CN108676243A - A kind of hybrid material, graphene modified heat resistant PE-RT tubing and preparation method thereof - Google Patents
A kind of hybrid material, graphene modified heat resistant PE-RT tubing and preparation method thereof Download PDFInfo
- Publication number
- CN108676243A CN108676243A CN201810523291.0A CN201810523291A CN108676243A CN 108676243 A CN108676243 A CN 108676243A CN 201810523291 A CN201810523291 A CN 201810523291A CN 108676243 A CN108676243 A CN 108676243A
- Authority
- CN
- China
- Prior art keywords
- temperature
- area
- graphene
- phyllosilicate
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The present invention provides a kind of hybrid materials, graphene modified heat resistant PE RT tubing and preparation method thereof, the hybrid material, its preparation includes the following steps, graphene oxide dispersion is uniformly mixed with plant polyphenol solution, then phyllosilicate is added, after being sufficiently stirred, 50~90 DEG C are heated to, reacts 6~15h；The mass ratio of the graphene oxide, plant polyphenol and phyllosilicate is 1：(0.5~1)：(0.1~1).The present invention prepares the heat-resisting PE RT tubing with excellent mechanical property, high temperature resistant croop property, heat aging property and extrusion processability energy using components such as heat-proof polythene, antioxidant, simple production process, suitable for industrialized production, can be widely used for preparing hot-water pipeline system tubing and pipe fitting.
Description
Technical field
The invention belongs to PE-RT tubing technical fields, more particularly, to a kind of hybrid material, graphene modified heat resistant PE-
RT tubing and preparation method thereof.
Background technology
Heat-proof polythene (PE-RT) tubing had both had the performance of common polythene tubing, such as weldable, recyclable profit again
With and processing and forming, it is easy for construction the features such as, also there is the long-term heat resistance energy close to cross-linked polyethylene pipe, while it also has
There is unique flexibility, is a kind of plastic pipe of energy-saving and environmental protection type.It is always PE-RT pipes to improve heat resistance and ageing properties
The key points and difficulties of material research.
Graphene be it is a kind of have the characteristics that superpower mechanical strength, high thermal conductivity, high transparency, high-specific surface area it is new
Type two dimension carbon material, good characteristic make it in necks such as high performance electronics, composite material, gas sensor and energy stores
Domain has a wide range of applications, especially the thermal conductivity of its superelevation, it is considered to be outstanding Heat Conduction Material.But graphene surface
Inert state, while graphene and interpolymer interaction are weaker, and each interlayer is easy due to there are stronger Van der Waals force
Assemble, it is difficult dispersion that these reasons, which lead to it in the polymer, and to graphene, application causes very big be stranded in the polymer
It is difficult.Therefore, the interaction between graphene and polymer is improved, graphene is improved and disperses to be to prepare high-performance in the polymer
The key of graphene/polymer nano composite material.
Invention content
In view of this, the present invention is directed to propose a kind of hybrid material, graphene modified heat resistant PE-RT tubing and its preparation side
Method improves the processing of PE-RT pipe composite materials, mechanics, heat-resisting and ageing-resistant etc. performances to overcome deficiency in the prior art.
The orderly aggregation that the present invention realizes graphene and phyllosilicate using straightforward procedure assembles, and realizes graphene in polymer
It is evenly dispersed in matrix.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A kind of graphene phyllosilicate hybrid material, preparation include the following steps, by graphene oxide dispersion with
Plant polyphenol solution is uniformly mixed, and phyllosilicate is then added, and after being sufficiently stirred, is heated to 50~90 DEG C, is reacted 6~15h；
The mass ratio of the graphene oxide, plant polyphenol and phyllosilicate is 1：(0.5~1)：(0.1~1)；Preferably, add
Heat reacts 8~10h to 60~80 DEG C.
Preferably, the plant polyphenol includes one in catechol, ferulic acid, catechin, gallic acid, Hydrolysable Tannins
Kind is a variety of；The phyllosilicate is montmorillonite, hydrotalcite, hectorite, kaolin, terre verte, illite, concave convex rod
One or more of stone, sepiolite, vermiculite, hydromica.
