CN109517516A - A kind of cerium bentonite modified watersoluble polyurethane paint and preparation method thereof - Google Patents
A kind of cerium bentonite modified watersoluble polyurethane paint and preparation method thereof Download PDFInfo
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- CN109517516A CN109517516A CN201811380494.5A CN201811380494A CN109517516A CN 109517516 A CN109517516 A CN 109517516A CN 201811380494 A CN201811380494 A CN 201811380494A CN 109517516 A CN109517516 A CN 109517516A
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- bentonite
- cerium
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- chitosan
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 55
- 239000000440 bentonite Substances 0.000 title claims abstract description 55
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 49
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003973 paint Substances 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011527 polyurethane coating Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 13
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 229940092782 bentonite Drugs 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 25
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 14
- 229940080314 sodium bentonite Drugs 0.000 claims description 14
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 11
- 229920002101 Chitin Polymers 0.000 claims description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000004069 aziridinyl group Chemical group 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- -1 poly- ammonia Ester Chemical class 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 20
- 229910001868 water Inorganic materials 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 230000003260 anti-sepsis Effects 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 230000008569 process Effects 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of cerium bentonite modified watersoluble polyurethane paints and preparation method thereof, by rare earth ion Ce3+It loads to and is prepared cerium bentonite on the pretreated bentonite of chitosan, then be distributed to cerium bentonite aqueous dispersion as modified filler in anionic water-based aliphaic polyurethane resin, be aided with a certain amount of crosslinking agent and auxiliary agent prepares modified coating.By mass percentage, the waterborne polyurethane resin 30~60%, deionized water 20~50%, cerium bentonite 1~5%, crosslinking agent 1~5%, other auxiliary agents 0.2~2%.Cerium bentonite modified watersoluble polyurethane paint prepared by the present invention substantially increases the adhesive force of aqueous polyurethane coating, and show preferable water resistance and corrosion resistance, it is suitable for more severe corrosive environment, is with a wide range of applications in heavy antisepsis field.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of cerium bentonite modified watersoluble polyurethane paint and its system
Preparation Method.
Technical background
Currently, anticorrosive paint is one of most common method of anticorrosion of steel structure.However, these coating are largely solvent types
Coating can release a large amount of volatile organic compounds (VOC) in the production and use process, not only a large amount of money of waste
Source can also bring huge environmental hazard.And water paint, using water as decentralized medium, VOC content is low, nontoxic, non-stimulated.Cause
This, under the overall background of " environmentally protective, energy-saving and emission-reduction ", it is inexorable trend that water-based anticorrosive paint, which replaces solvent type anticorrosive paint,.
Aqueous polyurethane (WPU) coating as a kind of environment-friendly type coating, have solvent borne polyurethane coating low film formation temperature,
The features such as strong adhesive force, good weatherability, flexibility are good, paint film is plentiful, but its water-fast etch resistant properties is poor, seriously restricts it anti-
Application in rotten field.Therefore aqueous polyurethane coating often need to carry out compound resin is modified, low-surface energy substance (organosilicon,
Organic fluoride) modified and inorganic micro Nano material (graphene, carbon nanotube, phyllosilicate, SiO2、TiO2) modified etc. modified
Processing.Number of patent application 201611262880.5 discloses a kind of graphene-organic silicon modified polyurethane water paint, patent Shen
Please numbers 201610640316.6 disclose it is a kind of using modified kaolin as the preparation method of the aqueous polyurethane coating of filler, patent
Application number 201510944523.6 discloses a kind of nano silicon dioxide modifying water polyurethane water-proof paint and preparation method thereof.
Different modified materials respectively have advantage and disadvantage, are promoted to a certain degree although etch resistant properties have, but still less than now widely used
Solvent type anticorrosive paint.Therefore, water-fast etch resistant properties difference be still limitation aqueous polyurethane coating applied in corrosion-resistant field it is main
Reason.Bentonitic main component montmorillonite is a kind of sheet aluminium silicate mineral, can not only be used for filler in coating to corruption
Lose medium (H2O、O2、Cl-Deng) play physical barrier, carrier loaded functional material is alternatively arranged as applied in coating.Cause
This, the present invention proposes that load is had to the Ce of catalytic action using aqueous polyurethane coating as matrix3+Bentonite introduce it is aqueous poly-
Urethane matrix, is aided with a certain amount of crosslinking agent to improve the hardness of waterborne polyurethane resin, adhesive force and water-fast etch resistant properties, with
Realize application of the aqueous polyurethane coating in heavy antisepsis field.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of paintings of cerium bentonite modified watersoluble polyurethane
Material and preparation method thereof.The modified aqueous polyurethane coating is water-fast, and etch resistant properties are excellent, adhesive force is strong, environmentally protective, processing work
Skill is simple, low in cost.
