CN106674811A - Tubing with high strength and high toughness for mining and preparation method thereof - Google Patents

Tubing with high strength and high toughness for mining and preparation method thereof Download PDF

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Publication number
CN106674811A
CN106674811A CN201611185709.9A CN201611185709A CN106674811A CN 106674811 A CN106674811 A CN 106674811A CN 201611185709 A CN201611185709 A CN 201611185709A CN 106674811 A CN106674811 A CN 106674811A
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graphene oxide
parts
nano imvite
ester
montmorillonite
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CN201611185709.9A
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宋志勇
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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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • 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
    • 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

Abstract

The invention discloses tubing with high strength and high toughness for mining and a preparation method thereof. The tubing is prepared by the following raw materials in parts by weight: 50-70 parts of polyvinyl chloride, 10-15 parts of diglycidyl 1,2-cyclohexanedicarboxylate, 18-26 parts of oxidized graphene, 11-18 parts of sub white corundum fine powder, 4-7 parts of tristearin, 10-15 parts of basic magnesium sulfate whisker, 9-14 parts of bis(2-ethylhexyl) phthalate, 12-19 parts of aerosol, 5-8 parts of montan wax, 24-37 parts of montmorillonite, 2-4 parts of aluminium stearate, 1-3 parts of magnesium stearate, and 16-23 parts of white onyx powder. Based on a high-molecular blend system of polyvinyl chloride, diglycidyl 1,2-cyclohexanedicarboxylate and bis(2-ethylhexyl) phthalate, the sub white corundum fine powder, the basic magnesium sulfate whisker, the white onyx powder, and other raw materials are added, so that tensile strength and toughness of the material are improved, and heat resistance, wear resistance and shock resistance of the material are improved.