Preferably, a concentration of 0.5~1.5mg/mL of the graphene oxide dispersion；The plant polyphenol solution it is dense
Degree is 0.5~1.5mg/mL；Preferably, a concentration of 1mg/mL of the graphene oxide dispersion；The plant polyphenol solution
A concentration of 1mg/mL.
Another object of the present invention is to provide the application of graphene phyllosilicate hybrid material as described above in the duct.
Invention also provides a kind of graphenes comprising graphene phyllosilicate hybrid material as described above to change
Property heat-resisting PE-RT pipe, it is characterised in that：Include the component of following parts by weight, PE-RT100 parts, 0.02~1 part of antioxidant, stone
Black 0.1~3 part of alkene phyllosilicate nano hybrid material.
Preferably, the antioxidant is the mixed of Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant
Object is closed, weight ratio is 0.05~0.5:0.1~0.5：0.05~0.5.
Preferably, the Hinered phenols antioxidant is selected from four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester, (2,4,6- trioxy- -1,3,5- triazines -1,3,5 (2H, 4H, 6H)-three base) [3- (bis- tertiary fourths of 3,5- of trivinyl three
Base -4- hydroxy phenyls) acrylate, 1,1,3- tri- (2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) butane, trimethyl -2 1,3,5-,
4,6- tri- (3,5- di-t-butyl -4- hydroxyls benzyl) benzene, 1,3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,
5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) guanamine, 4,6-
In (1H, 3H, 5H) triketone it is middle it is a kind of, two or more；The phosphite ester kind antioxidant is selected from three (2,4- bis- tertiary fourths
Base phenyl) one kind in phosphite ester or pentaerythrite diphosphite two (2,4- di-tert-butyl phenyl) ester；The thioesters class is anti-
Oxygen agent is bis- (18) esters of thio-2 acid or dilauryl thiodipropionate.
Present invention provides a kind of method preparing graphene modified heat resistant PE-RT pipes as described above, including it is as follows
Step,
1) antioxidant, graphene/phyllosilicate hybrid material, PE-RT are added in high-speed mixer, high-speed stirred
10~30min releases material, is then added to double screw extruder and carries out extruding pelletization；Driving screw 100~300r/min of rotating speed,
One area's temperature of barrel is 170~200 DEG C, and two area's temperature are 175~205 DEG C, and three area's temperature are 180~210 DEG C, and four area's temperature are
185~215 DEG C, five area's temperature are 180~210 DEG C, and head temperature is 175~205 DEG C, obtains graphene modified heat resistant PE-RT
Masterbatch；
2) PE-RT, graphene modified heat resistant PE-RT masterbatch are added in high-speed mixer, 5~10min of high-speed stirred,
Material is released, is then added in single screw extrusion machine, driving screw 300~500r/min of rotating speed, one area's temperature of barrel be 170~
200 DEG C, two area's temperature are 175~205 DEG C, and three area's temperature are 180~210 DEG C, and four area's temperature are 185~215 DEG C, five area's temperature
It it is 180~210 DEG C, head temperature is 175~205 DEG C.
Preferably, in step 1), one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C,
Four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C；
In step 2), one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, four area's temperature
It it is 200 DEG C, five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Compared with the existing technology, hybrid material and graphene modified heat resistant PE-RT tubing of the present invention and its system
It is standby, it has the advantage that：
(1) present invention realizes the hybridization compounding of graphene and nano layered silicate using LBL self-assembly method, realizes
Graphene, the total stripping of nano layered silicate and collaboration dispersion.Graphene/phyllosilicate nano prepared by the method for the present invention
Hybrid material production cost is low, required equipment is simple, and yield is high, is easily industrialized production；Graphene of the present invention
Phyllosilicate nano hybrid material can be used as the preparation of cold hot water piping in building, including industrial or civilian hot and cold
Water, drinking water and heating system pipeline make.
