CN111607168A - Graphene oxide modified polypropylene-based square corrugated pipe and manufacturing method thereof - Google Patents
Graphene oxide modified polypropylene-based square corrugated pipe and manufacturing method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 93
- -1 polypropylene Polymers 0.000 title claims abstract description 83
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 230000004048 modification Effects 0.000 claims abstract description 30
- 238000012986 modification Methods 0.000 claims abstract description 30
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 25
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 24
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims abstract description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000010287 polarization Effects 0.000 claims abstract description 10
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene oxide modified polypropylene-based square corrugated pipe and a manufacturing method thereof, wherein the raw material of the square corrugated pipe consists of three components, namely graphene oxide subjected to polarization modification treatment by 2, 3-epoxypropyltrimethylammonium chloride, hexamethylenediamine, epichlorohydrin and polypropylene grafted maleic anhydride, and polypropylene subjected to modification treatment matched with the polarization modification of the first component, wherein the modification treatment specifically comprises the modification of the polypropylene by dopamine hydrochloride, trihydroxymethylaminomethane and polyethyleneimine; the third component is flame-retardant master batch taking polypropylene as a carrier, and the mass ratio of the first component to the second component to the third component is (0.7-1.5): (8-10): 1. the invention has the advantages of compression resistance, high thermal conductivity, high temperature resistance, oxidation resistance, good self-combination and good corrosion resistance.
Description
Technical Field
The invention relates to the technical field of insulating materials, in particular to a graphene oxide modified polypropylene-based square corrugated pipe and a manufacturing method thereof.
Background
In the prior art, the HPPM square electric power double-wall corrugated pipe is mainly applied to urban and rural open excavation cable-digging pipe arrangement engineering for high-voltage transmission lines and cables above 10KV, and the pipe connection adopts special clamp connection. The HPPM square electric corrugated pipe, whether a double-wall or single-wall corrugated pipe, is a novel structural wall pipe material which is usually manufactured by adopting heat-resistant, thermal-oxidative-aging-resistant and nano flame-retardant modified polypropylene as a main raw material and adopting a high-strength waveform design and a processing technology. The structure is novel, the compressive strength is high, and the construction is rapid and convenient; high temperature resistance, flame retardance, shock resistance, long service life and the like.
The product performance of a general HPPM square electric double-wall corrugated pipe includes: the excellent flexibility can adapt to the ground settlement or the change of a construction foundation, and the protection effect of the pipe on the cable is ensured; on the premise that the pipe achieves the same performance, less materials can be put in; the main material is not compounded with polypropylene, the Vicat softening temperature is above 135C, and the external pressure resistance is still kept at high temperature; the main material consists of two elements of carbon and hydrogen, the waste pipe can be recycled for the second time, and no white pollution exists in the production and recycling processes; the cable is non-conductive, does not transfer heat, has good insulation performance and meets the safe use requirement of high-voltage power; the corrosion resistance to various chemical media such as acid, alkali, salt and the like and the electroless chemical corrosion are realized, and the service life is as long as more than 50 years; the inner surface of the tube is smooth, the friction coefficient is low, the tube is in a contact state with the cable, and the dragging resistance is small; the working temperature range span is large, and the construction under various climatic conditions can be adapted; the special card drawing connection can be adopted, no welding seam and flash exist, and the cable cannot be scratched; the special corrugated structure design and the material with high elastic modulus ensure that the material has high ring stiffness and high compressive strength.
However, in the prior art, there are several pain points corresponding to actual use conditions, which are: 1. the bearing capacity and the impact resistance of the general HPPM square electric double-wall corrugated pipe are lower than those of a metal pipe, and the pipe cannot be suitable for a deeper ground bottom or a higher-pressure area, such as the front and back of a high-rise building or an earthquake high-rise area; 2. the conventional HPPM square electric double-wall corrugated pipe is limited by materials, has poor heat conduction capability, high temperature resistance and oxidation resistance, and cannot adapt to areas with higher temperature, larger temperature difference or larger environmental temperature change, such as areas near forging and casting workshops, desert zones and the like; 3. the conventional HPPM square electric double-wall corrugated pipe raw materials are generally simple mixed materials, namely polypropylene or high-density polyethylene is taken as a base raw material, functional additives such as a flame retardant and the like are directly added into the base raw material, but the functional additives do not generate chemical reaction with each other to cause poor binding force, and an organic chain has poor fusion degree and is easy to corrode and age under the action of microorganisms in a high-humidity environment.
