CN104743539B - Modified carbon material, forming method thereof and coating - Google Patents
Modified carbon material, forming method thereof and coating Download PDFInfo
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- CN104743539B CN104743539B CN201410647140.8A CN201410647140A CN104743539B CN 104743539 B CN104743539 B CN 104743539B CN 201410647140 A CN201410647140 A CN 201410647140A CN 104743539 B CN104743539 B CN 104743539B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims description 37
- 238000000576 coating method Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 14
- 150000001721 carbon Chemical class 0.000 title abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229920002521 macromolecule Polymers 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 238000006206 glycosylation reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 5
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 229910021426 porous silicon Inorganic materials 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 229910021392 nanocarbon Inorganic materials 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011799 hole material Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- -1 acrylic acid form epoxy acrylate series Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002016 colloidosmotic effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
The modified carbon material provided by the invention comprises a carbon nanotube, wherein the surface of the carbon nanotube is provided with a first region surface and a second region surface; a porous silicon oxide shell layer covering the surface of the first region of the carbon nanotube; the macromolecule with epoxy group side chain is grafted on the surface of the second area of the carbon nano-tube.
Description
Technical field
The present disclosure generally relates to modify carbon materials, particularly apply with it with regard to its method for modifying.
Background technology
Commercial production and its daily life widely use metal, and metal erosion can cause great direct or indirect economy
Loss.According to statistics the economic loss caused by metal erosion industrially developed country account for national economy total output value 1.5%～
4%.Metal erosion causes equipment to drip or leak, and not only causes economic loss to also result in environmental pollution.Metal erosion affects industry raw
Product process and development in science and technology are very huge, are urgent problems.
The antirust paint being currently known generally comprises the antioxidant of metal ingredient and blends in resin or macromolecule.With the U.S.
As a example by patent US 6383271, in its anti-corrosive paints for disclosing, the filler included in resin is porous material, and antioxidant
It is contained in the hole of porous material if vanadate, zirconates or tungstates etc..Above-mentioned antioxidant is by by porous material
In hole slow release out, with up to long-acting antioxidant effect.General acid-proof etching ground needs very strict pre-treatment, applies
Break every with film thickness, its process is complicated, difficulty of construction is high, film thickness is thick, construction cost is big and difficult in some occasions
To reach technological requirement.The resin or macromolecule of especially above-mentioned anti-corrosive paints is necessary composition, and general resin or macromolecule
Glass transition temperature about between 80 DEG C to 140 DEG C.If ambient temperature is more than 65 DEG C, resin or the close glass of macromolecule turn
Change temperature and cannot effectively stop that extraneous aqueous vapor or soda acid liquid penetrate into metal base and causing corrosion.Volcano type underground heat is sent out
Electric module is because in high-temperature acidic environment, generation current module uses titanium alloy material, and development cost is too high.Traditional antirust,
Anti-corrosion coating typically for anti-" chlorine " corrosion of air, seldom inquires into anti-" sulfur " corrosion coating, and underground heat is good in order to require
Good heat exchanger effectiveness it is generally desirable to that thermal conductivity is high or the thin reduction thermal resistance of coating, the hundreds of microns of the usual thickness of current antirusting paint, heat
Resistance is too high.
In sum, new higher tolerable temperature rust-proof anti-corrosive paint is developed, can be applicable to hot spring system for geothermal production of electricity ring
Border, coating layer thickness is thin to have great heat radiation effect concurrently, is problem urgently to be resolved hurrily at present.
The content of the invention
The modification carbon materials that one embodiment of the invention is provided, including：CNT, the surface of the CNT has the firstth area
Field surface and second area surface；Porous silica shell (porous silica shell), covers the firstth area of CNT
Field surface；The macromolecule of tool epoxy base side chain (epoxy side chains), grafts on the second area surface of CNT.
The coating that one embodiment of the invention is provided, including：Above-mentioned modification carbon materials；Cross-linking agent；And organic solvent.
The forming method of the modification carbon materials that one embodiment of the invention is provided, including：The forming method of modification carbon materials, including：
(1) mix Amphiphatic high polymer and CNT in aqueous solution, make Amphiphatic high polymer wind CNT；(2) in step (1)
Afterwards, silicate is added into aqueous solution, and adjusts aqueous solution to acidity；(3) after step (2), plus hydrothermal solution is removing both sexes
Macromolecule, and form the portion of silicon oxide shell coating nano carbon pipe；(4) after step (3), sintering portion cladding
There is the CNT of the silicon oxide shell, to form the first area surface of porous silica shell coating nano carbon pipe；And
(5) after step (4), by the macromolecular grafted second area surface to CNT of tool epoxy base side chain, wherein the secondth area
Field surface is the surface of the CNT not coated by porous silica shell.