(2) present invention is modified heat-resisting PE-RT pipes with graphene, the PE-RT tubing that obtained graphene is modified, this
The PE-RT tubing of invention has excellent resistance to long-term hydrostatic ability, high temperature resistance and excellent shock resistance, flexibility
And heat conductivity, the PE-RT tubing of preparation can be used as the preparation of cold hot water piping in building.
(3) graphene phyllosilicate nano hybrid material and PE-RT tubing of the present invention, raw material type compared with
Few, preparation process is simple, and raw material is easy to get, and is suitble to industrialized production.
Specific implementation mode
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
With reference to embodiment, the present invention will be described in detail.
Embodiment 1
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Catechin is dissolved in water, 1mg/mL is made
Solution.By above two solution by volume 1:1 ratio is uniformly mixed, montmorillonite is added in above-mentioned solution, is added
Amount and solution in graphene oxide it is identical in quality, after being sufficiently stirred, be heated to 80 DEG C, 8h reacted, after reaction, by institute
Product is obtained to carry out being washed to neutrality, it is dry, obtain graphene/montmorillonite-based nano hybrid material.
(2) graphene modified heat resistant PE-RT masterbatch：By above-mentioned graphene/montmorillonite-based nano hybrid material, 1,1,3- tri-
(2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) butane (Hinered phenols antioxidant), (bis- uncles of 3,5- of 1,3,5- trimethyls -2,4,6- three
Butyl -4- hydroxyls benzyl) benzene (Hinered phenols antioxidant), three (2,4- di-tert-butyl-phenyls) phosphite ester (phosphorous acid esters antioxygens
Agent) and bis- (18) esters of thio-2 acid (sulphur ester antioxidant and PE-RT are according to following weight ratio 5:0.05:0.05:0.1:
0.05:100, it is added in high-speed mixer, high-speed stirred 10min releases material, is then added to double screw extruder and is squeezed
Go out to be granulated；Driving screw rotating speed 250r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195
DEG C, four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
The preparation of graphene modified heat resistant PE-RT tubing：Above-mentioned graphene modified heat resistant PE-RT masterbatch and PE-RT are pressed
According to following weight ratio 1:10, it is added in high-speed mixer, under the conditions of 45 DEG C, high-speed stirred 15min releases material, then adds
Into single screw extrusion machine, driving screw rotating speed 450r/min, one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, 3rd area
Temperature is 195 DEG C, and four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Embodiment 2
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Gallic acid is dissolved in the water, is made
The solution of 1mg/mL.By above two solution by volume 1:1 is uniformly mixed, and hectorite is added in above-mentioned solution, is added
Amount and solution in graphene oxide it is identical in quality, after being sufficiently stirred, be heated to 60 DEG C, react 10h, after reaction, will
Products therefrom carries out being washed to neutrality, dry, obtains graphene/hectorite nano-hybrid material.
(2) graphene modified heat resistant PE-RT masterbatch：By above-mentioned graphene/hectorite nano-hybrid material, 1,3,5- tri-
(Hinered phenols are anti-by (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone
Oxygen agent), (the 2,4- di-tert-butyls phenyl) ester (phosphite ester kind antioxidant) of pentaerythrite diphosphite two and thio-2 acid it is double
(18) ester (sulphur ester antioxidant), PE-RT press following weight ratio 5:0.2:0.05:0.05:100, it is added to high-speed mixer
In, high-speed stirred 30min releases material, is then added to double screw extruder and carries out extruding pelletization；Driving screw rotating speed 200r/
Min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are 200 DEG C, 5th area
Temperature is 195 DEG C, and head temperature is 190 DEG C.
The preparation of graphene modified heat resistant PE-RT tubing：By above-mentioned graphene modified heat resistant PE-RT masterbatch, PE-RT by weight
Measure ratio 1:10, it is added in high-speed mixer, material is released, is then added in single screw extrusion machine by high-speed stirred 5min, main spiral shell
Bar rotating speed 500r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are
200 DEG C, five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Embodiment 3
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Hydrolysable Tannins is dissolved in the water, is made
The solution of 1mg/mL.By above two solution by volume 2:1 is uniformly mixed, and hydrotalcite is added in above-mentioned solution, is added
Amount and solution in graphene oxide it is identical in quality, after being sufficiently stirred, be heated to 80 DEG C, 8h reacted, after reaction, by institute
Product is obtained to carry out being washed to neutrality, it is dry, obtain graphene/hydrotalcite nano hybrid material.