Technical scheme is as follows: a kind of cerium bentonite modified watersoluble polyurethane paint, it is characterised in that: described
Cerium bentonite modified watersoluble polyurethane paint, by mass percentage, the waterborne polyurethane resin 30~60%, go from
Sub- water 20~50%, cerium bentonite 1~5%, crosslinking agent 1~5%, other auxiliary agents 0.2~2%.
Further, the waterborne polyurethane resin selects anionic-aliphatic poly ether type waterborne polyurethane resin, institute
State crosslinking
Agent is aziridine, and other auxiliary agents are sodium hexametaphosphate dispersant and defoaming agent dimethicone.
Further, for the cerium bentonite using sodium bentonite as raw material, soluble cerium salt is modifying agent, will have and urge
Change the Ce for hydrolyzing the aqueous polyurethane function3+It loads to and is prepared on the pretreated bentonite of chitosan；Ceriumization is swollen
Moistening native specific preparation step includes:
(d) a certain amount of chitosan is dissolved in 2~8% acetic acid solution, is stirred to react 0.5~1h at normal temperature,
300~600r/min of revolving speed prepares chitosan-acetic acid solution；
(e) sodium bentonite shell is added to chitosan mass ratio according to sodium bentonite for 1:0.005~1:0.02 to gather
Sugar-acetic acid solution is washed with deionized after stirring 1~3h at normal temperature with the revolving speed of 500~800r/min, filters 2-5
Time, remaining chitosan and acetic acid are removed, chitin modified bentonite is obtained；
(f) it disperses chitin modified bentonite in and is configured to the suspension that concentration is 5~10% in deionized water, stirring
After 0.5~2h, by soluble cerium salt according to Ce3+It is added in suspension for the amount of 100mmol/100g sodium bentonite, adjustment is outstanding
Supernatant liquid pH to 4~6, and 4-6h is continuously stirred with the revolving speed of 500~800r/min in 40~50 DEG C of water-baths, then use deionized water
Washing filters 2-3 times；
(d) the cerium bentonite of preparation is placed in drying in 50~80 DEG C of vacuum oven, then in planetary ball mill
Grinding is to 75 μm or less.
Further, the preparation method of the cerium bentonite modified watersoluble polyurethane paint described in more than one, feature
It is, including following preparation method:
(1) cerium bentonite powder is added in deionized water by the component proportion, with magnetic stirrer 1~
2h, then disperse 30~60min in ultrasonic cleaner；
(2) aqueous gather is added by the component proportion under conditions of magnetic agitation in the cerium bentonite dispersion liquid of preparation
In urethane resin, after stirring 1~2h, aziridine crosslinker is added by the component proportion and other auxiliary agents are stirred for 1~3h, turn
600~1000r/min of speed.
The beneficial effects of the present invention are:
1, the present invention is modified aqueous polyurethane coating using cerium bentonite, and the special lamella of bentonite is utilized
Shape structure forms physical barrier in coating, secondly, load to be had to the Ce of catalytic action3+Bentonite introduce aqueous polyurethane
Matrix makes its reaction at the higher modified coating of the degree of cross linking, to significantly improve aqueous polyurethane after being aided with a certain amount of crosslinking agent
Adhesive force, hardness and the water-fast corrosion stability of coating, compared to water-based polyurethane resin, 3~4 times of adhesive force raising or more is resistance to
Corrosive salt spray can exceed that 700h, and electrochemical corrosion resistant impedance improves 2~3 orders of magnitude, is suitable for more severe corrosive environment,
In ocean and chemical industry etc., corrosion-resistant fields are with a wide range of applications；
2, the raw material of the cerium bentonite modified watersoluble polyurethane paint prepared by the present invention is environmentally protective, cheap easy
, cerium bentonite synthesis technology is simple, and coating material production is low in cost.
Detailed description of the invention
Fig. 1 is the shape appearance figure after cerium bentonite modified watersoluble polyurethane coating soaks 192 hours.
Fig. 2 is shape appearance figure of the cerium bentonite modified watersoluble polyurethane coating exposure neutral salt spray after 768 hours.
Fig. 3 is the Nyquist map of cerium bentonite modified watersoluble polyurethane coating.
Specific embodiment
Below in conjunction with preferred embodiment and subordinate list, specific embodiments of the present invention will be described in further detail.