Description of the drawings
Fig. 1 shown in one embodiment of the invention, modifies the schematic diagram of CNT.
Fig. 2 shown in one embodiment of the invention, the schematic diagram of heatproof acid-proof corrosion resistant coating.
Fig. 3 shown in one embodiment of the invention, the CNT of porous silica shell cladding and the nanometer of acid treatment
The thermogravimetric analysiss comparison diagram of carbon pipe.
Fig. 4 shown in one embodiment of the invention, PGMA grafting second area surfaces and porous silica shell cladding the
The CNT of one region surface, compares with the thermogravimetric analysiss of the CNT that porous silica shell coats first area surface
Figure.
Fig. 5 shows the heat flow versus temperature curve of the sample of the embodiment of the present invention 1, comparative example 1 and comparative example 2.
Fig. 6 illustrates the product on the first area surface of the porous silica shell coating nano carbon pipe of the embodiment of the present invention 1
Electron micrograph.
Specific embodiment
The forming method of the modification carbon materials that one embodiment of the invention is provided.Step (1) is carried out first：First mix both sexes high score
Son in aqueous solution, makes Amphiphatic high polymer wind CNT with CNT.This step can allow what CNT wound self
Degree is reduced, and macroscopic is being seen as being tied with Amphiphatic high polymer on the CNT for stretching.In an embodiment of the present invention, both sexes high score
Son can be gelatin, polyacrylic acid or poly- P-TOLUENE SULFO ACID 99.The weight ratio of CNT and Amphiphatic high polymer is about between 1:0.05 to 1:
Between 0.3.If the ratio of Amphiphatic high polymer is too low, cannot effectively disperse CNT and make sodium silicate be adsorbed in surface.If
The ratio of Amphiphatic high polymer is too high, then silicon oxide is easily formed beyond carbon pipe surface.In an embodiment of the present invention, both sexes are high
The weight average molecular weight of molecule is about between 4000 to 200000.If the weight average molecular weight of Amphiphatic high polymer is too high, silicon oxide
Can easily reunite and be easy to CNT surface topography into.If the weight average molecular weight of Amphiphatic high polymer is too low, silicon oxide is easy
In being partially formed in CNT.In an embodiment of the present invention, can optionally first with strong acid such as nitric acid, sulfur before step (1)
Acid, other strong acid or combinations of the above acid treatment CNT, to remove the metal solvent remained during synthesis of carbon nanotube, and
Reduce the degree of CNT wound upon themselves.
Step (2) is carried out after step (1), silicate is added into aqueous solution, and adjust aqueous solution to acidity.In the present invention
In one embodiment, silicate can be sodium silicate, sodium silicate potassium or lithium metasilicate.Functional group on silicate and Amphiphatic high polymer
Such as hydroxyl reaction.In an embodiment of the present invention, the weight ratio of CNT and silicate is about between 5:1 to 2.5:Between 1.If
The ratio of silicate is too high, then silicon oxide can easily reunite and be easy to CNT surface topography into.If the ratio of silicate
Too low, then silicon oxide can only be coated in the local surfaces of CNT.
Carry out step (3), plus hydrothermal solution after step (2) to form the part of silicon oxide shell coating nano carbon pipe 11
Surface.This step also decomposes the unnecessary Amphiphatic high polymer not being wound on CNT surface.In an embodiment of the present invention, on
State plus hydrothermal solution temperature between 350 to 450 DEG C, the time is between 30 to 60 minutes.If plus the temperature of hydrothermal solution
Height and/or overlong time are spent, is then easy to destroy CNT.If plus the temperature of hydrothermal solution is too low and/or the time is too short,
Can not completely decompose and remove Amphiphatic high polymer.
