CN108485021A - A kind of graphene/liquid crystal collaboration reinforced thermoplastics pipe and preparation method thereof - Google Patents
A kind of graphene/liquid crystal collaboration reinforced thermoplastics pipe and preparation method thereof Download PDFInfo
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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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- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention discloses a kind of graphene/liquid crystal to cooperate with reinforced thermoplastics pipe and preparation method thereof.Graphene/liquid crystal collaboration reinforced thermoplastics pipe is grouped as by the group of following parts by weight：40 ~ 60 parts of high-density polyethylene resins, 30 ~ 40 parts of active nano-powders, 1 ~ 2 part of three-dimensional netted graphene oxide, 4 ~ 7 parts of thermotropic liquid crystals, 5 ~ 10 parts of maleic anhydride stem grafting polyolefins, 0.5 ~ 2 part of lubricant, 0.5 ~ 0.9 part of antioxidant 1010,0.3 ~ 0.5 part of MB218 uvioresistant photo etching.It is added in high-speed mixer and is uniformly mixed, then rotating speed is set as 30 rpm, temperature is set as being granulated in 200 DEG C of double screw extruder, the finally extrusion molding at 200 DEG C, obtain graphene/liquid crystal collaboration reinforced thermoplastics pipe.Preparation method of the present invention is simple, can be produced on the basis of not changing existing plastic tube production technology, easy to utilize, and the hoop tensile strength of graphene obtained/liquid crystal collaboration reinforced thermoplastics pipe and thermal coefficient are significantly improved compared with common plastics tube.
Description
Technical field
The invention belongs to plastic pipe technical fields more particularly to a kind of graphene/liquid crystal to cooperate with reinforced thermoplastics
Pipe and preparation method thereof.
Background technology
Graphene be it is a kind of by single layer of carbon atom it is tightly packed made of bi-dimensional cellular shape lattice structure, have big pi bond total
Yoke system, unique physical arrangement feature and excellent performance, these excellent properties make it in field of polymer-base composite material
Using very extensive, it is only necessary to which few additive amount can be obviously improved the performances such as electricity, mechanics and the calorifics of composite material.But
The preparation method of current graphene is made a general survey of, mostly there is the defects of low yield, of high cost, of poor quality, limits answering for graphene
With and research.Simultaneously as the Van der Waals force between graphene sheet layer is stronger, be easy to happen reunion, and with matrix poor compatibility,
Graphene is caused to be extremely difficult to fine dispersion in the base.Graphene is widely used in nylon-6, epoxy resin, and polyurethane gathers
Styrene, polymethyl methacrylate, in the polymeric matrixs such as makrolon, but due in polyolefin substrate medium viscosity height and low
Surface energy, it is difficult to disperse and rare research.Graphene how is improved to ask with the good interfacial interaction of polyolefin and dispersibility
Topic is the key application for solving graphene in polyolefin plastic pipes.
Liquid crystal is a kind of fluid state between isotropy liquid and each diversity solid.Thermotropic liquid crystal unit
With auto-orientation, self-reinforcing characteristic, the height-oriented of this liquid crystal unit there is obstruction to make phon scattering in basis material
With so as to improve the heat conductivility of polymer.Meanwhile macromolecule matrix material, in melt blending process, liquid crystal will
It is scattered in basis material with the structure type of fiber, liquid crystal fiber is prone to streamwise with prodigious draw ratio and takes
To playing the role of reinforcing agent and processing aid in the composite, heat conduction and the mechanical property of composite material can be increased substantially
Energy.