Therefore, there is a need in the market for a graphene oxide modified polypropylene-based square corrugated tube with high pressure resistance, high thermal conductivity, high temperature resistance, oxidation resistance, good self-bonding property and good corrosion resistance, and a manufacturing method thereof.
Disclosure of Invention
The invention aims to provide a graphene oxide modified polypropylene-based square corrugated pipe which is resistant to pressure, high in thermal conductivity, high-temperature resistant, antioxidant, good in self-bonding and good in corrosion resistance and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a manufacturing method of a graphene oxide modified polypropylene-based square corrugated pipe comprises the following steps:
s1: preparing 88-90 parts of polypropylene, 8-10 parts of flame-retardant master batch taking polypropylene as a carrier, 8-10 parts of 2, 3-epoxypropyltrimethylammonium chloride, 14-16 parts of polypropylene grafted maleic anhydride, 18-20 parts of hexamethylenediamine, 9-10 parts of epichlorohydrin, 0.4-0.6 part of tetrabutylammonium bromide, 0.6-0.8 part of dopamine hydrochloride, 0.6-0.8 part of trihydroxymethyl aminomethane, 0.6-0.8 part of polyethyleneimine, 6.5-8 parts of potassium persulfate, 6.5-8 parts of phosphorus pentoxide, 260-280 parts of saturated concentrated sulfuric acid, 25-30 parts of potassium permanganate and 8-10 parts of graphite powder according to parts by weight; preparing enough ethanol, deionized water, hydrogen peroxide, 1mol/L hydrochloric acid aqueous solution and xylene;
s2: the method is adjusted on the basis of a Hummers method, graphite powder prepared by S1 is still used as a basic raw material, saturated concentrated sulfuric acid 35-40 parts, all phosphorus pentoxide, all potassium persulfate and all potassium permanganate are used as process raw materials, deionized water, hydrogen peroxide and hydrochloric acid aqueous solution with the concentration of 1mol/L are used as process auxiliary materials to prepare graphene oxide, and the method specifically comprises the following steps:
heating saturated concentrated sulfuric acid to 81-85 ℃, adding potassium persulfate and phosphorus pentoxide under the condition of continuous heat preservation, and stirring at a mechanical stirring speed of 100-120 rpm for 3-5 min to obtain a mixed solution;
secondly, adding graphite powder into the mixed solution, maintaining the stirring speed and keeping the temperature for 3.5-4 hours to obtain a pre-reaction solution;
thirdly, stopping stirring and preserving heat, after the pre-reaction solution is naturally cooled to room temperature, injecting 1800 to 2000 parts by weight of deionized water into the pre-reaction solution, fully stirring again, standing for 1.5 to 2 days, and finally filtering out solid substances;
fourthly, rinsing the solid content obtained by filtering out by using deionized water until the pH value is 6.5-7.5, and naturally drying the solid content to obtain a prefabricated product A;
fifthly, mixing the residual saturated concentrated sulfuric acid with the deionized water according to the mass ratio of 1: 2, cooling to room temperature, then carrying out ice bath to 0-5 ℃, adding the prefabricated product A and the potassium permanganate into the sulfuric acid aqueous solution subjected to the ice bath, stirring at a mechanical stirring speed of 100-120 rpm for 130-150 min, heating the reaction system to 38-40 ℃, continuously stirring and keeping the temperature for 90-100 min to obtain an intermediate reaction solution;
1400 to 1500 portions of deionized water and a proper amount of hydrogen peroxide by weight are added into the continuously stirred and insulated intermediate reaction solution, the addition amount of the hydrogen peroxide is to ensure that the molar concentration of the hydrogen peroxide in the reaction system is maintained between 10 and 12mol/L, and the final reaction solution is obtained after 20 to 25 min;
seventhly, centrifugally separating the final reaction solution, taking down turbid solution, drying to obtain final solid content, rinsing the final solid content to be stable in acidity by adopting 1mol/L hydrochloric acid aqueous solution, rinsing the final solid content to be stable in pH =6.5-7.5 by adopting deionized water, putting the rinsed final solid content into deionized water 18-20 times of the mass of the final solid content, and carrying out ultrasonic treatment until the final solid content is completely dispersed to obtain the required graphene oxide solution;
