CN106987165B - A kind of graphene polymer water-repellent paint masterbatch and preparation method - Google Patents
A kind of graphene polymer water-repellent paint masterbatch and preparation method Download PDFInfo
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- CN106987165B CN106987165B CN201710383147.7A CN201710383147A CN106987165B CN 106987165 B CN106987165 B CN 106987165B CN 201710383147 A CN201710383147 A CN 201710383147A CN 106987165 B CN106987165 B CN 106987165B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 144
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 239000003973 paint Substances 0.000 title claims abstract description 56
- 239000005871 repellent Substances 0.000 title claims abstract description 45
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 57
- 239000006185 dispersion Substances 0.000 claims abstract description 56
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 45
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 graphite alkene Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 45
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004078 waterproofing Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
- C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
It is an object of the invention to propose a kind of graphene polymer water-repellent paint masterbatch and preparation method.It disperses graphene in the micropore of poromerics, then initiator auxiliary under with the micro- crosslinking of polyacrylate dispersion, to which by graphene/poromerics coating, coating graphene/poromerics, which is scattered in polyacrylate dispersion in the form of protomere, obtains graphene polymer water-repellent paint masterbatch.In polymer waterproof coating material, masterbatch has good dispersibility for directly addition when use, and graphene winds polymer, increase flim forming molecule chain, not only make waterproof membrane activeness and quietness, and make waterproof that there is good corrosion-resistant, resistance to ag(e)ing, the service life of polymer waterproof coating material is substantially improved.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of graphene polymer water-repellent paint masterbatch and preparation side
Method.
Background technique
In recent years, green building material is continually developed, to adapt to new era engineering construction needs.Polymer waterproof coating material is as one
Kind waterproof material comes into being.Polymer waterproof coating material is flexible waterproof material, two-component-type, including liquid material and powder,
Be certain proportion liquid material and powder stirring is uniform, hydration reaction and water-based emulsion crosslinking curing through inorganic powder it is compound and
At.Suitable for roofing, kitchen and toilet, basement, pond and other construction waterproofing engineerings.It is using cement-based material and macromolecule material
Expect compound technology, compensate for that cement-based material is flexible insufficient and high score is in the defect of materials water-resistant, loss of properties on aging,
Compared with conventional flex waterproof material, have the characteristics that can be used for moisture substrate constructs, is pollution-free and harmless.Due to this
Kind coating is made of " polymer emulsion-cement " bi-component, therefore the characteristic with " tempering toughness with gentleness ", existing polymer coating film
Extensibility, waterproofness also have the advantages of hydraulic cementing materials intensity is high, easily bonds with wet base, adjustable polymer
The ratio of lotion and cement, meets requirement of the different engineerings to flexibility and intensity etc., and construction method is convenient.This kind of coating is with water
As dispersing agent, solve because being good for using the environmental pollution caused by tar, pitch equal solvent type water-repellent paint and to human body
Health generates the problem of harm.
Polymer waterproof coating material becomes the first choice of current buildings waterproof because having flexible and accurate water-proof function.By
In its waterproof principle be polymer emulsion polymerization film formation, therefore it is the durability of polymer film, impervious most important.However due to
Polymer film forming layer is usually together with cement grade high basic species, and therefore, over time, polymer film is inevitable
Aging occurs.Waterproof failure after building 3-5 is typically resulted in, and is difficult to repair.Polymer emulsion is at film strength, impervious
Property, the problems such as durability is poor, seriously limit the promotion and application of such coating.
Graphene is thickness minimum, maximum intensity in nano material, has both large specific surface area, good conductivity, chemical stabilization
Property strong, mechanical property and the advantages that excellent thermal conductivity, in electronics, optics, magnetics, biology, sensor, energy storage, catalysis etc.
Field shows its unique function and effect.Graphene application range is very wide, and coating, which is that current graphene is numerous, answers
With an important component in field.By various physics outstanding, chemical property, graphene is in conductive coating, anti-corrosion
Coating, water-repellent paint, heat-conductive coating and high-intensitive coating etc. suffer from good development prospect.