In work China Democratic National Construction Association field, metallic conduit is since there are perishable, easy fouling, service life is short, not foldable, installation
The shortcomings of difficult, is gradually replaced by various Polyolefin plastic pipes such as PPR/PE/PVC pipes.Compared with metal pipe material, polyolefin plastics
Pipe has many advantages, such as that light, corrosion-resistant, specific strength is high, long lifespan, is widely used in building water supply and drainage, heating pipe system, center
The fields such as air-conditioning system, chemical engineering piping systems.But these Polyolefin plastic pipes are used due to bearing under pressure is not high enough and high temperature
Service life shorter reason, is restricted to having in high temperature and pressure long-life and thermal conductivity demand field.For this problem, state
The interior report modified to Polyolefin plastic pipe enhancing there are many document patent.Such as " graphene enhances the patent of invention of Liu Zhi light
Thermal conductivity compound polyolefin tubing "（Application number：201610148355.4）, it was recently reported that Nomex modified graphene and polyethylene
It is compound, three-layer composite pipe material is prepared through techniques such as mixing, plasticizing, extrusions.These polyolefin pipes can be 95 in temperature
DEG C, under conditions of more than 1.6MPa, service life reaches 50 years or more pressure.Utility model patent " the enhancing heat of a Tang Yun men of virtue and ability
Thermoplastic plastic tubing "（Application number：200620074020.4）, it was recently reported that nano-material modified high density polyethylene (HDPE) and complex polyester
Fiber composite is squeezed into the reinforced thermoplastics tubing with three-decker.The plastic pipe has impact resistance, high pressure resistant
The high feature of property, tube wall also have Fouling resistant.The invention of Tao Si equalitys " a kind of polyolefin heat conduction tubing that high resistant oxygen is high-strength and its
Preparation method "（Application number：20151056370.0）, it was recently reported that it is grafted with high density polyethylene (HDPE), graphene sheet layer, maleic anhydride
Polyethylene compatilizer, antioxidant mixing, are molded through twin-screw extrusion and prepare the excellent polyvinyl piping materials of high heat conduction barrier property.Institute
The tubing thermal coefficient of preparation is 0.87w/mK, hoop tensile strength 69.5MPa, and oxygen permeability coefficient is at 25 DEG C
0.096g·mm2/(L·MPa)。
Patent of the present invention cooperates with enhancing using three-dimensional netted graphene oxide and thermotropic liquid crystal, utilizes thermotropic liquid crystal
Liquid crystal fine fibrilation is formed in process and is easily orientated characteristic, is acted synergistically by the bridging of liquid crystal fine fibrilation and graphene net,
Prepare the plastic tube for having effects that enhance thermoplasticity.
Invention content
The object of the present invention is to provide a kind of graphene/liquid crystal to cooperate with reinforced thermoplastics pipe and preparation method thereof.
The graphene of the present invention/liquid crystal cooperates with reinforced thermoplastics pipe, is grouped as by the group of following parts by weight：
40 ~ 60 parts of high-density polyethylene resins, 30 ~ 40 parts of active nano-powders, 1 ~ 2 part of three-dimensional netted graphene oxide, 4 ~ 7 parts
Thermotropic liquid crystal, 5 ~ 10 parts of maleic anhydride stem grafting polyolefins, 0.5 ~ 2 part of lubricant, 0.5 ~ 0.9 part of antioxidant 1010 and 0.3 ~
0.5 part of MB218 uvioresistant photo etching.
Prepare above-mentioned graphene/liquid crystal collaboration reinforced thermoplastics pipe the specific steps are：
Weigh each component by above-mentioned parts by weight, be added in high-speed mixer and be uniformly mixed, then rotating speed be set as 30 rpm,
Temperature is set as being granulated in 200 DEG C of double screw extruder, the finally extrusion molding at 200 DEG C, obtains graphene/liquid crystal association
With reinforced thermoplastics pipe.
The active nano-powder is nano-calcium carbonate, nano silicon dioxide, nano aluminium oxide or nano-titanium dioxide.
The three-dimensional netted graphene oxide is prepared according to the following steps：
Squamaceous expanded graphite is aoxidized using Hummers methods are improved, the 80 mL concentrated sulfuric acids are packed into the beaker of 800 mL
In, 10 g potassium peroxydisulfates and 10 g phosphorus pentoxides are added under stiring, after being completely dissolved, are warming up to 90 DEG C, slowly add
Enter 3 g expanded graphites, be stirred to react 5 h, 10 g potassium permanganate are then slowly added under water bath condition, is warming up to 35 DEG C instead
After answering 2 h, 600 mL deionized waters are slow added into, 7 h are persistently stirred, it is 30% that 60mL concentration of volume percent, which is then added,
Hydrogen peroxide until mixture be in glassy yellow, standing so that graphite oxide is precipitated, outwell upper liquid, be with mass percent concentration
10% hydrochloric acid solution cleans 4 ~ 5 times, after ultrasonic wave removes 0.5 h, graphene oxide water solution is obtained, by the graphene oxide
Aqueous solution is placed in Rotary Evaporators and is poured into culture dish after concentration, dry in freeze drier that three-dimensional netted oxidation stone is made
Black alkene.