Embodiment 1
A kind of cerium bentonite modified watersoluble polyurethane paint, the cerium bentonite modified watersoluble polyurethane paint
Raw material includes: that anionic water-based aliphaic polyurethane resin WPU3530 is 50% by mass percentage, deionized water
46.5%, cerium bentonite 1.25%, crosslinking agent aziridine SaC-100 is 2%, sodium hexametaphosphate dispersant and defoaming agent diformazan
Base silicone oil auxiliary agent 0.25%.
The bentonitic preparation of ceriumization: weigh 0.1g chitosan be dissolved in 200ml, 5% acetic acid solution in, stir at normal temperature
It mixes reaction 1h, revolving speed 500r/min and prepares chitosan-acetic acid solution；By sodium bentonite according to sodium bentonite and chitosan
Mass ratio is that 1:0.01 is added to chitosan-acetic acid solution, after stirring 2h at normal temperature with the revolving speed of 500r/min, uses deionized water
Washing filters 3 times, obtains chitin modified bentonite；Disperse chitin modified bentonite in deionized water be configured to it is dense
The suspension that degree is 5%, after stirring 1h, by Ce (NO3)3·6H2O is according to Ce3+Amount for 100mmol/100g sodium bentonite adds
Enter in suspension, adjusts pH of suspension=5, and 4h is continuously stirred with the revolving speed of 600r/min in 40 DEG C of water-baths.Spend again from
Sub- water washing filters 3 times；The cerium bentonite of preparation is placed in drying in 60 DEG C of vacuum oven, then in planetary ball mill
Middle grinding is to 75 μm or less.
The preparation of cerium bentonite modified watersoluble polyurethane paint: cerium bentonite powder is added to by the component proportion
In deionized water, with magnetic stirrer 1h, then disperse 1h in ultrasonic cleaner；The cerium bentonite of preparation is dispersed
Liquid is added in waterborne polyurethane resin under conditions of magnetic agitation by the component proportion, after stirring 2h, by described group of distribution
2h is stirred with the revolving speed of 800r/min again than aziridine crosslinker and other auxiliary agents is added.
Embodiment 2
A kind of cerium bentonite modified watersoluble polyurethane paint, the original of the cerium bentonite modified watersoluble polyurethane paint
Material includes: that anionic water-based aliphaic polyurethane resin WPU3530 is 50% by mass percentage, deionized water
45.25%, cerium bentonite 2.5%, crosslinking agent aziridine SaC-100 is 2%, sodium hexametaphosphate dispersant and defoaming agent diformazan
Base silicone oil auxiliary agent 0.25%.
The bentonitic preparation of ceriumization: weigh 0.1g chitosan be dissolved in 200ml, 5% acetic acid solution in, stir at normal temperature
It mixes reaction 1h, revolving speed 500r/min and prepares chitosan-acetic acid solution；By sodium bentonite according to sodium bentonite and chitosan
Mass ratio is that 1:0.01 is added to chitosan-acetic acid solution, after stirring 2h at normal temperature with the revolving speed of 500r/min, uses deionized water
Washing filters 3 times, obtains chitin modified bentonite；Disperse chitin modified bentonite in deionized water be configured to it is dense
The suspension that degree is 5%, after stirring 1h, by CeCl3·7H2O is according to Ce3+It is added for the amount of 100mmol/100g sodium bentonite
In suspension, pH of suspension=5 are adjusted, and 4h is continuously stirred with the revolving speed of 600r/min in 40 DEG C of water-baths.Deionization is used again
Water washing filters 3 times；The cerium bentonite of preparation is placed in drying in 60 DEG C of vacuum oven, then in planetary ball mill
Grinding is to 75 μm or less.
The preparation of cerium bentonite modified watersoluble polyurethane paint: cerium bentonite powder is added to by the component proportion
In deionized water, with magnetic stirrer 1h, then disperse 1h in ultrasonic cleaner；The cerium bentonite of preparation is dispersed
Liquid is added in waterborne polyurethane resin under conditions of magnetic agitation by the component proportion, after stirring 2h, by described group of distribution
2h is stirred with the revolving speed of 800r/min again than aziridine crosslinker and other auxiliary agents is added.
Implementation result comparison
By coating prepared by the embodiment of the present invention 1 and embodiment 2 and to be not added with ceriumization bentonitic unmodified aqueous poly-
Urethane coating is coated on (the metallic matrix Q235 steel plate is only specific embodiment, is not used to limit this hair on Q235 steel plate
Bright application range), hardness of paint film, HG/T are measured according to reference standard GB/T 6739-2006 paint and varnish pencil method
3344-2012 paint film water absorption rate measuring method, ISO4624-2016 coating and varnish adhesion strength pull open test, GB/T 1733-93 paint
Measurement of film water resistance measuring method and the resistance to neutral salt spray performance of GBT 1771-2007 paint and varnish etc. measures each property of coating
Energy index, test result is as shown in table 1 and Fig. 1-3.