Step (4) is carried out after step (3), the CNT 11 that portion coats silica shell is sintered, with shape
Into the surface of first area 12 of the coating nano carbon pipe 11 of porous silica shell 13.Above-mentioned sintering temperature is between 500 DEG C to 800 DEG C
Between, the time is between 30 minutes to 2 hours.If sintering temperature is too high and/or overlong time, silicon oxide easy disintegrating.If
Sintering temperature is too low and/or the time is too short, then the complete gel of sodium silicate is melted into silicon oxide.In an embodiment of the present invention, it is aforementioned
The area ratio on first area surface 12 and second area surface 14 is between 1:0.3 to 1:Between 0.6.If first area surface 12
Ratio it is too high, then the surfaction of CNT 11 is difficult to carry out.If the ratio on first area surface 12 is too low, carbon is modified
The obstruct aqueous vapor of material, oxygen ability are relatively low.
Step (5) is carried out after step (4), the macromolecule 15 of tool epoxy base side chain is grafted to into the second of CNT 11
Region surface 14, as shown in Figure 1.In FIG, n refers to the number of repetitives, about between 28 to 1400.At this
It is that the double bond monomer with epoxy radicals, radical initiator and first area surface 12 are coated with into porous in a bright embodiment
The CNT 11 of silicon oxide shell 13 is mixed in the organic solvent of eliminating water deoxygenation such as tetrahydrofuran.Heating or irradiation make freedom
Base initiator breaks are formed after free radical, and the second area surface 14 of CNT (is not covered by porous silica shell 13
CNT surface) produce free radical, double bond monomer and aggregate into the macromolecule 15 of tool epoxy base side chain and graft to CNT
On 11 second area surface 14.In an embodiment of the present invention, the double bond monomer with epoxy radicals can contract for methacrylic acid
Water glyceride (GMA), acrylic acid form epoxy acrylate series or combinations of the above with epoxy functionalized glycosylation reaction.Although
The macromolecule 15 of the tool epoxy base side chain shown in Fig. 1 is PGMA, but in the art the usually intellectual of having should be appreciated that and can be
The macromolecule of other tool epoxy base side chains, why end regards the double bond monomer with epoxy radicals.In an embodiment of the present invention, nanometer
The weight ratio of the macromolecule 15 of carbon pipe 11 and tool epoxy base side chain is between 1:1 to 1:Between 4.If the macromolecule 15 of epoxy base side chain
Ratio it is too high, then intercept aqueous vapor, oxygen ability relatively low.If the ratio of the macromolecule 15 of epoxy base side chain is too low, cannot have
Effect is attached to substrate.In an embodiment of the present invention, has the weight average molecular weight of macromolecule 15 of epoxy base side chain between 50,000
To between 300,000.If tool epoxy base side chain macromolecule 15 weight average molecular weight it is too high, paint viscosity it is too high and be difficult to plus
Work.If the weight average molecular weight of the macromolecule 15 of tool epoxy base side chain is too low, attaching substrates ability is weaker.Radical initiator can
For light trigger, thermal initiator or combinations of the above.In an embodiment of the present invention, the double bond monomer with epoxy radicals with from
By the weight ratio of base initiator between 1:0.02 to 1:Between 0.08.If the ratio of radical initiator is too high, have epoxy radicals
The weight average molecular weight of the macromolecule 15 of side chain is too low.If the ratio of radical initiator is too low, has the high score of epoxy base side chain
The weight average molecular weight of son 15 is too high.
Above-mentioned first area surface 12 is coated with porous silica shell 13, and second area surface grafting has tool epoxy radicals
The CNT 11 of the macromolecule 15 of side chain, i.e., so-called modification carbon materials.Take modification carbon materials, cross-linking agent to mix with organic solvent
Afterwards, that is, heatproof acid-proof etching ground is formed.In an embodiment of the present invention, cross-linking agent is diamidogen such as p-phenylenediamine or triethyl group two
Amine etc., diacid such as 1,3-propanedicarboxylic acid or terephthalic acids etc. or combinations of the above.In an embodiment of the present invention, carbon materials are modified with crosslinking
The part by weight of agent is between 1:0.3 to 1:Between 0.6.If the ratio of cross-linking agent is too high, unreacted cross-linking agent excessively affects to apply
Layer compactness extent.If the ratio of cross-linking agent is too low, cannot fully crosslinked epoxy polymeric impact coating compactness extent.At this
In a bright embodiment, organic solvent can be tetrahydrofuran, butanone, acetone or combinations of the above.In an embodiment of the present invention,
The part by weight of modification carbon materials and organic solvent is between 1:10 to 1:Between 30.If the ratio of organic solvent is too high, it is sprayed at
The coating that base material is formed is uneven.If the ratio of organic solvent is too low, unstable coating has sedimentation phenomenon.