s3: the graphene oxide modification treatment specifically comprises the following steps:
putting 2, 3-epoxypropyltrimethylammonium chloride prepared in S1 into the graphene oxide solution obtained in S2, dispersing for 40-50 min at the ultrasonic power of 120-150W and the ultrasonic frequency of 30-35 kHz, then stirring at the stirring speed of 40-60 rpm until no floccule is generated, rinsing the separated floccule with deionized water, and drying to obtain a reactant B;
uniformly mixing the hexamethylenediamine prepared in the step S1, epichlorohydrin and 100-120 parts by weight of deionized water, standing at room temperature for reaction for 7-8 h, heating to 68-75 ℃, refluxing for 50-55 min, and dehydrating and drying the obtained product to obtain a reactant C;
thirdly, uniformly mixing the reactant C and the polypropylene grafted maleic anhydride prepared by the S1, adding the mixture into sufficient xylene, heating the mixture to 135-140 ℃, refluxing the mixture for 6-6.5 hours, adding the mixture into sufficient ethanol, stirring the mixture for 8-10 min at a stirring speed of 40-60 rpm, and then carrying out suction filtration and drying to obtain a reactant D;
fourthly, uniformly mixing the reactant B and tetrabutylammonium bromide prepared by the reactant D, S1, then adding the mixture into sufficient xylene, heating to 135-140 ℃, refluxing for 6-6.5 h, and then performing suction filtration and drying to obtain a reactant E, wherein the reactant E is the required modified graphene oxide;
s4: modification treatment of polypropylene
Firstly, rinsing and drying the polypropylene prepared in the S1 by using sufficient ethanol to obtain clean polypropylene;
uniformly mixing dopamine hydrochloride, tris (hydroxymethyl) aminomethane and polyethyleneimine prepared in S1, dissolving the mixture into 800 parts by weight of deionized water, and titrating the mixture to pH =8-8.5 by adopting a hydrochloric acid aqueous solution with the concentration of 1mol/L to obtain a modified solution;
thirdly, putting clean polypropylene into the primary modified solution, stirring for 4.5-5 h at a stirring speed of 40-60 rpm, taking out the reacted polypropylene, washing with deionized water until the pH is =6.5-7.5, and naturally drying to obtain the required modified polypropylene;
s5: raw material mixing and square corrugated pipe forming
Uniformly mixing modified polypropylene, modified graphene oxide and flame-retardant master batches taking polypropylene as carriers, putting the mixture serving as a mixed raw material into a mixer, and uniformly stirring to obtain a mixed raw material;
heating the mixed raw materials to be molten, extruding the molten raw materials into a square inner cavity of a mold, filling the molten liquid into the mold, moving the molten liquid forwards along with the mold, hardening and forming the square corrugated pipe by a cooling system in the mold, opening the mold after forming, demolding, and completely hardening the square corrugated pipe by water cooling spraying after demolding, thus finishing the forming process of the square corrugated pipe.
In the manufacturing method of the graphene oxide modified polypropylene-based square corrugated pipe, the flame-retardant master batch with polypropylene as a carrier is specifically halogen-free petrochemical flame-retardant PP5000 (+).
The raw material of the square corrugated pipe consists of three components, wherein the first component is graphene oxide which is subjected to polarization modification treatment through 2, 3-epoxypropyltrimethylammonium chloride, hexamethylenediamine, epichlorohydrin and polypropylene grafted maleic anhydride, wherein the graphene oxide is easy-to-modify graphene oxide which is prepared by taking graphite powder as a basic raw material, saturated concentrated sulfuric acid, phosphorus pentoxide, potassium persulfate and potassium permanganate as process raw materials and deionized water, hydrogen peroxide and a 1mol/L hydrochloric acid aqueous solution as process auxiliary materials; the second component is polypropylene which is subjected to modification treatment matched with the polarization modification of the first component, wherein the modification treatment is to modify the polypropylene by dopamine hydrochloride, trihydroxymethyl aminomethane and polyethyleneimine; the third component is flame-retardant master batch taking polypropylene as a carrier, and the mass ratio of the first component to the second component to the third component is (0.7-1.5): (8-10): 1.