Description

A kind of high-strength and high ductility mining pipes and preparation method thereof
Technical field
The present invention relates to a kind of PVC and preparation method thereof, and in particular to a kind of high-strength and high ductility mining pipes and its system Preparation Method.
Background technology
Montmorillonite is a kind of typical natural clay mineral, with reserves height, various, the cheap, structure of species etc. Advantage.Montmorillonite also has good dispersive property, can be extensively using macromolecular material industry as nanometer polymer high score The additive of sub- material, improves mechanical property, dimensional stability, thermal stability and gas barrier property etc., so as to play increasing The effect of strength polymer comprehensive physical performance, while improving materiel machining performance, has a extensive future.
Zheng Yuying, Peng Chao are at it《The development of PVC-U/ montmorillonite Nanocomposite Pipes》With montmorillonite as main former in one text Material, is modified to it by suitable organic intercalation agent and have developed organo montmorillonite, then using the lipophile of polrvinyl chloride, fortune PVC solutions are inserted between organic cheating engaging layer with intercalation technique, montmorillonite layer is peeled off and with nano-size dispersion in PVC phases In, the compound of nano lamellar montmorillonite and PVC is realized, there is obtained PVC-U/ montmorillonite Nanocomposite Pipes excellent Physical and mechanical property.But composite pipe obtained in above-mentioned document has sheet resistance greatly, the shortcoming of antistatic behaviour difference, tubing Surface will produce electrostatic once friction, and be gathered in tube surfaces, if being applied to coal production operation, just have during static discharge Can fire hazard and gas explosion, it is impossible to meet the use requirement of mining pipes, limit its range of application.In addition, above-mentioned The intensity and toughness of composite pipe obtained in document is also unsatisfactory.
Graphene oxide is the oxide of Graphene, is a kind of important derivatives of Graphene, is had to Graphene similar Structure, with excellent optics, thermodynamics, mechanics and electric property, improving electric conductivity, heat conductivity, the mechanical property of material The combination properties such as energy aspect plays very important effect.
Therefore, the present invention first carries out ammonia using N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane to montmorillonite Baseization is modified, and is then lived using 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride and N-hydroxy-succinamide Change the carboxyl of surface of graphene oxide, the carboxyl of such surface of graphene oxide can carry out amide with the amino on montmorillonite surface Condensation, and then make graphene oxide layer be coated on montmorillonite surface, graphene oxide cladding nano imvite is obtained, then adopt Graft modification is carried out to it with butyl acrylate, its compatibility and dispersion stabilization with PVC matrix is improved, polyacrylic acid is obtained The graphene oxide cladding nano imvite of butyl ester graft modification, is applied in PVC as conductive filler, is improving PVC On the basis of the thermal stability and mechanical property of tubing, the sheet resistance of PVC is reduced, have obtained PVC There is excellent antistatic behaviour.The present invention is also in polrvinyl chloride, hexahydrophthalic acid 2-glycidyl ester, phthalic acid two On the basis of the polymer blends of (2- ethylhexyls) ester, sub-white corundum fine powder, alkali magnesium sulfate crystal whisker, micropowder silicon are added The raw materials such as glue, white jade stone powder, not only increase the tensile strength and toughness of material, further improve thermostability, the wearability of material And shock resistance.
The content of the invention
It is an object of the invention to provide a kind of high-strength and high ductility mining pipes and preparation method thereof, pipes for mining of the present invention Material intensity is high, and good toughness is heat-resist, and wearability is good, strong shock resistance.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of high-strength and high ductility mining pipes, are made up of the raw material of following weight portion：Polrvinyl chloride 50-70, hexahydro neighbour's benzene two Formic acid 2-glycidyl ester 10-15, graphene oxide 18-26, sub-white corundum fine powder 11-18, glyceryl tristearate 4-7, alkali Formula magnesium sulfate crystal whisker 10-15, phthalic acid two (2- ethylhexyls) ester 9-14, micropowder silica gel 12-19, lignite wax 5-8, illiteracy are de- Native 24-37, aluminium stearate 2-4, magnesium stearate 1-3, white jade stone powder 16-23.
A kind of preparation method of high-strength and high ductility mining pipes, comprises the following steps：
(1) according to solid-to-liquid ratio 1:10-20 is added to montmorillonite in 95% dehydrated alcohol, stirs, Ran Houjia Enter N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane equivalent to montmorillonite quality 3-6%, oil bath heating to 65- 70 DEG C, 1.5-2h is stirred, be cooled to room temperature, respectively cleaned three times with ethanol, deionized water respectively, lyophilization is crushed to nanometer Particle diameter, sieves, and obtains final product amination nano imvite；
(2) graphene oxide is added water and stirs the graphene oxide dispersion for making that mass concentration is 0.6-1.2mg/mL, It is subsequently adding 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride equivalent to graphene oxide quality 46-52% With the N-hydroxy-succinamide of 42-48%, amination nanometer obtained in step (1) is added to cover de- after supersound process 20-30min Soil, stirs 3-6h under the rotating speed of 600-900r/min, filters, and is respectively cleaned three times with methanol, deionized water respectively, and freezing is dry Dry, 730-770 DEG C of calcining 0.5-1.5h is cooled to room temperature, obtains final product graphene oxide cladding nano imvite；