The thermotropic liquid crystal is 4,4 '-two (β-hydroxy ethoxy) biphenyl or 4,4 '-two (β-hydroxyl hexyloxy) biphenyl.
The maleic anhydride stem grafting polyolefin is maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene.
The lubricant is polyethylene wax, ethylene bis stearamide, stearic acid or paraffin.
Compared with the prior art, the present invention has the following advantages：
(1) preparation method of the invention is simple, can be produced on the basis of not changing existing plastic tube production technology, convenient for promoting
Using.
(2) hoop tensile strength of graphene of the invention/liquid crystal collaboration reinforced thermoplastics pipe and thermal coefficient compared with
Common plastics tube is significantly improved, and can solve the problems, such as that existing plastic tube intensity low heat conductivity is poor.
Specific implementation mode
In order to enable those skilled in the art to be further understood that the feature and technology contents of the present invention, below with embodiment
It is described further, but protection domain is not limited by this.Primary raw material used in following embodiment：Three-dimensional netted graphite oxide
Alkene（It makes by oneself in laboratory）, 4,4 '-two (β-hydroxy ethoxy) biphenyl（It makes by oneself in laboratory）, 4,4 '-two (β-hydroxyl hexyloxy) connection
Benzene（It makes by oneself in laboratory）, high density polyethylene (HDPE)（Technical grade）, nano-calcium carbonate（Technical grade）, nano silicon dioxide（Technical grade）,
Nano aluminium oxide（Technical grade）, maleic anhydride grafted polyethylene（Technical grade）, polyethylene wax（Technical grade）, antioxidant 1010（Work
Industry grade）, MB218 uvioresistant photo etchings（Technical grade）.
Embodiment 1：
（1）Each component is weighed according to following parts by weight：58 parts of high-density polyethylene resin, 30 parts of active nano-calcium carbonate, three
Tie up 1 part of netted graphene oxide, 4,4 '-two (β-hydroxyl hexyloxy) 4 parts of biphenyl, 6 parts of maleic anhydride grafted polyethylene, polyethylene
0.3 part of 1 part of wax, 0.5 part of antioxidant 1010 and MB218 uvioresistants photo etching.
（2）By step（1）The component weighed is added in high-speed mixer and is uniformly mixed, and is then set as 30 in rotating speed
Rpm, temperature are set as being granulated in 200 DEG C of double screw extruder, and the finally extrusion molding at 200 DEG C obtains graphene/liquid
Crystalline substance collaboration reinforced thermoplastics pipe.
Graphene made from the present embodiment/liquid crystal cooperates with reinforced thermoplastics pipe, hoop tensile strength 22.5
MPa, thermal coefficient 0.38W/mK.
Embodiment 2：
（1）Each component is weighed according to following parts by weight：60 parts of high-density polyethylene resin, 30 parts of nano silicon dioxide, three-dimensional
1 part of netted graphene oxide, 4,4 '-two (β-hydroxyl hexyloxy) 4 parts of biphenyl, 6 parts of maleic anhydride grafted polyethylene, polyethylene wax
0.3 part of 1 part, 0.5 part of antioxidant 1010 and MB218 uvioresistants photo etching.
（2）By step（1）The component weighed is added in high-speed mixer and is uniformly mixed, and is then set as 30 in rotating speed
Rpm, temperature are set as being granulated in 200 DEG C of double screw extruder, and the finally extrusion molding at 200 DEG C obtains graphene/liquid
Crystalline substance collaboration reinforced thermoplastics pipe.
Graphene made from the present embodiment/liquid crystal cooperates with reinforced thermoplastics pipe, hoop tensile strength 23.4
MPa, thermal coefficient 0.37W/mK.
Embodiment 3：
（1）Each component is weighed according to following parts by weight：60 parts of high-density polyethylene resin, 30 parts of nano-aluminium oxide, three
Tie up 1 part of netted graphene oxide, 4,4 '-two 4 parts of (β-hydroxy ethoxy) biphenyl, 6 parts of maleic anhydride grafted polyethylene, polyethylene
0.3 part of 1.2 parts of wax, 0.5 part of antioxidant 1010 and MB218 uvioresistants photo etching.