compared with the prior art, the invention has the following advantages: (1) according to the invention, on the basis of improving the compatibility, thermal stability and mechanical property of the graphene oxide and PP blend, a product obtained by polarization modification of specially prepared easily-modified graphene oxide and a product obtained by corresponding modification of polypropylene are respectively used as two main monomers with groups easy to combine and compatibilize, and the PP-g-GO-flame retardant (the flame retardant is also a PP-based material) composite material is prepared by melt blending, so that the interfacial tension among three phases is reduced, a good interfacial compatibilization effect is achieved, and the binding force among the components is well increased. (2) The graphene oxide prepared by the improved Hummers method can more uniformly and fully complete polarization modification due to the surface structure (larger specific surface area and more appropriate surface groups), and compared with the conventional graphene oxide prepared by the Hummers method, the graphene oxide prepared by the improved Hummers method has the advantages that the modification efficiency and the coverage rate of modified groups are improved by about 5% and 7% on average, and the cost is not increased. (3) The average tensile strength, the compression strength and the cantilever beam impact strength of the graphene oxide modified polypropylene-based square corrugated pipe are respectively 45-48MPa, 56-63MPa and 42-46J/m, and compared with the conventional graphene oxide modified polypropylene or common PP, the graphene oxide modified polypropylene-based square corrugated pipe is obviously improved (but is lower than glass fiber reinforced PP). (4) The chemical stability of the modified polypropylene is superior to that of the conventional graphene oxide modified polypropylene or the common PP due to the self-bonding force caused by the modification treatment, and the modified polypropylene is mainly embodied in two aspects, namely that the thermal conductivity is about 10 times of that of the common PP, about 1.5 times of that of the conventional graphene oxide modified polypropylene, and that the softening temperature is higher than 135 ℃ of the conventional graphene oxide modified polypropylene, so that the modified polypropylene can endure 150 ℃ for at least 4 hours without softening, and the technical principle of the modified polypropylene is about that the modified polypropylene integrates the dual functions of grafting modification and crosslinking (to be further researched). (5) The modified graphene oxide of the invention has polar and nonpolar end groups respectively, wherein most of the polar groups are combined with polypropylene ends in a reaction way, and the nonpolar groups are used as free bulge groups to stretch outwards, so that the material of the invention also has quite good hydrophobic/hydrophobic performance, and the service life and the stability of the buried pipe are further improved. Therefore, the invention has the characteristics of compression resistance, high thermal conductivity, high temperature resistance, oxidation resistance, good self-combination and good corrosion resistance.
Detailed Description
Example 1:
the raw material of the square corrugated pipe consists of three components, wherein the first component is graphene oxide which is subjected to polarization modification treatment through 2, 3-epoxypropyltrimethylammonium chloride, hexamethylenediamine, epichlorohydrin and polypropylene grafted maleic anhydride, wherein the graphene oxide is easy-to-modify graphene oxide which is prepared by taking graphite powder as a basic raw material, saturated concentrated sulfuric acid, phosphorus pentoxide, potassium persulfate and potassium permanganate as process raw materials and deionized water, hydrogen peroxide and a 1mol/L hydrochloric acid aqueous solution as process auxiliary materials; the second component is polypropylene which is subjected to modification treatment matched with the polarization modification of the first component, wherein the modification treatment is to modify the polypropylene by dopamine hydrochloride, trihydroxymethyl aminomethane and polyethyleneimine; the third component is halogen-free polytechnology flame-retardant PP5000(+), and the mass ratio of the first component to the second component to the third component is (0.7-1.5): (8-10): 1;