After above-mentioned heatproof acid-proof etching ground is coated on metal base 21, heating makes the acidic group or amido of cross-linking agent 23
Ring-opening reaction is carried out from the epoxy radicals for grafting on the macromolecule 15 for having epoxy base side chain on different CNTs 11, different nanometers are made
It is as shown in Figure 2 that carbon pipe 11 produces crosslinking.In an embodiment of the present invention, plus hot coating temperature between 100 DEG C to 130 DEG C it
Between, and the time is between 30 minutes to 60 minutes.If heating-up temperature is too high and/or heat time heating time too long, epoxy macromolecule
It is easy to part thermal cracking.If heating-up temperature is too low and/or heat time heating time is too short, epoxy macromolecule cannot be fully crosslinked.So far
Formation heatproof acid-proof corrosion resistant coating is on metal base 21.In an embodiment of the present invention, above-mentioned heatproof acid-proof corrosion resistant coating
Thickness is between 10 μm to 50 μm.If coating layer thickness is excessively thin, the effect of anti-acid corrosion is unable to reach.If but coating layer thickness mistake
Thickness, then can increase cost.
Embodiment
Embodiment 1
This embodiment first by the first area Surface coating poriness silicon oxide of CNT, then by Glycidyl methacrylate
Glyceride (glycidyl methacrylater, GMA), the second area surface for being polymerized and directly grafting on CNT.Will
The CNT of above-mentioned modification, cross-linking agent and organic solvent are mixed to form after coating, then are sprayed on substrate surface, then
Heat hardening can form the coating of the anti-acid corrosion of heatproof.
Because there is self strong agglomeration of CNT that is commercially available or voluntarily synthesizing to touch with the metal of portion of residual
Matchmaker, therefore the CNT (Ming Xin scientific ＆ technical corporation, model C F182C) of 30g and the strong acid of 1000mL are first taken (such as the nitre of 1 parts by volume
Acid and the combination of the sulphuric acid of 3 parts by volume) mix post-heating and flowed back about 1 hour to 130 DEG C, to remove metal solvent and aoxidize
Part CNT is reducing agglomeration.Then by the acid solution dilute after backflow, centrifugation is gone the removal of impurity and is cleaned multiple times,
The CNT for being dried to obtain preliminary purification is dried again.Then the CNT of 20g is scattered in the water of 200mL, is added
The gelatin (gelatin) of 4g is stirred one day, makes gelatin wind CNT.The sodium silicate of 6g is subsequently added into, then water is adjusted with HCl
The pH value of solution is between 4～6.Finally whole solution is inserted into pyroreaction tank carries out hydro-thermal reaction (400 DEG C) (response time
1 hour), you can the first area Coated by Silica of carbon materials is made, and decomposes the extra gelatin of removal.Filter first area surface
After the nano carbon material of cladding silica is to go the removal of impurity and unreacted reactant, filter cake is collected and dries, then at 700 DEG C of sintering filter cakes
One hour, obtain final product the product on the first area surface of porous silica shell coating nano carbon pipe.The electron microscopic of above-mentioned product
Mirror photo exposes CNT as shown in fig. 6, the first area surface 12 of the coating nano carbon pipe 11 of porous silica shell 13
Second area surface 14.The thermogravimetric analysiss of the CNT after above-mentioned product and pickling are as shown in Figure 3.Can substantially be seen by Fig. 3
Go out CNT to burn in 800 DEG C i.e. complete oxidation, it is known that the weight of the CNT that porous silica shell is coated with it
Than being about 53:47.
First area Surface coating is then had the CNT of porous silica shell, the poly- methyl-prop of surface grafting is carried out
The reaction of olefin(e) acid ethylene oxidic ester.Taking 10g first areas Surface coating has the CNT of porous silica shell, is scattered in
In glycidyl methacrylate (GMA) monomer solution (concentration 50%) of 200g.The solvent of GMA monomer solutions is tetrahydrochysene furan
Mutter (THF).Heat the solution to 80 DEG C and coordinate ultrasonic vibrating one hour.Then using 10g as radical initiator
Benzoyl peroxide (benzoyl peroxide, BPO) be dissolved in tetrahydrofuran after, inject above-mentioned GMA monomers and first area
Surface coating has in the solution of the CNT of porous silica shell.BPO can allow the second area surface of CNT (not wrapped
Cover the surface of porous silica shell) free radical is produced, allow the double bond of GMA to produce Raolical polymerizable, and allow polymerization to be formed
PGMA graft to the second area surface (temperature 80 DEG C with 1 hour response time) of CNT.Finally gone with centrifugation
Except non-grafted macromolecule, obtain final product PGMA grafting second area surfaces and porous silica shell coats receiving for first area surface
Rice carbon pipe, its thermogravimetric analysis are as shown in Figure 4.The high score on the second area surface of CNT is grafted on as ise apparent from FIG. 4
Heat decomposition temperature of the son under nitrogen atmosphere is about between 200 DEG C to 300 DEG C, can estimate macromolecule by weight loss and account for changing
The 80wt% of matter CNT.