The performance of 1 cerium bentonite modified watersoluble polyurethane coating of table
As known from Table 1: embodiment 1 and coating prepared by embodiment 2 with to be not added with ceriumization bentonitic unmodified aqueous
Polyurethane coating, adhesive force are significantly improved, and improve 4 times or more；
From fig. 1, it can be seen that after coating soaks 192 hours, there are a large amount of bubbles and bright in unmodified aqueous polyurethane coating surface
Aobvious corrosion, and the naked eyes of coating prepared by embodiment 1 and embodiment 2 have no corrosion, show that aqueous polyurethane coating is swollen through ceriumization
Profit soil is modified, and water resistance greatly improves.
As can be seen from Figure 2, after coating is exposed to neutral salt spray 768 hours, unmodified aqueous polyurethane coating surface occurs tight
Heavy corrosion, and embodiment 1 is only corroded at scratch with coating prepared by embodiment 2, shows that aqueous polyurethane coating passes through
After ceriumization is bentonite modified, corrosion resistance is significantly improved.
As can be seen from Figure 3, after aqueous polyurethane coating addition cerium bentonite, coating prepared by embodiment 1 and embodiment 2
Electrochemical corrosion resistant impedance is respectively by original 105Ω·cm-2Increase to 107Ω·cm-2With 108Ω·cm-2, show that ceriumization is swollen
Profit soil can increase the corrosion resistance of aqueous polyurethane coating.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
The variation or simple replacement expected without creative work, should all be included within the scope of the present invention.
Claims (4)
1. a kind of cerium bentonite modified watersoluble polyurethane paint, it is characterised in that: the cerium bentonite modified watersoluble is poly-
Urethane coating, by mass percentage, the waterborne polyurethane resin 30~60%, deionized water 20~50%, cerium swelling
Soil 1~5%, crosslinking agent 1~5%, other auxiliary agents 0.2~2%.
2. cerium bentonite modified watersoluble polyurethane paint according to claim 1, it is characterised in that: the aqueous poly- ammonia
Ester resin selects anionic-aliphatic poly ether type waterborne polyurethane resin, and the crosslinking agent is aziridine, other auxiliary agents
For sodium hexametaphosphate dispersant and defoaming agent dimethicone.
3. cerium bentonite modified watersoluble polyurethane paint according to claim 1 or 2, it is characterised in that: the cerium
For bentonite using sodium bentonite as raw material, soluble cerium salt is modifying agent, will be with the catalyzing hydrolysis aqueous polyurethane function
Ce3+It loads to and is prepared on the pretreated bentonite of chitosan；The bentonitic specific preparation step of ceriumization includes:
(a) a certain amount of chitosan is dissolved in 2~8% acetic acid solution, is stirred to react 0.5~1h, revolving speed at normal temperature
300~600r/min prepares chitosan-acetic acid solution；
It (b) is that 1:0.005~1:0.02 is added to chitosan-second according to sodium bentonite and chitosan mass ratio by sodium bentonite
Acid solution is washed with deionized, filters 2-5 times after stirring 1~3h at normal temperature with the revolving speed of 500~800r/min, removes
Remaining chitosan and acetic acid obtain chitin modified bentonite；
(c) it disperses chitin modified bentonite in and is configured to the suspension that concentration is 5~10% in deionized water, stirring 0.5
After~2h, by soluble cerium salt according to Ce3+It is added in suspension for the amount of 100mmol/100g sodium bentonite, adjusts suspension
PH to 4~6, and 4-6h is continuously stirred with the revolving speed of 500~800r/min in 40~50 DEG C of water-baths, then be washed with deionized water
It washs, filter 2-3 times；
(d) the cerium bentonite of preparation is placed in drying in 50~80 DEG C of vacuum oven, then the grinding in planetary ball mill
To 75 μm or less.
4. a kind of preparation method of cerium bentonite modified watersoluble polyurethane paint according to claim 3, feature exist
In, including following preparation method:
(1) cerium bentonite powder is added in deionized water by the component proportion, with 1~2h of magnetic stirrer, then
Disperse 30~60min in ultrasonic cleaner；
(2) aqueous polyurethane is added by the component proportion under conditions of magnetic agitation in the cerium bentonite dispersion liquid of preparation
In resin, after stirring 1~2h, aziridine crosslinker is added by the component proportion and other auxiliary agents are stirred for 1~3h, revolving speed
600~1000r/min.
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