the specific manufacturing method comprises the following steps:
s1: preparing 89.3kg of polypropylene, 9.2kg of halogen-free petrochemical flame-retardant PP5000(+), 8.3kg of 2, 3-epoxypropyltrimethylammonium chloride, 14.7kg of polypropylene grafted maleic anhydride, 19.2kg of hexamethylenediamine, 9.6kg of epichlorohydrin, 0.5kg of tetrabutylammonium bromide, 0.7kg of dopamine hydrochloride, 0.7kg of trihydroxymethyl aminomethane, 0.7kg of polyethyleneimine, 7.1kg of potassium persulfate, 7.3kg of phosphorus pentoxide, 273kg of saturated concentrated sulfuric acid, 28kg of potassium permanganate and 8.8kg of graphite powder; preparing enough ethanol, deionized water, hydrogen peroxide, 1mol/L hydrochloric acid aqueous solution and xylene;
s2: the method is adjusted on the basis of a Hummers method, graphite powder prepared by S1 is still used as a basic raw material, saturated concentrated sulfuric acid 38kg, all phosphorus pentoxide, all potassium persulfate and all potassium permanganate are used as process raw materials, deionized water, hydrogen peroxide and a 1mol/L hydrochloric acid aqueous solution are used as process auxiliary materials to prepare graphene oxide, and the method specifically comprises the following steps:
heating saturated concentrated sulfuric acid to 81-85 ℃, adding potassium persulfate and phosphorus pentoxide under the condition of continuous heat preservation, and stirring at a mechanical stirring speed of 100-120 rpm for 3-5 min to obtain a mixed solution;
secondly, adding graphite powder into the mixed solution, maintaining the stirring speed and keeping the temperature for 3.5-4 hours to obtain a pre-reaction solution;
thirdly, stopping stirring and preserving heat, after the pre-reaction solution is naturally cooled to room temperature, injecting 1800kg-2000kg of deionized water into the pre-reaction solution, fully stirring again, standing for 1.5-2 days, and finally filtering out solid substances;
fourthly, rinsing the solid content obtained by filtering out by using deionized water until the pH value is 6.5-7.5, and naturally drying the solid content to obtain a prefabricated product A;
fifthly, mixing the residual saturated concentrated sulfuric acid with the deionized water according to the mass ratio of 1: 2, cooling to room temperature, then carrying out ice bath to 0-5 ℃, adding the prefabricated product A and the potassium permanganate into the sulfuric acid aqueous solution subjected to the ice bath, stirring at a mechanical stirring speed of 100-120 rpm for 130-150 min, heating the reaction system to 38-40 ℃, continuously stirring and keeping the temperature for 90-100 min to obtain an intermediate reaction solution;
adding 1400-1500 kg of deionized water and a proper amount of hydrogen peroxide into the continuously stirred and heat-insulated intermediate reaction solution, wherein the addition amount of the hydrogen peroxide is to ensure that the molar concentration of the hydrogen peroxide in the reaction system is maintained at 10-12 mol/L, and obtaining a final reaction solution after the reaction system lasts for 20-25 min;
seventhly, centrifugally separating the final reaction solution, taking down turbid solution, drying to obtain final solid content, rinsing the final solid content to be stable in acidity by adopting 1mol/L hydrochloric acid aqueous solution, rinsing the final solid content to be stable in pH =6.5-7.5 by adopting deionized water, putting the rinsed final solid content into deionized water 18-20 times of the mass of the final solid content, and carrying out ultrasonic treatment until the final solid content is completely dispersed to obtain the required graphene oxide solution;
s3: the graphene oxide modification treatment specifically comprises the following steps:
putting 2, 3-epoxypropyltrimethylammonium chloride prepared in S1 into the graphene oxide solution obtained in S2, dispersing for 40-50 min at the ultrasonic power of 120-150W and the ultrasonic frequency of 30-35 kHz, then stirring at the stirring speed of 40-60 rpm until no floccule is generated, rinsing the separated floccule with deionized water, and drying to obtain a reactant B;
uniformly mixing the hexamethylenediamine prepared in the step S1, epichlorohydrin and 100kg-120kg of deionized water, standing at room temperature for reaction for 7h-8h, heating to 68-75 ℃, refluxing for 50min-55min, and dehydrating and drying the obtained product to obtain a reactant C;