(2) graphene modified heat resistant PE-RT masterbatch：By above-mentioned graphene/hydrotalcite nano hybrid material, 1,3,5- tri-
(3,5- di-tert-butyl-4-hydroxyl benzyls) guanamine, 4,6- (1H, 3H, 5H) triketone (Hinered phenols antioxidant), pentaerythrite
(thioesters class is anti-for (the 2,4- di-tert-butyls phenyl) ester (phosphite ester kind antioxidant) of diphosphite two and dilauryl thiodipropionate
Oxygen agent), PE-RT, by following weight ratio 5:0.05:0.15:0.05:100, it is added in high-speed mixer, high-speed stirred 5min,
Material is released, double screw extruder is then added to and carries out extruding pelletization；Driving screw rotating speed 200r/min, one area's temperature of barrel are
185 DEG C, two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, head temperature
Degree is 190 DEG C.
The preparation of graphene modified heat resistant PE-RT tubing：By above-mentioned graphene modified heat resistant PE-RT masterbatch, PE-RT by weight
Measure ratio 1:10, it is added in high-speed mixer, under the conditions of 30 DEG C, material is released, is then added to single screw rod by high-speed stirred 30min
In extruder, driving screw rotating speed 400r/min, one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195
DEG C, four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Embodiment 4
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Catechin is dissolved in water, 1mg/mL is made
Solution.By above two solution by volume 2:1, it is uniformly mixed, 0.1g montmorillonites is added in above-mentioned solution, addition
Amount in solution graphene oxide it is identical in quality, after being sufficiently stirred, be heated to 60 DEG C, reaction 10h, after reaction, by institute
Product is obtained to carry out being washed to neutrality, it is dry, obtain graphene/montmorillonite-based nano hybrid material.
(2) graphene modified heat resistant PE-RT masterbatch：By above-mentioned graphene/phyllosilicate nano hybrid material, four [β-
(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Hinered phenols antioxidant), (2- methyl -4- hydroxyls of 1,1,3- tri-
Base -5- 2-methyl-2-phenylpropanes base) butane (Hinered phenols antioxidant), pentaerythrite diphosphite two (2,4- di-tert-butyls phenyl) ester be (sub-
Phosphoric acid ester antioxidant) and dilauryl thiodipropionate (sulphur ester antioxidant), PE-RT press following weight ratio 5:0.1:0.1:
0.1:0.05:100, be added in high-speed mixer, high-speed stirred 20min releases material, be then added to double screw extruder into
Row extruding pelletization；Driving screw rotating speed 200r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are
195 DEG C, four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
The preparation of graphene modified heat resistant PE-RT tubing：By above-mentioned graphene modified heat resistant PE-RT masterbatch, PE-RT according to
Weight ratio 1:5, it is added in high-speed mixer, under the conditions of 50 DEG C, material is released, is then added to single screw rod by high-speed stirred 5min
In extruder, driving screw rotating speed 400r/min, one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195
DEG C, four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Embodiment 5
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Gallic acid is dissolved in water, 1mg/ is made
The solution of mL.By above two solution by volume 1:1, it is uniformly mixed, will, montmorillonite is added in above-mentioned solution, addition
Amount in solution graphene oxide it is identical in quality, after being sufficiently stirred, be heated to 80 DEG C, reaction 8h, after reaction, by gained
Product carries out being washed to neutrality, dry, obtains graphene/montmorillonite-based nano hybrid material.