Graphene is significant in high-intensitive paint field.Since the specific surface area of graphene is very high, added in coating
After graphene, reticular structure is formed during film curing, significantly enhances the caking property of paint film and ground, paint film
More stable, intensity is more preferable.After graphene is added, the impact resistance of coating, crocking resistance has larger improvement.Graphite
Alkene anticorrosive paint becomes the star in graphene composite material.Anticorrosive paint is always one of important branch of coating, in industry
Using very extensive in production.In national economy production, a large amount of metal products use the requirement for making equipment anticorrosion very high,
The market demand presentation of anticorrosive paint persistently rises situation.Statistical data shows that the whole world is every year because of economy caused by corrosion
Loss is up to trillion dollars, economic loss brought by remote supernatural disaster.Experiment shows to be added in existing anticorrosive paint
Graphene handles outside original performance, more improves the indexs such as impact resistance, adhesive force, water resistance, hardness.
The characteristics such as its excellent electric conductivity, unique two-dimensional slice structure and its surface hydrophobicity, graphite due to graphene
The experimental work of alkene incorporation water-repellent paint is carried out extensively.Experiment shows to be prepared for graphene/silicon acrylic emulsion using solution ultrasonic method
Composite material, composite material have lower percolation threshold (about 0.5%, mass fraction, similarly hereinafter).Graphene dosage is 0.7%
When, in the good situation of dispersity in macromolecule matrix, compared with the silicone acrylic emulsion film that graphene is not added, composite wood
The tensile strength of material improves 15.5%, and elongation at break has dropped 3.6%, and water resistance improves 14%, and Corrosion Protection also obtains
Significant increase.
With the development of novel urbanization, demand of the mankind for high-performance waterproof paint, especially building water-proof paint
Can more come it is bigger, and in terms of water-repellent paint, the attention of the outstanding representation of graphene doping vario-property by everybody.But graphene
The problem of being in two applied to water-repellent paint can not avoid, first is that entire preparation cost needs further compression, second is that graphite
The dispersion stabilization problem of alkene.It is therefore desirable to prepare a kind of graphene polymer waterproof painting using economically viable process
Material.Pushing the upgrading of paint industry has vital meaning.
Summary of the invention
It is an object of the invention to propose a kind of graphene polymer water-repellent paint masterbatch and preparation method.Utilize graphene
The characteristic of enhancing, disperses graphene in the micropore of poromerics, then initiator auxiliary under with polyacrylate dispersion
Micro- crosslinking, so that coating graphene/poromerics is scattered in polypropylene in the form of protomere by graphene/poromerics coating
Graphene polymer water-repellent paint masterbatch is obtained in acid esters lotion.Directly addition is in polymer waterproof coating material when use, masterbatch
With good dispersibility, graphene winds polymer, increases flim forming molecule chain, not only makes waterproof membrane activeness and quietness, and
Make waterproof that there is good corrosion-resistant, resistance to ag(e)ing, the service life of polymer waterproof coating material is substantially improved.
A kind of preparation method of graphene polymer water-repellent paint masterbatch, specific preparation step include:
(1) graphene/poromerics preparation
The graphene of 20-30 parts by weight is placed in deionized water to that evenly dispersed graphene is obtained after ultrasonic disperse is water-soluble
Liquid pours into the poromerics of 15-30 parts by weight in graphene aqueous solution, and mechanical stirring is spraying to pulpous state at 60 ~ 100 DEG C
The dry graphene dispersion that obtains forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Then the polyacrylate dispersion of 15-30 parts by weight is added in material, initiator and NaHCO are added in whipping process3, room temperature is anti-
1-2h is answered, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/poromerics under initiation form coating graphite
Alkene/poromerics, graphene is stably fixed in the micropore of poromerics；The initiator amount is polyacrylate cream
The 0.3-0.5% of fluid solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, is then emulsified with 0.5-1 parts by weight
Agent, 20-30 parts by weight polyacrylate dispersion, 0.5 h of dispersion and emulsion under high velocity agitation, coating graphene/poromerics
It is scattered in polyacrylate dispersion in the form of protomere, obtains a kind of graphene polymer water-repellent paint masterbatch.
Preferably, the ultrasonic disperse, jitter time are 1 ~ 6 hour.
