CN104151695B - The preparation method of the polypropylene composite pipe that a kind of Graphene is modified - Google Patents
The preparation method of the polypropylene composite pipe that a kind of Graphene is modified Download PDFInfo
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- CN104151695B CN104151695B CN201410190682.7A CN201410190682A CN104151695B CN 104151695 B CN104151695 B CN 104151695B CN 201410190682 A CN201410190682 A CN 201410190682A CN 104151695 B CN104151695 B CN 104151695B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention provides the preparation method of the modified polypropylene composite pipe of a kind of Graphene, its step includes: the preparation of (1) modified graphene powder；(2) preparation of modified graphene powder/polypropene blended master batch；(3) with the preparation of the polypropylene composite pipe of Graphene modification.The present invention makes full use of existing equipment in polypropylene composite pipe industry, and a small amount of modified graphene powder only need to be utilized on formula can be obviously improved tubing in terms of mechanical strength and ageing resistace, and low cost, effect is obvious, has the strongest practicality.
Description
Technical field
The present invention relates to plastic conduit field, specifically refer to the polypropylene that a kind of Graphene is modified
The preparation method of composite pipe.
Background technology
Plastic conduit, due to the performance of its excellence, has been widely used in each field such as engineering discharge
Water, energy heating system, gas pipeline system etc..But it is as progress and state's people's livelihood of society
The raising that running water is flat, the requirement to the performance particularly combination property of pipeline improves day by day.These
Performance requirement includes (as further improved resistance to compression and the shock resistance of pipeline, carrying of power
The cold-check resistance etc. of high pipeline), heat (as improved the heat conduction of pipeline in heating pipe system
Coefficient etc.), (as improved the antistatic property etc. of pipeline) of electricity, (such as the carrying of chemical stability
The ageing resistace etc. of high pipeline) etc. performance.But on the whole, how to keep pipe
On the basis of the original performance in road, particular characteristic is promoted, be that pendulum is in face of plastic processing industry
A difficult problem.
The appearance of Graphene brings hope to cracking of this difficult problem.Graphene is the current world
Upper known mechanical strength the highest (fracture strength 130GPa, Young's modulus 1.0TPa),
(resistivity 10-6 Ω cm conducts electricity most for thin (thickness 0.3nm), conduction
Argent), (under room temperature, thermal conductivity reaches 5000W/m k, exceedes and is currently known in heat conduction
The diamond that thermal conductivity is the highest) etc. performance.These excellent properties of Graphene so that Graphene
Very likely become the material improving plastic conduit combination property.
Although the report of Graphene polymer composite or patent have occurred (such as application number
ZL201110313859.4, ZL201310034290.7, ZL201110337141.9 etc.), but
It is really for pipeline material and lifting to be had to have not been reported correlated performance Graphene.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art to provide the modification of a kind of Graphene
The preparation method of polypropylene composite pipe, the polypropylene composite pipe prepared by this method has good
Good mechanical property and ageing resistace.
The present invention is achieved through the following technical solutions: the polypropylene that a kind of Graphene is modified
The preparation method of composite pipe, its step includes: (1) is by 1 × 10-3The surface of-1 parts by weight
Inorganic agent, adds to 1-1000 parts by weight solvent, the two is stirring evenly and then adding into
The graphene powder of 1-100 parts by weight, prepares ultrasonic disperse after mixture high-speed stirred and changes
Property graphene dispersing solution；Again this modified graphene dispersion liquid it is dried and after spheroidal graphite, prepares modified stone
Ink alkene powder；(2) by the modified graphene of the 0.1-30 parts by weight described in step (1)
Powder, joins in the acrylic resin of 100 parts by weight, adds 0.1-1 parts by weight
Antioxidant and the dispersant of 0.1-1 parts by weight, mixing dispersion after again extruding pelletization prepare changes
Property graphene powder/polypropene blended master batch；(3) by the 1-100 weight described in step (2)
Modified graphene powder/polypropene blended the master batch of amount number is with the polypropylene of 100 parts by weight
After resin agitating is uniform, extrusion molding prepares the polypropylene composite pipe modified with Graphene.
Described surface conditioning agent is silane coupler, titanate coupling agent, octadecylamine, different
One or more in cyanic acid.
Described solvent is ethanol/water solution or ethanol/acetum.
Described acrylic resin is tubing grade polypropylene resin, including true qualities particulate material, coloured
Pellet, powder.
Described antioxidant is one or more in hindered phenol or phosphite antioxidant.
Described dispersant is paraffin, Tissuemat E or fatty acid dispersant.
Mixing in described step (2) is to utilize Z-shaped kneader, high-speed mixer, mill
Machine or banbury mix.