(2) graphene modified heat resistant PE-RT masterbatch：By 40 parts of above-mentioned graphene/montmorillonite-based nano hybrid materials, 0.05 part
1,3,5- trimethyls -2,4,6- three (3,5- di-t-butyl -4- hydroxyls benzyl) benzene (Hinered phenols antioxidant), 0.2 part of pentaerythrite
(the 2,4- di-tert-butyls phenyl) ester (phosphite ester kind antioxidant) of diphosphite two and 0.05 part of dilauryl thiodipropionate (sulphur
Esters antioxidant), 100 parts of PE-RT be added in high-speed mixer, material is released, is then added to twin-screw by high-speed stirred 5min
Extruder carries out extruding pelletization；Driving screw rotating speed 200r/min, one area's temperature of barrel be 185 DEG C, two area's temperature be 190 DEG C, three
Area's temperature is 195 DEG C, and four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
The preparation of graphene modified heat resistant PE-RT tubing：By above-mentioned graphene modified heat resistant PE-RT masterbatch, PE-RT according to
Weight ratio 3:10, it is added in high-speed mixer, material is released, is then added in single screw extrusion machine by high-speed stirred 10min,
Driving screw rotating speed 400r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, four area's temperature
Degree is 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Performance measurement is carried out to graphene modified heat resistant PE-RT pipes according to GB/T 28799.1-2012, test result is shown in Table
1。
Comparative example 1
The preparation of modified heat resistant PE-RT tubing：By PE-RT, four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] seasons
Doutrate (Hinered phenols antioxidant), three (2,4- di-tert-butyl-phenyls) phosphite esters (phosphite ester kind antioxidant) and thio
Bis- (18) esters (sulphur ester antioxidant) of dipropionic acid are according to weight ratio 100:0.1:0.1:0.1, it is added in single screw extrusion machine,
Driving screw rotating speed 300r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, four area's temperature
Degree is 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Comparative example 2
(1) graphene oxide is obtained by Hummers legal systems.Particular reference：Hummers Jr,W.S.；Offeman,
R.E.J Am Chem Soc 1958,80,1339。
Graphene oxide is distributed in water, the dispersion liquid of 1mg/mL is made.Catechol is dissolved in water, 1mg/mL is made
Solution.By above two solution by volume 1:1, it is uniformly mixed, after being sufficiently stirred, is heated to 80 DEG C, react 8h, reaction knot
Shu Hou carries out products therefrom to be washed to neutrality, dry, obtains graphene.
(2) graphene modified heat resistant PE-RT masterbatch：Will (2,4,6- trioxy- -1,3,5- triazines -1,3,5 (2H, 4H,
6H)-three base) trivinyl three [3- (3,5- di-tert-butyl-hydroxy phenyls) acrylate (Hinered phenols antioxidant), three (2,
4- di-tert-butyl-phenyls) phosphite ester (phosphite ester kind antioxidant) and bis- (18) ester (the thioesters class antioxygens of thio-2 acid
Agent), graphene, PE-RT is by weight 0.1:0.1:0.1:5:100 are added in high-speed mixer, high-speed stirred 20min, will
Material is released, and is then added to double screw extruder and is carried out extruding pelletization；Driving screw rotating speed 200r/min, one area's temperature of barrel are 185
DEG C, two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are 200 DEG C, and five area's temperature are 195 DEG C, and head temperature is
190℃。
The preparation of graphene modified heat resistant PE-RT tubing：By above-mentioned graphene modified heat resistant PE-RT masterbatch, PE-RT by weight
Measure ratio 1:10, it is added in high-speed mixer, material is released, is then added in single screw extrusion machine by high-speed stirred 10min, main
Screw speed 400r/min, one area's temperature of barrel are 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, four area's temperature
It it is 200 DEG C, five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Performance measurement is carried out to graphene modified heat resistant PE-RT pipes, test result is shown in Table 1.
The performance of 1 graphene modified heat resistant PE-RT pipes of table
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention
Protection domain within.
Claims (9)
1. a kind of graphene phyllosilicate hybrid material, it is characterised in that：Its preparation includes the following steps, by graphene oxide
Dispersion liquid is uniformly mixed with plant polyphenol solution, and phyllosilicate is then added, and after being sufficiently stirred, is heated to 50~90 DEG C, instead
Answer 6~15h；The mass ratio of the graphene oxide, plant polyphenol and phyllosilicate is 1：(0.5~1)：(0.1~1)；
Preferably, 60~80 DEG C are heated to, 8~10h is reacted.