Preferably, the poromerics in porous carbon, diatomite, zeolite powder, aerosil at least one
Kind, after poromerics needs to carry out high-temperature calcination, 20 microns of powder below are crushed to, the aperture of poromerics preferably selects
Being can will be graphene-supported.
Preferably, the initiator is selected from one of potassium peroxydisulfate and ammonium persulfate.
Preferably, the emulsifier is selected from one of OP-10, AEO-9.
Preferably, the solid content of the polyacrylate dispersion is 25-35%.
A kind of graphene polymer water-repellent paint masterbatch, it is characterized in that polymer waterproof prepared by the above method applies
Expect dedicated parent material.By dispersing graphene in the micropore of poromerics, further in its surface-crosslinked coating, spy outstanding
Point is so that graphene is dispersed in polyacrylate dispersion in the form of protomere.The masterbatch is compatible with polymer waterproof coating material
Property, favorable dispersibility, after use, coating graphene/poromerics is scattered in polymer waterproof coating material in the form of protomere, and
Graphene and polymer sufficiently wind enhancing in waterproof film forming procedure, and graphene is enabled preferably to play humidification.No
But makes waterproof membrane activeness and quietness, and make waterproof that there is good corrosion-resistant, resistance to ag(e)ing, polymer waterproof coating material is substantially improved
Service life.
Compared with prior art, the prominent feature of the present invention and excellent effect are:
1, the present invention provides a kind of graphene polymer water-repellent paint masterbatch, and directly addition is applied in polymer waterproof when use
In material, graphene sufficiently winds enhancing to polymer, and graphene is enabled preferably to play humidification, reinforcement film mechanics
Performance, itself has hydrophobic and lyophobic property, and lamellar structure has " labyrinth " effect, water, corrosive ion etc. can be hindered to coating
The infiltration of internal layer delays paint film corrosion rate, and then plays the role of corrosion-resistant.In short, the addition of graphene not only makes waterproof
Film activeness and quietness, and make waterproof that there is good corrosion-resistant, resistance to ag(e)ing, polymer waterproof coating material is substantially improved uses the longevity
Life.
2, the present invention a kind of process of preparing of graphene polymer water-repellent paint masterbatch is provided, by by graphene with
Poromerics load, and micro- crosslinking film forming package, so that coating graphene/poromerics is dispersed in the form of protomere, realization is received
Meter level dispersion, to effectively assign and improve the performance of polymer.
3, the present invention provides a kind of process of preparing of graphene polymer water-repellent paint masterbatch, preparation method operation
Simple and easy to do, Preparation equipment is common common apparatus, and easy control of reaction conditions technique is easy, is beneficial to industrialized production.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) graphene/poromerics preparation
The graphene of 20 parts by weight is placed in deionized water after ultrasonic disperse 1 hour, evenly dispersed graphene is obtained
Aqueous solution pours into the poromerics diatomite of 15 parts by weight in graphene aqueous solution, and mechanical stirring is sprayed to pulpous state at 60 DEG C
The dry graphene dispersion that obtains of mist forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Then material is added the polyacrylate dispersion that the solid content of 15 parts by weight is 35%, initiator persulfuric acid is added in whipping process
Potassium and NaHCO3, react at room temperature 1h, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/micropore material under initiation
Material forms coating graphene/poromerics, and graphene is stably fixed in the micropore of poromerics；The initiator amount
It is the 0.3% of polyacrylate dispersion solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 0.5 parts by weight Emulsifier
OP-10,20 parts by weight solid content be 25% polyacrylate dispersion, 0.5 h of dispersion and emulsion under high velocity agitation, coating stone
Black alkene/poromerics is scattered in polyacrylate dispersion in the form of protomere, obtains a kind of graphene polymer water-repellent paint
Masterbatch.