Extruding pelletization in described step (2) is to utilize single screw extrusion machine, twin-screw extrusion
Machine or Planetary Screw Extruder are carried out.
The polypropylene composite pipe of Graphene of the present invention modification can apply to building
Give/drainage pipe, municipal administration tubing, industrial pipes, chemical industry tubing, protecting pipe field etc..This
Invention makes full use of existing equipment in polypropylene composite pipe industry, only need to utilize on formula
A small amount of modified graphene powder can to tubing in terms of mechanical strength and ageing resistace bright
Aobvious lifting, low cost, effect is obvious, has the strongest practicality.
Accompanying drawing explanation
Fig. 1 is the preparation method schematic flow sheet of the present invention.
Detailed description of the invention
By the following specific examples further illustrate the invention, the preparation method stream of the present invention
Journey is as shown in Figure 1:
Embodiment 1
(1) preparation of modified graphene powder: by the silane coupler of 1 parts by weight, add
Entering in 100 parts by weight ethanol/water solution (ethanol: water=95:5, weight ratio), stirring is all
Adding the graphene powder of 10 parts by weight after even, after high-speed stirred, ultrasonic disperse is prepared again changes
Property graphene dispersing solution；Ball mill is utilized to prepare modified graphite the most after drying this dispersion liquid again
Alkene powder；
(2) preparation of modified graphene powder/polypropene blended master batch: described in (1)
The modified graphene powder of 30 parts by weight, join the polypropylene tree of 100 parts by weight
In fat, add irgasfos 168 and the 1010 2:1 in mass ratio mixing of 0.5 parts by weight
Mixture, the Tissuemat E of 0.5 parts by weight, utilize banbury mixing dispersion, then will altogether
Mixed thing joins extruding pelletization in double screw extruder, and to prepare modified graphene powder/polypropylene common
Mixed master batch, described acrylic resin is tubing grade polypropylene resin, including true qualities particulate material, has
Coloured particles material, powder；
(3) with the preparation of the polypropylene composite pipe of Graphene modification: described in (2)
The modified graphene powder of 5 parts by weight/polypropene blended master batch gathering with 100 parts by weight
After propylene multiple tube material stirs, join prepared Graphene in plastic pipe extruder
Modified polypropylene composite pipe 1.
Embodiment 2
(1) preparation of modified graphene powder: by the titanate esters coupling of 0.001 parts by weight
Agent, adds in 1 parts by weight ethanol/acetum (ethanol: acetic acid=95:5, weight ratio),
It is stirring evenly and then adding into the graphene powder of 1 parts by weight, ultrasonic disperse system again after high-speed stirred
Obtain modified graphene dispersion liquid；This dispersion liquid utilize ball mill prepare modification more after drying
Graphene powder；
(2) preparation of modified graphene powder/polypropene blended master batch: described in (1)
The modified graphene powder of 0.1 parts by weight, join the polypropylene tree of 100 parts by weight
In fat, add the irgasfos 168 of 0.1 parts by weight, the paraffin of 0.1 parts by weight, profit
Disperse with the mixing of Z-shaped kneader, then blend is joined extruding pelletization in single screw extrusion machine
Preparing modified graphene powder/polypropene blended master batch, described acrylic resin is that tubing level is gathered
Allyl resin, including true qualities particulate material, coloured particle material, powder；
(3) with the preparation of the polypropylene composite pipe of Graphene modification: described in (2)
The modified graphene powder of 1 parts by weight/polypropene blended master batch gathering with 100 parts by weight
After propylene multiple tube material stirs, join prepared Graphene in plastic pipe extruder
Modified polypropylene composite pipe 2.
Embodiment 3
(1) preparation of modified graphene powder: by the octadecylamine of 0.8 parts by weight and
Isocyanic acid coupling agent, add 1000 parts by weight ethanol/water solution (ethanol: water=95:5,
Weight ratio) in, it is stirring evenly and then adding into the graphene powder of 100 parts by weight, high-speed stirred
After again ultrasonic disperse prepare modified graphene dispersion liquid；Again this dispersion liquid is utilized the most after drying
Ball mill prepares modified graphene powder；
(2) preparation of modified graphene powder/polypropene blended master batch: described in (1)
The modified graphene powder of 10 parts by weight, join the polypropylene tree of 100 parts by weight
In fat, add the antioxidant 1010 of 1 parts by weight, the aliphatic acid of 1 parts by weight, utilize
Mill mixing dispersion, then blend is joined extruding pelletization in Planetary Screw Extruder prepare
Modified graphene powder/polypropene blended master batch, described acrylic resin is tubing grade polypropylene
Resin, including true qualities particulate material, coloured particle material, powder；
(3) with the preparation of the polypropylene composite pipe of Graphene modification: described in (2)
The modified graphene powder of 100 parts by weight/polypropene blended master batch is with 100 parts by weight
After polypropylene composite pipe material stirs, join prepared graphite in plastic pipe extruder
The polypropylene composite pipe 3 that alkene is modified.
Embodiment 4
(1) preparation of modified graphene powder: by the octadecylamine of 0.1 parts by weight and
Isocyanic acid coupling agent, adds 500 parts by weight ethanol/water solution (ethanol: water=95:5, weight
Amount ratio) in, it is stirring evenly and then adding into the graphene powder of 50 parts by weight, after high-speed stirred
Ultrasonic disperse prepares modified graphene dispersion liquid again；Again this dispersion liquid is utilized ball the most after drying
Grinding machine prepares modified graphene powder；
(2) preparation of modified graphene powder/polypropene blended master batch: described in (1)
The modified graphene powder of 20 parts by weight, join the polypropylene tree of 100 parts by weight
In fat, add the antioxidant 1010 of 0.3 parts by weight, the aliphatic acid of 0.6 parts by weight,
Utilize high-speed mixer mixing dispersion, then blend is joined extrusion in Planetary Screw Extruder
Granulation prepares modified graphene powder/polypropene blended master batch, and described acrylic resin is tubing
Grade polypropylene resin, including true qualities particulate material, coloured particle material, powder；
(3) with the preparation of the polypropylene composite pipe of Graphene modification: described in (2)
The modified graphene powder of 50 parts by weight/polypropene blended master batch gathering with 100 parts by weight
After propylene multiple tube material stirs, join prepared Graphene in plastic pipe extruder
Modified polypropylene composite pipe 4.
The present invention prepares the polypropylene composite pipe using modified graphene of gained, relative to not adding
Adding the polypropylene composite pipe of Graphene, hot strength improves 30%, and low temperature notched impact is strong
Degree improves 50%, and additionally this tubing has been also equipped with the merits such as antistatic, electromagnetic shielding, high heat conduction
Energy.
Other unaccounted part is prior art.
Claims (7)
1. with a preparation method for the polypropylene composite pipe of Graphene modification, its step bag
Include: (1) is by 1 × 10-3The surface conditioning agent of-1 parts by weight, adds to 1-1000 weight portion
In number solvent, the two is stirring evenly and then adding into the graphene powder of 1-100 parts by weight, will
After mixture high-speed stirred, ultrasonic disperse prepares modified graphene dispersion liquid；Again by this modified graphite
Alkene dispersion liquid is dried and prepares modified graphene powder after spheroidal graphite；Described solvent is that ethanol/water is molten
Liquid or ethanol/acetum；(2) by the 0.1-30 parts by weight described in step (1)
Modified graphene powder, joins in the acrylic resin of 100 parts by weight, adds 0.1-1
The antioxidant of parts by weight and the dispersant of 0.1-1 parts by weight, after mixing dispersion, extrusion is made again
Grain prepared modified graphene powder/polypropene blended master batch；(3) by described in step (2)
The modified graphene powder of 1-100 parts by weight/polypropene blended master batch is with 100 parts by weight
Acrylic resin stir after, extrusion molding prepares the polypropylene composite materials modified with Graphene
Tubing.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: described surface conditioning agent be silane coupler, titanate coupling agent,
One or more in octadecylamine, isocyanic acid.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: described acrylic resin is tubing grade polypropylene resin, including true qualities
Particulate material, coloured particle material, powder.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: described antioxidant is the one in hindered phenol or phosphite antioxidant
Or it is multiple.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: described dispersant is paraffin, Tissuemat E or fatty acid dispersant.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: the mixing in described step (2) is to utilize Z-shaped kneader, height
Speed mixer, mill or banbury mixing.
The most according to claim 1 with the preparation of the polypropylene composite pipe of Graphene modification
Method, it is characterised in that: the extruding pelletization in described step (2) is to utilize Single screw extrusion
Machine, double screw extruder or Planetary Screw Extruder are carried out.
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| CN201410190682.7A CN104151695B (en) | 2014-05-07 | 2014-05-07 | The preparation method of the polypropylene composite pipe that a kind of Graphene is modified |
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| CN201410190682.7A CN104151695B (en) | 2014-05-07 | 2014-05-07 | The preparation method of the polypropylene composite pipe that a kind of Graphene is modified |
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| CN104151695B true CN104151695B (en) | 2016-09-07 |
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| CN109251429A (en) * | 2018-08-08 | 2019-01-22 | 多凌新材料科技股份有限公司 | The graphene/carbon nano-tube master batch and its preparation method that are easily dispersed in PVC and application |
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