2. graphene phyllosilicate hybrid material according to claim 1, it is characterised in that：The plant polyphenol packet
Include one or more of catechol, ferulic acid, catechin, gallic acid, Hydrolysable Tannins；The phyllosilicate is to cover
De- soil, hydrotalcite, hectorite, kaolin, terre verte, illite, attapulgite, sepiolite, vermiculite, one kind in hydromica or two
Kind or more.
3. graphene phyllosilicate hybrid material according to claim 1, it is characterised in that：The graphene oxide point
A concentration of 0.5~1.5mg/mL of dispersion liquid；A concentration of 0.5~1.5mg/mL of the plant polyphenol solution；Preferably, the oxygen
A concentration of 1mg/mL of graphite alkene dispersion liquid；A concentration of 1mg/mL of the plant polyphenol solution.
4. according to the application of claims 1 to 3 any one of them graphene phyllosilicate hybrid material in the duct.
5. a kind of graphene comprising such as claims 1 to 3 any one of them graphene phyllosilicate hybrid material is modified
Heat-resisting PE-RT pipes, it is characterised in that：Include the component of following parts by weight, PE-RT100 parts, 0.02~1 part of antioxidant, graphite
0.1~3 part of alkene phyllosilicate nano hybrid material.
6. graphene modified heat resistant PE-RT pipes according to claim 5, it is characterised in that：The antioxidant is hindered phenol
The mixture of kind antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant, weight ratio are 0.05~0.5:0.1~0.5：
0.05~0.5.
7. graphene modified heat resistant PE-RT pipes according to claim 6, it is characterised in that：The Hinered phenols antioxidant
Selected from four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, (triazine -1 2,4,6- trioxy- -1,3,5-,
3,5 (2H, 4H, 6H)-three base) trivinyl three [3- (3,5- di-tert-butyl-hydroxy phenyls) acrylate, tri- (2- of 1,1,3-
Methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) butane, 1,3,5- trimethyls -2,4,6- three (3,5- di-t-butyl -4- hydroxyls benzyl) benzene, 1,
3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 1,3,
5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) guanamine, in 4,6- (1H, 3H, 5H) triketone it is middle it is a kind of, two kinds or two kinds
More than；The phosphite ester kind antioxidant is selected from three (2,4- di-tert-butyl-phenyl) phosphite esters or pentaerythrite diphosphite two
One kind in (2,4- di-tert-butyl phenyl) ester；The sulphur ester antioxidant is bis- (18) esters of thio-2 acid or thio dipropyl
Sour dilauryl.
8. a kind of preparing the method such as claim 5~7 any one of them graphene modified heat resistant PE-RT pipes, feature exists
In：Include the following steps,
1) antioxidant, graphene/phyllosilicate hybrid material, PE-RT are added in high-speed mixer, high-speed stirred 10~
30min releases material, is then added to double screw extruder and carries out extruding pelletization；Driving screw 100~300r/min of rotating speed, barrel
One area's temperature is 170~200 DEG C, and two area's temperature are 175~205 DEG C, and three area's temperature are 180~210 DEG C, and four area's temperature are 185
~215 DEG C, five area's temperature are 180~210 DEG C, and head temperature is 175~205 DEG C, and it is female to obtain graphene modified heat resistant PE-RT
Material；
2) PE-RT, graphene modified heat resistant PE-RT masterbatch are added in high-speed mixer, 5~10min of high-speed stirred, by object
Material is released, and is then added in single screw extrusion machine, driving screw 300~500r/min of rotating speed, and one area's temperature of barrel is 170~200 DEG C,
Two area's temperature are 175~205 DEG C, and three area's temperature are 180~210 DEG C, and four area's temperature are 185~215 DEG C, and five area's temperature are 180
~210 DEG C, head temperature is 175~205 DEG C.