thirdly, uniformly mixing the reactant C and the polypropylene grafted maleic anhydride prepared by the S1, adding the mixture into sufficient xylene, heating the mixture to 135-140 ℃, refluxing the mixture for 6-6.5 hours, adding the mixture into sufficient ethanol, stirring the mixture for 8-10 min at a stirring speed of 40-60 rpm, and then carrying out suction filtration and drying to obtain a reactant D;
fourthly, uniformly mixing the reactant B and tetrabutylammonium bromide prepared by the reactant D, S1, then adding the mixture into sufficient xylene, heating to 135-140 ℃, refluxing for 6-6.5 h, and then performing suction filtration and drying to obtain a reactant E, wherein the reactant E is the required modified graphene oxide;
s4: modification treatment of polypropylene
Firstly, rinsing and drying the polypropylene prepared in the S1 by using sufficient ethanol to obtain clean polypropylene;
uniformly mixing dopamine hydrochloride, tris (hydroxymethyl) aminomethane and polyethyleneimine prepared in S1, dissolving the mixture into 800kg of deionized water 600, and titrating the mixture to pH =8-8.5 by adopting a hydrochloric acid aqueous solution with the concentration of 1mol/L to obtain a modified solution;
thirdly, putting clean polypropylene into the primary modified solution, stirring for 4.5-5 h at a stirring speed of 40-60 rpm, taking out the reacted polypropylene, washing with deionized water until the pH is =6.5-7.5, and naturally drying to obtain the required modified polypropylene;
s5: raw material mixing and square corrugated pipe forming
Uniformly mixing modified polypropylene, modified graphene oxide and flame-retardant master batches taking polypropylene as carriers, putting the mixture serving as a mixed raw material into a mixer, and uniformly stirring to obtain a mixed raw material;
heating the mixed raw materials to be molten, extruding the molten raw materials into a square inner cavity of a mold, filling the molten liquid into the mold, moving the molten liquid forwards along with the mold, hardening and forming the square corrugated pipe by a cooling system in the mold, opening the mold after forming, demolding, and completely hardening the square corrugated pipe by water cooling spraying after demolding, thus finishing the forming process of the square corrugated pipe.
Comparison of the detection Performance of the PP-g-GO flame retardant of example 1 with that of a conventional GO-PP flame retardant and that of a conventional PP flame retardant
| Index (I) | Unit of | PP flame retardant | Go-PP flame retardant | PP-g-GO-flame retardant |
| Load resistant to external pressure | N/200mm | ≥5000 | ≥5000 | ≥6000 |
| Ring segment thermal compression force | kN/200mm | ≥1.0 | ≥1.0 | ≥1.2 |
| Flat test 40% | Whether or not to break | Whether or not | Whether or not | Whether or not |
| Recovery rate | % | ≥95 | ≥95 | ≥95 |
| Impact of drop hammer | - | 9/10 | 10/10 | 10/10 |
| Longitudinal shrinkage | % | ≤2 | ≤3 | ≤2 |
| Vicat softening temperature | ℃ | ≥135 | ≥135 | ≥150 |
| Volume resistivity | Ω·m | ≈1×1010 | ≥1×1011 | ≥1×1011 |
| Flame retardant properties | - | V-2 | V-0 | V-0 |
| Oxygen index | % | ≥30 | ≥27.5 | ≥30 |
| Tensile strength | MPa | 30-35 | 38-42 | 45-48 |
| Compressive strength | MPa | 36-42 | 50-55 | 56-63 |
| Impact strength of cantilever beam | J/m | 25-30 | 35-40 | 42-46 |
Example 2:
the whole is in accordance with example 1, with the difference that:
s1: preparing 90kg of polypropylene, 8kg of brominated petrochemical flame retardant, 8kg of 2, 3-epoxypropyltrimethylammonium chloride, 14kg of polypropylene grafted maleic anhydride, 18kg of hexamethylene diamine, 9kg of epichlorohydrin, 0.4kg of tetrabutylammonium bromide, 0.6kg of dopamine hydrochloride, 0.6kg of trihydroxymethyl aminomethane, 0.6kg of polyethyleneimine, 6.5kg of potassium persulfate, 6.5kg of phosphorus pentoxide, 260kg of saturated concentrated sulfuric acid, 25 kg of potassium permanganate and 8kg of graphite powder; preparing enough ethanol, deionized water, hydrogen peroxide, 1mol/L hydrochloric acid aqueous solution and xylene;
example 3:
the whole is in accordance with example 1, with the difference that:
s1: preparing 88kg of polypropylene, 10kg of magnesium hydroxide flame retardant, 10kg of 2, 3-epoxypropyltrimethylammonium chloride, 16kg of polypropylene grafted maleic anhydride, 20kg of hexamethylene diamine, 10kg of epoxy chloropropane, 0.6kg of tetrabutylammonium bromide, 0.8kg of dopamine hydrochloride, 0.8kg of tris (hydroxymethyl) aminomethane, 0.8kg of polyethyleneimine, 8kg of potassium persulfate, 8kg of phosphorus pentoxide, 280kg of saturated concentrated sulfuric acid, 30kg of potassium permanganate and 10kg of graphite powder; preparing enough ethanol, deionized water, hydrogen peroxide, 1mol/L hydrochloric acid aqueous solution and xylene;
