CN104151696B - The preparation method of the polypropylene steel-plastic composite pipe that a kind of Graphene is modified - Google Patents
The preparation method of the polypropylene steel-plastic composite pipe that a kind of Graphene is modified Download PDFInfo
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- CN104151696B CN104151696B CN201410190683.1A CN201410190683A CN104151696B CN 104151696 B CN104151696 B CN 104151696B CN 201410190683 A CN201410190683 A CN 201410190683A CN 104151696 B CN104151696 B CN 104151696B
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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 steel-plastic composite pipe of a kind of Graphene, its step includes: the preparation of (1) modified graphene powder;(2) preparation of blended master batch moulded by modified graphene powder/polypropylene steel;(3) with the preparation of the polypropylene steel-plastic composite pipe of Graphene modification.The present invention makes full use of existing equipment in polypropylene steel-plastic composite pipe industry, a small amount of modified graphene powder only need to be utilized on formula can tubing to be obviously improved in terms of mechanical strength and ageing resistace, 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 steel-plastic composite pipe.
Background technology
Polypropylene steel moulds pipe as a kind of emerging composite pipe, performance all ten in a lot of aspects
Point excellence, the bearing capacity possessed due to its steel band so that steel moulds pipe as a kind of engineering tubing,
At municipal administration, chemical industry, find broad application in the field such as mining.But, common polypropylene steel is moulded
Pipe transports various industrial liquids due to long-term, and liquid often has corrosivity and temperature change very
Greatly, the impact on multiple tube layers cementing intensity and intermediate layer steel band is very big, and this is with regard to an urgent demand
Steel is moulded inside pipe wall and is had the most wear-resistant and resistance to chemical corrosion.
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 steel-plastic composite pipe, the polypropylene steel-plastics composite pipe prepared by this method
Material has good mechanical property, wear resistance and corrosion resistance.
The present invention is achieved through the following technical solutions: the polypropylene that a kind of Graphene is modified
The preparation method of steel-plastic composite pipe, its step includes: (1) is by 1 × 10-3-1 parts by weight
Surface conditioning agent, adds to 1-1000 parts by weight solvent, adds after the two being stirred
Enter the graphene powder of 1-100 parts by weight, ultrasonic disperse after mixture high-speed stirred is prepared
Modified graphene dispersion liquid;Again this modified graphene dispersion liquid it is dried and after spheroidal graphite, prepares modification
Graphene powder;(2) by the modified graphite of the 0.1-30 parts by weight described in step (1)
Alkene powder, joins in the acrylic resin of 100 parts by weight, adds 0.1-1 weight portion
The antioxidant of number and the dispersant of 0.1-1 parts by weight, after mixing dispersion, extruding pelletization prepares again
Modified graphene powder/polypropene blended master batch;(3) by the 1-100 described in step (2)
The modified graphene powder of parts by weight/polypropene blended master batch is with poly-the third of 100 parts by weight
After olefine resin stirs, extrusion molding prepares the polypropylene inner tube modified with Graphene, finally
The polypropylene inner tube modified with described Graphene by steel band and unmodified outer layer polypropylene
Hot melt adhesion gets up and prepares the polypropylene steel-plastic 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, polypropylene wax 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 steel-plastic composite pipe of Graphene of the present invention modification can apply to
Building gives/drainage pipe, municipal pipeline, industrial pipeline, chemical pipeline, protecting pipe etc..This
Invention makes full use of existing equipment in polypropylene steel-plastic composite pipe industry, only need to be on formula
Utilize a small amount of modified graphene powder can to tubing wear-resistant undermine decay resistance in terms of
Being obviously improved, 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, the irgasfos 168 and 1010 adding 0.5 parts by weight mixes according to mass ratio 2:1
The mixture closed, the polypropylene wax of 0.5 parts by weight, utilize banbury mixing dispersion, then will
Blend joins extruding pelletization in double screw extruder and prepares modified graphene powder/polypropylene
Be 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 steel-plastic composite pipe of Graphene modification: by institute in (2)
The modified graphene powder of 5 parts by weight stated/polypropene blended master batch is with 100 parts by weight
Polypropylene composite pipe material stir after, join prepared stone in plastic pipe extruder
The polypropylene inner tube that ink alkene is modified, finally by polypropylene modified with described Graphene for steel band
Pipe and fusible the preparing of unmodified outer layer polypropylene thermal use poly-the third of Graphene modification
Alkene steel-plastic 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 steel-plastic composite pipe of Graphene modification: by institute in (2)
The modified graphene powder of 1 parts by weight stated/polypropene blended master batch is with 100 parts by weight
Polypropylene composite pipe material stir after, join prepared stone in plastic pipe extruder
The polypropylene inner tube that ink alkene is modified, finally by polypropylene modified with described Graphene for steel band
Pipe and fusible the preparing of unmodified outer layer polypropylene thermal use poly-the third of Graphene modification
Alkene steel-plastic 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 steel-plastic composite pipe of Graphene modification: by institute in (2)
The modified graphene powder of 100 parts by weight stated/polypropene blended master batch is with 100 weight portions
After the polypropylene composite pipe material of number stirs, join plastic pipe extruder prepares and use
The polypropylene inner tube that Graphene is modified, finally by polypropylene modified with described Graphene for steel band
Inner tube and fusible the preparing of unmodified outer layer polypropylene thermal use modified the gathering of Graphene
Propylene steel-plastic composite pipe 3.
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 steel-plastic composite pipe of Graphene modification: by institute in (2)
The modified graphene powder of 50 parts by weight stated/polypropene blended master batch is with 100 parts by weight
Polypropylene composite pipe material stir after, join prepared stone in plastic pipe extruder
The polypropylene inner tube that ink alkene is modified, finally by polypropylene modified with described Graphene for steel band
Pipe and fusible the preparing of unmodified outer layer polypropylene thermal use poly-the third of Graphene modification
Alkene steel-plastic composite pipe.
The present invention prepares the polypropylene steel-plastic composite pipe using modified graphene of gained, relative to
Being not added with the polypropylene steel-plastic composite pipe of Graphene, layers cementing intensity improves 30%, expands
Mouth hot strength improves 24%, and ageing resistace improves 20%, and additionally this composite pipe is also
Possess high heat conduction, resistance to chemical attack, the function such as wear-resistant.
Other unaccounted part is prior art.
Claims (7)
1., by a preparation method for the polypropylene steel-plastic composite pipe of Graphene modification, its step includes: (1) is by 1 × 10-3The surface conditioning agent of-1 parts by weight, 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, ultrasonic disperse after mixture high-speed stirred is prepared modified graphene dispersion liquid;Again this modified graphene dispersion liquid it is dried and after ball milling, prepares modified graphene powder;Described solvent is ethanol/water solution or ethanol/acetum;(2) by the modified graphene powder of the 0.1-30 parts by weight described in step (1), join in the acrylic resin of 100 parts by weight, adding antioxidant and the dispersant of 0.1-1 parts by weight of 0.1-1 parts by weight, after mixing dispersion, extruding pelletization prepares modified graphene powder/polypropene blended master batch again;(3) after the modified graphene powder/polypropene blended master batch of the 1-100 parts by weight described in step (2) being stirred with the acrylic resin of 100 parts by weight, extrusion molding prepares the polypropylene inner tube modified with Graphene, finally prepares the polypropylene steel-plastic composite pipe modified with Graphene by fusible to polypropylene inner tube modified with described Graphene for steel band and unmodified outer layer polypropylene thermal.
The most according to claim 1 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, it is characterised in that: described surface conditioning agent is one or more in silane coupler, titanate coupling agent, octadecylamine, isocyanic acid.
The most according to claim 1 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, 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 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, it is characterised in that: described antioxidant is one or more in hindered phenol or-phosphite antioxidant.
The most according to claim 1 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, it is characterised in that: described dispersant is paraffin, polypropylene wax or fatty acid dispersant.
The most according to claim 1 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, it is characterised in that: the mixing in described step (2) utilizes Z-shaped kneader, high-speed mixer, mill or banbury mixing.
The most according to claim 1 by the preparation method of the polypropylene steel-plastic composite pipe of Graphene modification, it is characterised in that: the extruding pelletization in described step (2) utilizes single screw extrusion machine, double screw extruder or Planetary Screw Extruder to carry out.
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CN104795781A (en) * | 2015-04-30 | 2015-07-22 | 赵朝端 | Low-friction modified polypropylene/glass fiber reinforced plastic composite electrical tube and manufacturing method thereof |
US9777547B1 (en) | 2015-06-29 | 2017-10-03 | Milanovich Investments, L.L.C. | Blowout preventers made from plastic enhanced with graphene, phosphorescent or other material, with sleeves that fit inside well pipes, and making use of well pressure |
NO20151457A1 (en) | 2015-10-27 | 2017-04-28 | Cealtech As | Graphene-reinforced polymer, additive for producing graphene-reinforced polymers, process for producing graphene-reinforced polymers and the use of said additive |
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CN107129635A (en) * | 2017-04-28 | 2017-09-05 | 上海烯古能源科技有限公司 | The master batch and its synthetic method of high barrier cast polypropylene film can be prepared |
CN107286473A (en) * | 2017-08-01 | 2017-10-24 | 山东圣泉新材料股份有限公司 | A kind of modified polypropylene agglomerate, fusion spray cloth and its preparation method and application |
CN113717466A (en) * | 2021-08-24 | 2021-11-30 | 湖北万锦科技有限公司 | Graphene-enhanced PP/LDPE (polypropylene/low-density polyethylene) nano composite pipe |
CN114213759B (en) * | 2022-01-04 | 2023-11-07 | 深圳中塑化工高性能材料有限公司 | Preparation method and application of polyphosphonate grafted graphene flame-retardant modified polypropylene |
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