9. the method for graphene modified heat resistant PE-RT pipes according to claim 8, it is characterised in that：In step 1), barrel
One area's temperature is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are 200 DEG C, and five area's temperature are 195
DEG C, head temperature is 190 DEG C；
In step 2), one area's temperature of barrel is 185 DEG C, and two area's temperature are 190 DEG C, and three area's temperature are 195 DEG C, and four area's temperature are
200 DEG C, five area's temperature are 195 DEG C, and head temperature is 190 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810523291.0A CN108676243B (en) | 2018-05-28 | 2018-05-28 | Hybrid material, graphene modified heat-resistant PE-RT pipe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810523291.0A CN108676243B (en) | 2018-05-28 | 2018-05-28 | Hybrid material, graphene modified heat-resistant PE-RT pipe and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108676243A true CN108676243A (en) | 2018-10-19 |
| CN108676243B CN108676243B (en) | 2021-02-09 |
Family
ID=63808849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810523291.0A Active CN108676243B (en) | 2018-05-28 | 2018-05-28 | Hybrid material, graphene modified heat-resistant PE-RT pipe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108676243B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275524A (en) * | 2013-05-27 | 2013-09-04 | 淮北师范大学 | Preparation method of graphene kaolin composite nanometer rubber fillers |
| CN103787322A (en) * | 2014-01-25 | 2014-05-14 | 华南理工大学 | Graphene-carrying phyllosilicate nano composite material and preparation method thereof |
| CN103865114A (en) * | 2014-02-27 | 2014-06-18 | 上海工程技术大学 | Imvite/natural rubber composite and preparation method thereof |
| CN104004251A (en) * | 2014-05-07 | 2014-08-27 | 武汉金牛经济发展有限公司 | Preparation method of graphene-modified heat-resistant polyethylene composite tubing |
| CN104529382A (en) * | 2015-01-14 | 2015-04-22 | 哈尔滨工业大学 | Graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and preparation method thereof |
| US20160160017A1 (en) * | 2014-12-03 | 2016-06-09 | Hyundai Motor Company | High-flow and high-impact polyolefin resin composition |
| CN106146886A (en) * | 2016-06-30 | 2016-11-23 | 常州第六元素材料科技股份有限公司 | A kind of composite of Graphene intercalation silicate and preparation method thereof |
| CN106517993A (en) * | 2016-10-18 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Graphene/montmorillonite compound porous thin film and preparation method thereof |
| CN106832513A (en) * | 2016-12-30 | 2017-06-13 | 洛阳国润新材料科技股份有限公司 | A kind of ultrahigh molecular weight polyethylene tubing and preparation method thereof |
| CN107216593A (en) * | 2017-06-02 | 2017-09-29 | 吉林省慧燊节能科技有限公司 | A kind of graphene enhancing heat-proof polythene composite pipe and preparation method thereof |
| CN107266951A (en) * | 2017-05-25 | 2017-10-20 | 北京化工大学 | A kind of preparation method and applications of silicate mineral reductive modification graphene oxide |
| CN108048170A (en) * | 2017-12-20 | 2018-05-18 | 南京理工大学 | The lube oil additive of functionalization graphene load montmorillonite, preparation method and applications |
-
2018
- 2018-05-28 CN CN201810523291.0A patent/CN108676243B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275524A (en) * | 2013-05-27 | 2013-09-04 | 淮北师范大学 | Preparation method of graphene kaolin composite nanometer rubber fillers |
| CN103787322A (en) * | 2014-01-25 | 2014-05-14 | 华南理工大学 | Graphene-carrying phyllosilicate nano composite material and preparation method thereof |
| CN103865114A (en) * | 2014-02-27 | 2014-06-18 | 上海工程技术大学 | Imvite/natural rubber composite and preparation method thereof |
| CN104004251A (en) * | 2014-05-07 | 2014-08-27 | 武汉金牛经济发展有限公司 | Preparation method of graphene-modified heat-resistant polyethylene composite tubing |
| US20160160017A1 (en) * | 2014-12-03 | 2016-06-09 | Hyundai Motor Company | High-flow and high-impact polyolefin resin composition |
| CN104529382A (en) * | 2015-01-14 | 2015-04-22 | 哈尔滨工业大学 | Graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and preparation method thereof |