(3) according to solid-to-liquid ratio 1:21-29 by graphene oxide cladding nano imvite be added to the water, add equivalent to Graphene oxide coats the sodium lauryl sulphate of nano imvite quality 2.5-4.5%, ultrasonic disperse 1.5-2.5h, Ran Houshui Bath heating, is heated to being passed through nitrogen when 75-80 DEG C, when heating 80-85 DEG C, adds and covers de- equivalent to graphene oxide cladding nanometer The Ammonium persulfate. of soil property amount 0.6-0.7%, when being heated to 85-90 DEG C, adds and coats nano imvite equivalent to graphene oxide The butyl acrylate of quality 48-54%, stirring reaction 2-5h is filtered, and washing, drying, comminution by gas stream obtains final product butyl polyacrylate The graphene oxide cladding nano imvite of graft modification；
(4) by polrvinyl chloride, alkali magnesium sulfate crystal whisker, hydrogen o-phthalic acid diglycidyl ester, aluminium stearate at a high speed Plus in Hot mixer, 65-85 DEG C is heated to, and mix 14-22min, add sub-white corundum fine powder, micropowder silica gel, lignite wax, neighbour Phthalic acid two (2- ethylhexyls) ester, is heated to 75-95 DEG C, mixes 12-19min, adds when material temperature is down to 60-80 DEG C poly- The graphene oxide cladding nano imvite of butyl acrylate graft modification and remaining raw material, mix 8-16min, obtain final product mixing Material；
(5) compound obtained in step (4) is added in double screw extruder and is extruded, double screw extruder barrel zone temperature For 175-195 DEG C, die head temperature is 165-185 DEG C, and screw speed is 30-60r/min, then Jing trombone slides, cooling, cutting, system Into tubing.
Beneficial effects of the present invention：
(1) present invention first carries out amino using N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane to montmorillonite Change and be modified, then activated using 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride and N-hydroxy-succinamide The carboxyl of surface of graphene oxide, the carboxyl of such surface of graphene oxide can carry out amide contracting with the amino on montmorillonite surface Close, and then make graphene oxide layer be coated on montmorillonite surface, graphene oxide cladding nano imvite is obtained, then adopt Butyl acrylate carries out graft modification to it, improves its compatibility and dispersion stabilization with PVC matrix, and polyacrylic acid fourth is obtained The graphene oxide cladding nano imvite of ester graft modification, is applied in PVC as conductive filler, is improving pvc pipe On the basis of the thermal stability and mechanical property of material, the sheet resistance of PVC is reduced, there is obtained PVC Excellent antistatic behaviour；
(2) present invention is in polrvinyl chloride, hexahydrophthalic acid 2-glycidyl ester, (the 2- ethyl hexyls of phthalic acid two Base) ester polymer blends on the basis of, add sub-white corundum fine powder, alkali magnesium sulfate crystal whisker, micropowder silica gel, white jade stone The raw materials such as powder, not only increase the tensile strength and toughness of material, further improve thermostability, wearability and the impact resistance of material Energy.
Specific embodiment
A kind of high-strength and high ductility mining pipes, are made up of the raw material of following weight (kg)：Polrvinyl chloride 60, hexahydro O-phthalic Sour 2-glycidyl ester 12, graphene oxide 22, sub-white corundum fine powder 15, glyceryl tristearate 5, alkali magnesium sulfate crystal whisker 13rd, phthalic acid two (2- ethylhexyls) ester 11, micropowder silica gel 16, lignite wax 6.5, montmorillonite 31, aluminium stearate 3, Hard Fat Sour magnesium 2, white jade stone powder 19.
A kind of preparation method of high-strength and high ductility mining pipes, comprises the following steps：
(1) according to solid-to-liquid ratio 1:10-20 is added to montmorillonite in 95% dehydrated alcohol, stirs, Ran Houjia Enter N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane equivalent to montmorillonite quality 3-6%, oil bath heating to 65- 70 DEG C, 1.5-2h is stirred, be cooled to room temperature, respectively cleaned three times with ethanol, deionized water respectively, lyophilization is crushed to nanometer Particle diameter, sieves, and obtains final product amination nano imvite；
(2) graphene oxide is added water and stirs the graphene oxide dispersion for making that mass concentration is 0.6-1.2mg/mL, It is subsequently adding 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride equivalent to graphene oxide quality 46-52% With the N-hydroxy-succinamide of 42-48%, amination nanometer obtained in step (1) is added to cover de- after supersound process 20-30min Soil, stirs 3-6h under the rotating speed of 600-900r/min, filters, and is respectively cleaned three times with methanol, deionized water respectively, and freezing is dry Dry, 730-770 DEG C of calcining 0.5-1.5h is cooled to room temperature, obtains final product graphene oxide cladding nano imvite；
(3) according to solid-to-liquid ratio 1:21-29 by graphene oxide cladding nano imvite be added to the water, add equivalent to Graphene oxide coats the sodium lauryl sulphate of nano imvite quality 2.5-4.5%, ultrasonic disperse 1.5-2.5h, Ran Houshui Bath heating, is heated to being passed through nitrogen when 75-80 DEG C, when heating 80-85 DEG C, adds and covers de- equivalent to graphene oxide cladding nanometer The Ammonium persulfate. of soil property amount 0.6-0.7%, when being heated to 85-90 DEG C, adds and coats nano imvite equivalent to graphene oxide The butyl acrylate of quality 48-54%, stirring reaction 2-5h is filtered, and washing, drying, comminution by gas stream obtains final product butyl polyacrylate The graphene oxide cladding nano imvite of graft modification；
(4) by polrvinyl chloride, alkali magnesium sulfate crystal whisker, hydrogen o-phthalic acid diglycidyl ester, aluminium stearate at a high speed Plus in Hot mixer, 65-85 DEG C is heated to, and mix 14-22min, add sub-white corundum fine powder, micropowder silica gel, lignite wax, neighbour Phthalic acid two (2- ethylhexyls) ester, is heated to 75-95 DEG C, mixes 12-19min, adds when material temperature is down to 60-80 DEG C poly- The graphene oxide cladding nano imvite of butyl acrylate graft modification and remaining raw material, mix 8-16min, obtain final product mixing Material；
(5) compound obtained in step (4) is added in double screw extruder and is extruded, double screw extruder barrel zone temperature For 175-195 DEG C, die head temperature is 165-185 DEG C, and screw speed is 30-60r/min, then Jing trombone slides, cooling, cutting, system Into tubing.
The main performance testing result of PVC obtained in above-described embodiment is as shown in the table：
Detection project Unit Testing result
Tensile strength MPa 73
Longitudinal welds % 2.9
Sheet resistance Ω 3.5×106
Aging coefficient (70 DEG C, 144h) — 0.87

Claims (2)

1. a kind of high-strength and high ductility mining pipes, it is characterised in that be made up of the raw material of following weight portion：Polrvinyl chloride 50-70, six Hydrogen o-phthalic acid diglycidyl ester 10-15, graphene oxide 18-26, sub-white corundum fine powder 11-18, three glycerol stearates Ester 4-7, alkali magnesium sulfate crystal whisker 10-15, phthalic acid two（2- ethylhexyls）Ester 9-14, micropowder silica gel 12-19, lignite wax 5-8, montmorillonite 24-37, aluminium stearate 2-4, magnesium stearate 1-3, white jade stone powder 16-23.
2. a kind of preparation method of high-strength and high ductility mining pipes as claimed in claim 1, it is characterised in that including following step Suddenly：
（1）According to solid-to-liquid ratio 1:10-20 is added to montmorillonite in 95% dehydrated alcohol, stirs, and is subsequently adding quite In the N- of montmorillonite quality 3-6%（β-aminoethyl）- γ-aminopropyltriethoxy dimethoxysilane, oil bath heating is stirred to 65-70 DEG C 1.5-2h is mixed, room temperature is cooled to, is respectively cleaned three times with ethanol, deionized water respectively, lyophilization is crushed to nanometer particle size, mistake Sieve, obtains final product amination nano imvite；
（2）Graphene oxide is added water and stirs the graphene oxide dispersion for making that mass concentration is 0.6-1.2mg/mL, then Add equivalent to graphene oxide quality 46-52% 1- ethyls-（3- dimethylaminopropyls）Carbodiimide hydrochloride and 42- 48% N-hydroxy-succinamide, adds step after supersound process 20-30min（1）Obtained amination nano imvite, 3-6h is stirred under the rotating speed of 600-900r/min, is filtered, and respectively cleaned three times with methanol, deionized water respectively, lyophilization, 730-770 DEG C of calcining 0.5-1.5h, is cooled to room temperature, obtains final product graphene oxide cladding nano imvite；
（3）According to solid-to-liquid ratio 1:21-29 is added to the water graphene oxide cladding nano imvite, adds equivalent to oxidation The sodium lauryl sulphate of graphene coated nano imvite quality 2.5-4.5%, ultrasonic disperse 1.5-2.5h, then water-bath adds Heat, is heated to being passed through nitrogen when 75-80 DEG C, when heating 80-85 DEG C, adds and coats nano imvite matter equivalent to graphene oxide The Ammonium persulfate. of amount 0.6-0.7%, when being heated to 85-90 DEG C, adds and coats nano imvite quality equivalent to graphene oxide The butyl acrylate of 48-54%, stirring reaction 2-5h is filtered, washing, drying, comminution by gas stream, obtains final product butyl polyacrylate grafting Modified graphene oxide cladding nano imvite；
（4）By polrvinyl chloride, alkali magnesium sulfate crystal whisker, hydrogen o-phthalic acid diglycidyl ester, aluminium stearate to heated at high speed In mixer, 65-85 DEG C is heated to, mixes 14-22min, add sub-white corundum fine powder, micropowder silica gel, lignite wax, adjacent benzene two Formic acid two（2- ethylhexyls）Ester, is heated to 75-95 DEG C, mixes 12-19min, and polypropylene is added when material temperature is down to 60-80 DEG C The graphene oxide cladding nano imvite of acid butyl ester graft modification and remaining raw material, mix 8-16min, obtain final product compound；
（5）By step（4）Obtained compound is added in double screw extruder and extrudes, and double screw extruder barrel zone temperature is 175-195 DEG C, die head temperature is 165-185 DEG C, and screw speed is 30-60r/min, then Jing trombone slides, cooling, and cutting is made Tubing.
CN201611185709.9A 2016-12-20 2016-12-20 Tubing with high strength and high toughness for mining and preparation method thereof Pending CN106674811A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400313A (en) * 2017-08-10 2017-11-28 温州市环美建筑工程有限公司 High-temperature resistance plastice pipeline and its manufacture method
CN115011043A (en) * 2022-06-13 2022-09-06 东南大学 Ethylene propylene rubber insulating composition and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400313A (en) * 2017-08-10 2017-11-28 温州市环美建筑工程有限公司 High-temperature resistance plastice pipeline and its manufacture method
CN115011043A (en) * 2022-06-13 2022-09-06 东南大学 Ethylene propylene rubber insulating composition and preparation method thereof

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Application publication date: 20170517