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. A manufacturing method of a graphene oxide modified polypropylene-based square corrugated pipe is characterized by comprising the following steps:
s1: preparing 88-90 parts of polypropylene, 8-10 parts of flame-retardant master batch taking polypropylene as a carrier, 8-10 parts of 2, 3-epoxypropyltrimethylammonium chloride, 14-16 parts of polypropylene grafted maleic anhydride, 18-20 parts of hexamethylenediamine, 9-10 parts of epichlorohydrin, 0.4-0.6 part of tetrabutylammonium bromide, 0.6-0.8 part of dopamine hydrochloride, 0.6-0.8 part of trihydroxymethyl aminomethane, 0.6-0.8 part of polyethyleneimine, 6.5-8 parts of potassium persulfate, 6.5-8 parts of phosphorus pentoxide, 260-280 parts of saturated concentrated sulfuric acid, 25-30 parts of potassium permanganate and 8-10 parts of graphite powder according to parts by weight; preparing enough ethanol, deionized water, hydrogen peroxide, 1mol/L hydrochloric acid aqueous solution and xylene;
s2: the method is adjusted on the basis of a Hummers method, graphite powder prepared by S1 is still used as a basic raw material, saturated concentrated sulfuric acid 35-40 parts, all phosphorus pentoxide, all potassium persulfate and all potassium permanganate are used as process raw materials, deionized water, hydrogen peroxide and hydrochloric acid aqueous solution with the concentration of 1mol/L are used as process auxiliary materials to prepare graphene oxide, and the method specifically comprises the following steps:
heating saturated concentrated sulfuric acid to 81-85 ℃, adding potassium persulfate and phosphorus pentoxide under the condition of continuous heat preservation, and stirring at a mechanical stirring speed of 100-120 rpm for 3-5 min to obtain a mixed solution;
secondly, adding graphite powder into the mixed solution, maintaining the stirring speed and keeping the temperature for 3.5-4 hours to obtain a pre-reaction solution;
thirdly, stopping stirring and preserving heat, after the pre-reaction solution is naturally cooled to room temperature, injecting 1800 to 2000 parts by weight of deionized water into the pre-reaction solution, fully stirring again, standing for 1.5 to 2 days, and finally filtering out solid substances;
fourthly, rinsing the solid content obtained by filtering out by using deionized water until the pH value is 6.5-7.5, and naturally drying the solid content to obtain a prefabricated product A;
fifthly, mixing the residual saturated concentrated sulfuric acid with the deionized water according to the mass ratio of 1: 2, cooling to room temperature, then carrying out ice bath to 0-5 ℃, adding the prefabricated product A and the potassium permanganate into the sulfuric acid aqueous solution subjected to the ice bath, stirring at a mechanical stirring speed of 100-120 rpm for 130-150 min, heating the reaction system to 38-40 ℃, continuously stirring and keeping the temperature for 90-100 min to obtain an intermediate reaction solution;
1400 to 1500 portions of deionized water and a proper amount of hydrogen peroxide by weight are added into the continuously stirred and insulated intermediate reaction solution, the addition amount of the hydrogen peroxide is to ensure that the molar concentration of the hydrogen peroxide in the reaction system is maintained between 10 and 12mol/L, and the final reaction solution is obtained after 20 to 25 min;
seventhly, centrifugally separating the final reaction solution, taking down turbid solution, drying to obtain final solid content, rinsing the final solid content to be stable in acidity by adopting 1mol/L hydrochloric acid aqueous solution, rinsing the final solid content to be stable in pH =6.5-7.5 by adopting deionized water, putting the rinsed final solid content into deionized water 18-20 times of the mass of the final solid content, and carrying out ultrasonic treatment until the final solid content is completely dispersed to obtain the required graphene oxide solution;
s3: the graphene oxide modification treatment specifically comprises the following steps:
putting 2, 3-epoxypropyltrimethylammonium chloride prepared in S1 into the graphene oxide solution obtained in S2, dispersing for 40-50 min at the ultrasonic power of 120-150W and the ultrasonic frequency of 30-35 kHz, then stirring at the stirring speed of 40-60 rpm until no floccule is generated, rinsing the separated floccule with deionized water, and drying to obtain a reactant B;
uniformly mixing the hexamethylenediamine prepared in the step S1, epichlorohydrin and 100-120 parts by weight of deionized water, standing at room temperature for reaction for 7-8 h, heating to 68-75 ℃, refluxing for 50-55 min, and dehydrating and drying the obtained product to obtain a reactant C;
thirdly, uniformly mixing the reactant C and the polypropylene grafted maleic anhydride prepared by the S1, adding the mixture into sufficient xylene, heating the mixture to 135-140 ℃, refluxing the mixture for 6-6.5 hours, adding the mixture into sufficient ethanol, stirring the mixture for 8-10 min at a stirring speed of 40-60 rpm, and then carrying out suction filtration and drying to obtain a reactant D;
fourthly, uniformly mixing the reactant B and tetrabutylammonium bromide prepared by the reactant D, S1, then adding the mixture into sufficient xylene, heating to 135-140 ℃, refluxing for 6-6.5 h, and then performing suction filtration and drying to obtain a reactant E, wherein the reactant E is the required modified graphene oxide;
s4: modification treatment of polypropylene
Firstly, rinsing and drying the polypropylene prepared in the S1 by using sufficient ethanol to obtain clean polypropylene;
uniformly mixing dopamine hydrochloride, tris (hydroxymethyl) aminomethane and polyethyleneimine prepared in S1, dissolving the mixture into 800 parts by weight of deionized water, and titrating the mixture to pH =8-8.5 by adopting a hydrochloric acid aqueous solution with the concentration of 1mol/L to obtain a modified solution;
thirdly, putting clean polypropylene into the primary modified solution, stirring for 4.5-5 h at a stirring speed of 40-60 rpm, taking out the reacted polypropylene, washing with deionized water until the pH is =6.5-7.5, and naturally drying to obtain the required modified polypropylene;
s5: raw material mixing and square corrugated pipe forming
Uniformly mixing modified polypropylene, modified graphene oxide and flame-retardant master batches taking polypropylene as carriers, putting the mixture serving as a mixed raw material into a mixer, and uniformly stirring to obtain a mixed raw material;
heating the mixed raw materials to be molten, extruding the molten raw materials into a square inner cavity of a mold, filling the molten liquid into the mold, moving the molten liquid forwards along with the mold, hardening and forming the square corrugated pipe by a cooling system in the mold, opening the mold after forming, demolding, and completely hardening the square corrugated pipe by water cooling spraying after demolding, thus finishing the forming process of the square corrugated pipe.
2. The method for manufacturing a graphene oxide-modified polypropylene-based square corrugated tube according to claim 1, wherein: the flame-retardant master batch with the polypropylene as a carrier is specifically halogen-free petrochemical flame-retardant PP5000 (+).
3. The graphene oxide modified polypropylene-based square corrugated pipe is characterized in that: the raw material of the square corrugated pipe comprises three components, wherein the first component is graphene oxide subjected to polarization modification treatment by 2, 3-epoxypropyltrimethylammonium chloride, hexamethylenediamine, epichlorohydrin and polypropylene grafted maleic anhydride, wherein the graphene oxide is easily modified graphene oxide prepared by taking graphite powder as a basic raw material, saturated concentrated sulfuric acid, phosphorus pentoxide, potassium persulfate and potassium permanganate as process raw materials and deionized water, hydrogen peroxide and 1mol/L hydrochloric acid aqueous solution as process auxiliary materials; the second component is polypropylene which is subjected to modification treatment matched with the polarization modification of the first component, wherein the modification treatment is to modify the polypropylene by dopamine hydrochloride, trihydroxymethyl aminomethane and polyethyleneimine; the third component is flame-retardant master batch taking polypropylene as a carrier, and the mass ratio of the first component to the second component to the third component is (0.7-1.5): (8-10): 1.
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