The CNT of 10g above-mentioned modification is scattered in into the mixed of the dimethyl sulfoxide of 40mL and the tetrahydrofuran of 160mL
In bonding solvent, and the 1,3-propanedicarboxylic acid cross-linking agent of 4g is added, that is, complete heatproof acid-proof etching ground.By the spraying of heatproof acid-proof etching ground
On the aluminium flake of 60mm × 60mm × 10mm, and baking makes the open loop cross-linking reaction of diamidogen and epoxy radicals for 30 minutes at 100 DEG C
Completely, i.e. formation coating is on aluminium flake.So far the sample of embodiment 1 is completed.
Comparative example 1
Mainly using synthetic epoxy resin as acid-proof acid-proof etching ground.The GMA monomers for taking 100g add the THF of 100ml,
The BPO of 0.04g is added in THF solution again, is heated to 85 DEG C and is reacted two hours, be eventually adding a large amount of methanol and separate out precipitation, will
Precipitate filters cleaning after bake dry stool and obtains poly (glycidyl methacrylate) (PMGA).By the PGMA for preparing with colloid osmotic
It is for about 200,000 that chromatograph (Gel Permeation Chromatography) measures its Weight-average molecular weight, and PDI is for about
1.85.The macromolecule that this has epoxide functional groups is configured in the mixed solvent (body of tetrahydrofuran, toluene and dimethyl sulfoxide
Product is than being the solution for 7/2/2) forming solid content about 10wt%.The 1,3-propanedicarboxylic acid cross-linking agent (5g) of relative PGMA weight 50% is added
Enter above-mentioned solution, that is, complete acid-proof etching ground.Acid-proof etching ground is sprayed on the aluminium flake of 60mm × 60mm × 10mm, with
100 DEG C of bakings make diamidogen complete with the open loop cross-linking reaction of epoxy radicals for 30 minutes, i.e., formation coating is on aluminium flake.Repeat spraying and
Twice, coating of the formation thickness more than 100 μm is on aluminium flake for baking procedure.So far the sample of comparative example 1 is completed.
Comparative example 2
In the sample of this comparative example, hole is filled with the hole carbon materials of tungstates (as antioxidant) and blends in comparative example
In 1 PGMA.With reference to United States Patent (USP) US 6383271, multi-layer nano carbon pipe is aoxidized with strong acid, destroy the end knot of CNT
Structure is forming hole material with carbon element.20g CNT powder body (Ming Xin scientific ＆ technical corporation, model C F182C) is taken, the dense sulfur of mixing is added
Acid and nitric acid volume ratio 3:1 cumulative volume 100mL post-heating to 130 DEG C are flowed back 1 hour, and centrifugal filtration removes unnecessary strong acid.Jing
After strong acid treatment, the specific surface area of multi-layer nano carbon pipe by script 130m2/ g increases to 190m2/ g, improves nearly 50%.
By the CNT immersion 1M (NH after 10g acid treatments4)6W7O24·6H2O aqueous solutions, centrifugal filtration removes excessive salt, is dried
The CNT comprising tungstates is obtained afterwards.Its is whole to account for the CNT containing tungstates with tungstates ratio knowable to thermogravimetry
About the 5% of body weight.The CNT containing tungstates of 20 weight portions is mixed with the PMGA of the comparative example 1 of 80 weight portions, i.e.,
Form acid-proof etching ground.Etching ground is sprayed on the aluminium flake of 60mm × 60mm × 10mm, i.e. formation coating is on aluminium flake.
So far the sample of comparative example 2 is completed.