（2）By step（1）The component weighed is added in high-speed mixer and is uniformly mixed, and is then set as 30 in rotating speed
It is granulated in rpm, the double screw extruder that temperature is 200 DEG C, the finally extrusion molding at 200 DEG C, obtains graphene/liquid crystal association
With reinforced thermoplastics pipe.
Graphene made from the present embodiment/liquid crystal cooperates with reinforced thermoplastics pipe, hoop tensile strength 23.8
MPa, thermal coefficient 0.46W/mK.
Claims (2)
1. a kind of graphene/liquid crystal cooperates with reinforced thermoplastics pipe, it is characterised in that the graphene/liquid crystal collaboration enhancing thermoplastic
Property plastic tube is grouped as by the group of following parts by weight：
40 ~ 60 parts of high-density polyethylene resins, 30 ~ 40 parts of active nano-powders, 1 ~ 2 part of three-dimensional netted graphene oxide, 4 ~ 7 parts
Thermotropic liquid crystal, 5 ~ 10 parts of maleic anhydride stem grafting polyolefins, 0.3 ~ 1 part of lubricant, 0.5 ~ 0.9 part of antioxidant 1010 and 0.3 ~
0.5 part of MB218 uvioresistant photo etching；
The active nano-powder is nano-calcium carbonate, nano silicon dioxide, nano aluminium oxide or nano-titanium dioxide；
The three-dimensional netted graphene oxide is prepared according to the following steps：Using improvement Hummers methods to squamaceous expanded graphite
It is aoxidized, the 80 mL concentrated sulfuric acids is fitted into the beaker of 800 mL, 10 g potassium peroxydisulfates and 10 g five oxidations are added under stiring
Two phosphorus are warming up to 90 DEG C after being completely dissolved, and are slowly added to 3 g expanded graphites, 5 h are stirred to react, then in water bath condition
Under be slowly added to 10 g potassium permanganate, after being warming up to 35 DEG C of 2 h of reaction, be slow added into 600 mL deionized waters, it is lasting to stir
7 h, the hydrogen peroxide that then addition 60mL concentration of volume percent is 30% are in glassy yellow until mixture, and standing makes graphite oxide
Precipitation, outwells upper liquid, and the hydrochloric acid solution for being 10% with mass percent concentration cleans 4 ~ 5 times, after ultrasonic wave removes 0.5 h, obtains
To graphene oxide water solution, which is placed in Rotary Evaporators after concentrating and is poured into culture dish,
It is dry in freeze drier that three-dimensional netted graphene oxide is made；
The thermotropic liquid crystal is 4,4 '-two (β-hydroxy ethoxy) biphenyl or 4,4 '-two (β-hydroxyl hexyloxy) biphenyl；
The maleic anhydride stem grafting polyolefin is maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene；
The lubricant is polyethylene wax, ethylene bis stearamide, stearic acid or paraffin.
2. a kind of preparation method of graphene as described in claim 1/liquid crystal collaboration reinforced thermoplastics pipe, it is characterised in that
The specific steps are：
All components are added in high-speed mixer and are uniformly mixed, then rotating speed is set as 30 rpm, temperature is set as 200 DEG C
Double screw extruder in be granulated, the finally extrusion molding at 200 DEG C obtains the collaboration enhancing thermoplasticity modeling of graphene/liquid crystal
Expects pipe.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113561444A (en) * | 2021-06-21 | 2021-10-29 | 安徽杰蓝特新材料有限公司 | High-strength wear-resistant PE gas pipe and processing method thereof |
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2018
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Patent Citations (4)
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| CN103756088A (en) * | 2013-12-26 | 2014-04-30 | 宁波波尔管业开发有限公司 | High-temperature, temperature-resisting and wear-resisting polyethylene pipe |
| CN104059395A (en) * | 2014-06-29 | 2014-09-24 | 桂林理工大学 | Preparation method for perylene bisimide polyurethane liquid crystal non-covalent modified graphene |
| CN105131385A (en) * | 2015-07-29 | 2015-12-09 | 天津金发新材料有限公司 | High-oxygen barrier property high-strength polyolefin heat conduction pipe and preparation method thereof |
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| CN113561444A (en) * | 2021-06-21 | 2021-10-29 | 安徽杰蓝特新材料有限公司 | High-strength wear-resistant PE gas pipe and processing method thereof |
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