| CN106146886A (en) * | 2016-06-30 | 2016-11-23 | 常州第六元素材料科技股份有限公司 | A kind of composite of Graphene intercalation silicate and preparation method thereof |
| CN106517993A (en) * | 2016-10-18 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Graphene/montmorillonite compound porous thin film and preparation method thereof |
| CN106832513A (en) * | 2016-12-30 | 2017-06-13 | 洛阳国润新材料科技股份有限公司 | A kind of ultrahigh molecular weight polyethylene tubing and preparation method thereof |
| CN107266951A (en) * | 2017-05-25 | 2017-10-20 | 北京化工大学 | A kind of preparation method and applications of silicate mineral reductive modification graphene oxide |
| CN107216593A (en) * | 2017-06-02 | 2017-09-29 | 吉林省慧燊节能科技有限公司 | A kind of graphene enhancing heat-proof polythene composite pipe and preparation method thereof |
| CN108048170A (en) * | 2017-12-20 | 2018-05-18 | 南京理工大学 | The lube oil additive of functionalization graphene load montmorillonite, preparation method and applications |
Non-Patent Citations (1)
| Title |
|---|
| 廖瑞娟: "茶多酚修饰石墨烯及其橡胶复合材料", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108676243B (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106750988B (en) | A kind of PPR pipe and preparation method thereof with excellent low temperature toughness | |
| CN110591209A (en) | Polymer heat-conducting film containing uniformly-dispersed and highly-oriented graphene and preparation method thereof | |
| CN109575551B (en) | Modified resin material for heat conduction and heat dissipation and preparation method and application thereof | |
| CN103627088A (en) | Reinforced and toughened anti-bacterial polypropylene composition and preparation method thereof | |
| CN106589581B (en) | A kind of air-conditioning wind wheel PP Pipe Compound and preparation method thereof | |
| CN103897241A (en) | Heat conductive plastics and manufacturing method thereof | |
| CN105199304A (en) | Polymer composite high in heat-conducting property | |
| CN105384965B (en) | Carbon nanotube/expanded graphite composite filling and the heat-conducting polymer material containing composite filling | |
| CN102040776A (en) | Antibacterial polypropylene material and preparation method thereof | |
| CN103897331B (en) | A kind of Heat-conduction polyformaldehyde composite material and preparation method thereof | |
| CN104292631A (en) | Heat-conducting wear-resisting polypropylene resin and preparation method thereof | |
| CN105524425A (en) | Heat conduction epoxy resin composite material used for 3D printing, and preparation method thereof | |
| CN101891928A (en) | PCTFE modified filling composite material and production method thereof | |
| CN108676243A (en) | A kind of hybrid material, graphene modified heat resistant PE-RT tubing and preparation method thereof | |
| CN106243463B (en) | A kind of preparation method of Polymer/nano graphite flake/silicon dioxide composite material | |
| CN110746654A (en) | Halloysite-containing flame-retardant antibacterial compound and preparation method thereof | |
| CN108727817A (en) | A kind of polyimides chopped strand enhancing master batch and preparation method thereof | |
| Wang et al. | Morphology and properties of poly (vinyl alcohol)/MMT nanocomposite prepared by solid-state shear milling (S3M) | |
| CN104845150A (en) | PET/PTT/carbon nano-tube composite material and preparation method thereof | |
| Chen | Preparation of a poly (vinyl chloride)/layered double hydroxide nanocomposite with a reduced heavy‐metal thermal stabilizer | |
| CN107189220A (en) | Antibiotic property PP/PA composite and preparation method thereof | |
| CN115926249A (en) | Composite powder and preparation method thereof, resin modified master batch and preparation method and application thereof | |
| CN112552604B (en) | Heat-conducting and insulating polypropylene composite material and preparation method and application thereof | |
| CN104893176A (en) | CNT (carbon nano-tube)-based polymer modified cable material with hollow glass beads added as well as preparation method of cable material | |
| CN103450557A (en) | Preparation method of polypropylene PP (propene polymer) nanoscale reinforced and modified particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |