 2019-11-19 住华科技股份有限公司 Surface treatment liquid and optical film

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435904A (en) * 2013-09-18 2013-12-11 中国石油化工股份有限公司 Antistatic high-rigidity rotational-moulded polyethylene composition and preparation method thereof
CN104530527A (en) * 2014-12-24 2015-04-22 陈程 High-strength PE (polyethylene) conducting composite material and preparation method thereof
CN105693937A (en) * 2016-02-24 2016-06-22 湖南琦琳高分子导电材料有限公司 Conducting composite material with ultrahigh molecular weights and method for manufacturing conducting composite material
CN107602984A (en) * 2017-09-27 2018-01-19 江苏瑞腾涂装科技有限公司 A kind of ultra-high molecular weight polyethylene composite material
CN107663328A (en) * 2017-10-13 2018-02-06 扬州大学 The preparation method of carbon fiber and the ultrahigh molecular weight polyethylene abrasion-proof material of silica nanosphere collaboration filling
CN107663328B (en) * 2017-10-13 2020-02-07 扬州大学 Preparation method of ultrahigh molecular weight polyethylene wear-resistant material cooperatively filled with carbon fibers and silicon dioxide nanospheres
CN107746497A (en) * 2017-11-21 2018-03-02 广东工业大学 A kind of anti-static composite material and preparation method thereof
CN107746497B (en) * 2017-11-21 2021-03-16 广东工业大学 Antistatic composite material and preparation method thereof
CN110471134A (en) * 2018-05-11 2019-11-19 住华科技股份有限公司 Surface treatment liquid and optical film

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