Graphene polymer water-repellent paint masterbatch obtained is applied to exterior wall waterproofing coating, raw material is main by weight
It include: 10 parts of graphene polymer water-repellent paint masterbatch, 40 parts of polyurethane-polyacrylate composite emulsion, 40 parts of silica solution,
6 parts of dodecyltrichlorosilane, 0.5 part of octyl phenol polyoxyethylene ether, 1.5 parts of fatty acid sorbitan, 3 parts of asbestos powder, lignin
15 parts, 1 part of hydroxyethyl cellulose, 2 parts of Kynoar micro mist, 1 part of ammonium hydroxide, 2 parts of perchloroethylene, 1 part of wetting agent, defoaming agent 2
Part, 20 parts of water.
After testing, the resulting water-repellent paint of the embodiment has characteristics that
Alkali resistance experiment (saturated calcium hydroxide and 0.1% sodium hydroxide mixed solution, 20 °C impregnate 30 days): do not play drum,
It does not fall off；
Acid resistance experiment (0.1% hydrochloric acid solution, 20 °C are impregnated 30 days): drum is not played, is not fallen off；
Heat resistance experiment (100 ± 1 DEG C, 240 hours): drum is not played, is not trickled, is not fallen off；
Impermeability (0.5 MPa, 30min): waterproof.
Embodiment 2
(1) graphene/poromerics preparation
The graphene of 30 parts by weight is placed in deionized water and obtains evenly dispersed graphene aqueous solution after ultrasonic disperse,
After zeolite powder high-temperature calcination, 20 microns of powder below are crushed to, the poromerics zeolite powder of 20 parts by weight is taken to pour into graphite
In aqueous solution, mechanical stirring to pulpous state, spray drying obtains graphene dispersion and is formed in poromerics micropore at 100 DEG C
Graphene/poromerics；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Material, is then added the polyacrylate dispersion of the solid content 30% of 30 parts by weight, initiator ammonium persulfate is added in whipping process
And NaHCO3, react at room temperature 2h, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/poromerics under initiation
Coating graphene/poromerics is formed, graphene is stably fixed in the micropore of poromerics；The initiator amount is
The 0.5% of polyacrylate dispersion solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 1 parts by weight Emulsifier
AEO-9,20 parts by weight solid contents are 25% polyacrylate dispersion, under high velocity agitation 0.5 h of dispersion and emulsion, coating graphite
Alkene/poromerics is scattered in polyacrylate dispersion in the form of protomere, and it is female to obtain a kind of graphene polymer water-repellent paint
Material.
Graphene polymer water-repellent paint masterbatch obtained is applied to exterior wall waterproofing coating, raw material is main by weight
Adjustment are as follows: 10 parts of graphene polymer water-repellent paint masterbatch, 30 parts of polyurethane-polyacrylate composite emulsion, remaining and implementation
Example 1 is consistent.
After testing, the resulting water-repellent paint of the embodiment has characteristics that
Alkali resistance experiment (saturated calcium hydroxide and 0.1% sodium hydroxide mixed solution, 20 °C impregnate 30 days): do not play drum,
It does not fall off；
Acid resistance experiment (0.1% hydrochloric acid solution, 20 °C are impregnated 30 days): drum is not played, is not fallen off；
Heat resistance experiment (100 ± 1 DEG C, 240 hours): drum is not played, is not trickled, is not fallen off；
Impermeability (0.5MPa, 30min): waterproof；
Embodiment 3
(1) graphene/poromerics preparation
The graphene of 25 parts by weight is placed in deionized water after ultrasonic disperse 3 hours, evenly dispersed graphene is obtained
Aqueous solution pours into the poromerics aerosil of 15 parts by weight in graphene aqueous solution, the mechanical stirring at 60 DEG C
To pulpous state, spray drying obtains graphene dispersion and forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Then material is added the polyacrylate dispersion that the solid content of 20 parts by weight is 30%, initiator persulfuric acid is added in whipping process
Potassium and NaHCO3, react at room temperature 1h, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/micropore material under initiation
Material forms coating graphene/poromerics, and graphene is stably fixed in the micropore of poromerics；The initiator amount
It is the 0.4% of polyacrylate dispersion solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 1 parts by weight Emulsifier
OP-10,25 parts by weight solid content be 25% polyacrylate dispersion, 0.5 h of dispersion and emulsion under high velocity agitation, coating stone
Black alkene/poromerics is scattered in polyacrylate dispersion in the form of protomere, obtains a kind of graphene polymer water-repellent paint
Masterbatch.
Graphene polymer water-repellent paint masterbatch obtained is applied to exterior wall waterproofing coating, raw material is main by weight
Adjustment are as follows: 10 parts of graphene polymer water-repellent paint masterbatch, 10 parts of polyurethane-polyacrylate composite emulsion, remaining and implementation
Example 1 is consistent.
After testing, the resulting water-repellent paint of the embodiment has characteristics that
Alkali resistance experiment (saturated calcium hydroxide and 0.1% sodium hydroxide mixed solution, 20 °C impregnate 30 days): do not play drum,
It does not fall off；
Acid resistance experiment (0.1% hydrochloric acid solution, 20 °C are impregnated 30 days): drum is not played, is not fallen off；
Heat resistance experiment (100 ± 1 DEG C, 240 hours): drum is not played, is not trickled, is not fallen off；
Impermeability (0.5MPa, 30min): waterproof；
Embodiment 4
(1) graphene/poromerics preparation
The graphene of 30 parts by weight is placed in deionized water after ultrasonic disperse 1 hour, evenly dispersed graphene is obtained
Aqueous solution pours into the poromerics porous carbon of 15 parts by weight in graphene aqueous solution, and mechanical stirring is sprayed to pulpous state at 80 DEG C
The dry graphene dispersion that obtains of mist forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Then material is added the polyacrylate dispersion that the solid content of 15 parts by weight is 35%, initiator persulfuric acid is added in whipping process
Potassium and NaHCO3, react at room temperature 1h, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/micropore material under initiation
Material forms coating graphene/poromerics, and graphene is stably fixed in the micropore of poromerics；The initiator amount
It is the 0.3% of polyacrylate dispersion solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 0.5 parts by weight Emulsifier
OP-10,20 parts by weight solid content be 25% polyacrylate dispersion, 0.5 h of dispersion and emulsion under high velocity agitation, coating stone
Black alkene/poromerics is scattered in polyacrylate dispersion in the form of protomere, obtains a kind of graphene polymer water-repellent paint
Masterbatch.
Graphene polymer water-repellent paint masterbatch obtained is applied to exterior wall waterproofing coating, raw material is main by weight
Adjustment are as follows: 10 parts of graphene polymer water-repellent paint masterbatch, 25 parts of polyurethane-polyacrylate composite emulsion, remaining and implementation
Example 1 is consistent.
After testing, the resulting water-repellent paint of the embodiment has characteristics that
Alkali resistance experiment (saturated calcium hydroxide and 0.1% sodium hydroxide mixed solution, 20 °C impregnate 30 days): do not play drum,
It does not fall off；
Acid resistance experiment (0.1% hydrochloric acid solution, 20 °C are impregnated 30 days): drum is not played, is not fallen off；
Heat resistance experiment (100 ± 1 DEG C, 240 hours): drum is not played, is not trickled, is not fallen off；
Impermeability (0.5MPa, 30min): waterproof.
Embodiment 5
(1) graphene/poromerics preparation
The graphene of 20 parts by weight is placed in deionized water after ultrasonic disperse 1 hour, evenly dispersed graphene is obtained
Aqueous solution pours into the poromerics zeolite of 15 parts by weight in graphene aqueous solution, and mechanical stirring is spraying to pulpous state at 60 DEG C
The dry graphene dispersion that obtains forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/micropore material of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser
Then material is added the polyacrylate dispersion that the solid content of 30 parts by weight is 30%, initiator persulfuric acid is added in whipping process
Potassium and NaHCO3, react at room temperature 1h, polyacrylate dispersion micro- crosslinking film forming, coated graphite alkene/micropore material under initiation
Material forms coating graphene/poromerics, and graphene is stably fixed in the micropore of poromerics；The initiator amount
It is the 0.3% of polyacrylate dispersion solid content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 0.5 parts by weight Emulsifier
OP-10,30 parts by weight solid content be 25% polyacrylate dispersion, 0.5 h of dispersion and emulsion under high velocity agitation, coating stone
Black alkene/poromerics is scattered in polyacrylate dispersion in the form of protomere, obtains a kind of graphene polymer water-repellent paint
Masterbatch.
Graphene polymer water-repellent paint masterbatch obtained is used to waterproof coating material of cement based polymer to test:
Blank sample proportion are as follows: 42.5 300 parts of ordinary portland cements；80 parts of quartz sand；5 parts of dicalcium powder (325 mesh)；It is high
0.3 part of water-reducing agent of effect；5 parts of re-dispersible glue powder；200 parts of water.
Directly add the proportion of commercially available graphene slurry are as follows: 42.5 300 parts of ordinary portland cements；80 parts of quartz sand；Coarse whiting
5 parts of powder (325 mesh)；0.3 part of high efficiency water reducing agent；5 parts of re-dispersible glue powder；200 parts of water；10 parts of commercially available graphene slurry.
Add the proportion of the present embodiment masterbatch are as follows: 42.5 300 parts of ordinary portland cements；80 parts of quartz sand；Dicalcium powder
5 parts of (325 mesh)；0.3 part of high efficiency water reducing agent；5 parts of re-dispersible glue powder；200 parts of water；10 parts of the present embodiment masterbatch.
By GB/T 23445-2009, by its mechanical property of film property test, specific test can be as shown in table 1.
Table 1:
Claims (7)
1. a kind of preparation method of graphene polymer water-repellent paint masterbatch, specific preparation step include:
(1) graphene/poromerics preparation
The graphene of 20-30 parts by weight is placed in deionized water and obtains evenly dispersed graphene aqueous solution after ultrasonic disperse,
The poromerics of 15-30 parts by weight is poured into graphene aqueous solution, mechanical stirring is spray-dried to pulpous state at 60 ~ 100 DEG C
It obtains graphene dispersion and forms graphene/poromerics in poromerics micropore；
(2) micro- crosslinking
Graphene/poromerics of step (1) preparation is added in the reaction kettle equipped with thermometer, blender and condenser, so
The polyacrylate dispersion of 15-30 parts by weight is added afterwards, initiator and NaHCO are added in whipping process3, react at room temperature 1-
2h, polyacrylate dispersion micro- crosslinking film forming under initiation, coated graphite alkene/poromerics formation coating graphene/micro-
Graphene is stably fixed in the micropore of poromerics by Porous materials；The initiator amount is solid for polyacrylate dispersion
The 0.3-0.5% of content quality；The NaHCO3Dosage, which is subject to, is adjusted to system pH 8-9；
(3) coating graphene/poromerics pH that step (2) obtains is adjusted to neutrality, then with 0.5-1 parts by weight Emulsifier,
The polyacrylate dispersion of 20-30 parts by weight, 0.5 h of dispersion and emulsion under high velocity agitation, coating graphene/poromerics is with micro-
Micellar form is scattered in polyacrylate dispersion, obtains a kind of graphene polymer water-repellent paint masterbatch.
2. a kind of preparation method of graphene polymer water-repellent paint masterbatch according to claim 1, it is characterised in that: described
Ultrasonic disperse, jitter time are 1 ~ 6 hour.
3. a kind of preparation method of graphene polymer water-repellent paint masterbatch according to claim 1, it is characterised in that: described
Poromerics is selected from least one of porous carbon, diatomite, zeolite powder, aerosil, and poromerics needs to carry out
After high-temperature calcination, be crushed to 20 microns of powder below, the aperture of poromerics preferably select be can will be graphene-supported.
4. a kind of preparation method of graphene polymer water-repellent paint masterbatch according to claim 1, it is characterised in that: described
Initiator is selected from one of potassium peroxydisulfate and ammonium persulfate.
5. a kind of preparation method of graphene polymer water-repellent paint masterbatch according to claim 1, it is characterised in that: described
Emulsifier is selected from one of OP-10, AEO-9.
6. a kind of preparation method of graphene polymer water-repellent paint masterbatch according to claim 1, it is characterised in that: described
The solid content of polyacrylate dispersion is 25-35%.
7. a kind of graphene polymer water-repellent paint masterbatch, it is characterized in that the masterbatch is by any one of the claim 1-6 side
The graphene polymer water-repellent paint masterbatch that method is prepared.
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