Salt spray test is carried out 400 hours such as to the sample of embodiment 1, comparative example 1 and comparative example 2 according to CNS8886 standards
Shown in 1st table.The coating layer thickness of the sample of embodiment 1, comparative example 1 and comparative example 2, tack (test of hundred lattice), the glass of coating
Glass transition temperature and fusing point (with the measurement of Differential Scanning Calorimeter analyser) are as shown in table 1 below.Embodiment 1, comparative example 1 with compare
The heat flow versus temperature curve of the sample of example 2 is as shown in Figure 5.
The sample of embodiment 1, comparative example 1 and comparative example 2 is inserted into the H of 0.5M2SO4In, respectively at room temperature, 65 DEG C and
To measure tower husband's curve under+1～-1V voltages at 80 DEG C, and then calculate that its corrosion current is as shown in table 1.The bigger table of corrosion current
Show that the anti-corrosion effects of coating are poorer.
Table 1
From the comparison of table 1, the anti-corrosion effects of the coating of embodiment 1 under room temperature and relatively-high temperature are above ratio
Compared with the coating and the anti-corrosion effects of aluminium flake of example 1-2.
Although the present invention is disclosed above with embodiment, so it is not limited to the present invention, any art
Middle tool usually intellectual, it is without departing from the spirit and scope of the present invention, therefore of the invention when a little change and retouching can be made
Protection domain when being defined depending on the appended claim person of defining.
Symbol description
11 CNTs；
12 first areas surface；
13 porous silica shells；
14 second area surfaces；
The macromolecule of 15 tool epoxy base side chains；
21 metal bases；
23 cross-linking agent.
Claims (12)
1. it is a kind of to modify carbon materials, including：
CNT, the surface of the CNT has first area surface and second area surface；
Porous silica shell, covers the first area surface of the CNT；
The macromolecule of tool epoxy base side chain, grafts on the second area surface of the CNT.
2. it is as claimed in claim 1 to modify carbon materials, the wherein area ratio on the first area surface and the second area surface
Between 1:0.3 to 1:Between 0.6.
3. it is as claimed in claim 1 to modify carbon materials, the wherein high molecular weight of the CNT and the tool epoxy base side chain
Than between 1:1 to 1:Between 4.
4. modification carbon materials as claimed in claim 1, should wherein have the macromolecule of epoxy radicals by methyl propenoic acid glycidyl
Ester (GMA), acrylic acid and epoxy functionalized glycosylation reaction form epoxy acrylate series or combinations of the above is polymerized and obtains.
5. a kind of coating, including：
Modification carbon materials described in claim 1；
Cross-linking agent；And
Organic solvent.
6. coating as claimed in claim 5, the wherein cross-linking agent include diamidogen, diacid or combinations of the above, and modify carbon materials
With the weight ratio of the cross-linking agent between 1:0.3 to 1:Between 0.6.
7. the weight ratio of coating as claimed in claim 5, wherein the modification carbon materials and the organic solvent is between 1:10 to 1:30
Between.
8. it is a kind of modification carbon materials forming method, including：
(1) mix Amphiphatic high polymer and CNT in aqueous solution, make the Amphiphatic high polymer wind the CNT；
(2) after step (1), silicate is added into the aqueous solution, and adjusts the aqueous solution to acidity；
(3) after step (2), the aqueous solution is heated to remove the Amphiphatic high polymer, and form silicon oxide shell and coat the nanometer
The portion of carbon pipe；
(4) after step (3), the CNT that the portion is coated with the silicon oxide shell is sintered, to form porous oxidation
Silicon shell coats the first area surface of the CNT；And
(5) after step (4), by the macromolecular grafted second area surface to the CNT of tool epoxy base side chain, wherein
The second area surface is not by the surface of the CNT of the porous silica shell cladding.
9. the forming method of carbon materials, wherein the first area surface and the second area surface are modified as claimed in claim 8
Area ratio between 1:0.3 to 1:Between 0.6.
10. the forming method of carbon materials, the wherein height of the CNT and the tool epoxy base side chain are modified as claimed in claim 8
The weight ratio of molecule is between 1:1 to 1:Between 4.
The forming method of 11. modification carbon materials as claimed in claim 8, the wherein weight of the CNT and the Amphiphatic high polymer
Than between 1:0.05 to 1:Between 0.3.
The forming methods of 12. modification carbon materials as claimed in claim 8, the wherein Amphiphatic high polymer include gelatin, polyacrylic acid,
Or poly- P-TOLUENE SULFO ACID 99.
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| TW102149208A TWI530454B (en) | 2013-12-31 | 2013-12-31 | Modified carbon material and method for manufacturing the same and paint |
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