CN106750355A - A kind of nano silicon water alcohol acid hybrid resin and preparation method - Google Patents
A kind of nano silicon water alcohol acid hybrid resin and preparation method Download PDFInfo
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- CN106750355A CN106750355A CN201611152513.XA CN201611152513A CN106750355A CN 106750355 A CN106750355 A CN 106750355A CN 201611152513 A CN201611152513 A CN 201611152513A CN 106750355 A CN106750355 A CN 106750355A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention belongs to water paint field, a kind of nano silicon water alcohol acid hybrid resin and preparation method are particularly related to, nano silicon water alcohol acid hybrid resin is obtained by the raw material of following weight：20 70 parts of water silica sol；0 25 parts of deionized water；560 26 51.5 parts of KH；98.5 99.5 parts of aqueous alkide resin；0.01 0.03 parts of catalyst.The present invention prepares aqueous alkide resin/nano silicon dioxide hybridization resin by sol-gal process, the present invention carries out surface modification to resin and Nano silica sol respectively by same dressing agent, make both compatibilities more preferable, obtain nano-particle finely dispersed composite coating in paint film, therefore improve the antiseptic effect of paint film, the coating salt fog time is compared with alkyd resin up to 4 times of raising, it is adaptable to which anticorrosion of steel structure can coordinate rust resisting pigment to prepare Water-based alkyd anti-corrosive paint.
Description
Technical field
The invention belongs to water paint field, a kind of nano silicon-water alcohol acid hybrid resin and system are particularly related to
Preparation Method.
Background technology
Water alcohol acid coating has pliability excellent because of it, one-component easy construction, the advantages of low VOC and low flame spread and general
All over suitable for the protection of indoor steel construction and inner cabin of ship.However, due to water paint generally existing poor water resistance, corrosion-resistant
The features such as ability is weak, thus limit its range of application.
To improve the antiseptic property of coating, nano material can be used.Inorganic nano material has that size is small, specific surface area is big
The characteristics of, when being applied to coating, the gap of the filler in paint film is smaller, therefore improves shielding effect of the coating to corrosive medium
Rate.Someone adds nano silicon in aqueous epoxy coating, improves the antiseptic effect of coating.Also someone is by CNT
Be added to aqueous acrylamide it is acid coated in, find coating antiseptic property increase.However, nano material powder has dispersion being stranded
It is difficult, the characteristics of easily reunite in coating, therefore above two is modified and is both needed in the special dispersing technology condition such as ultrasound or ball milling
Lower section is capable of achieving, range of application and application effect which has limited nano material in coating.
To solve the above problems, currently available technology is modified typically by way of preparing hybrid inorganic-organic particle and sets
Fat.Someone by KH-560 modified silicon dioxide sols, and by sol-gal process by itself and the epoxy for being dissolved in toluene/n-butanol
Resin is mutually crosslinked, and obtains hybrid resin antiseptic property and improves；Also someone passes through situ aggregation method by acrylic compounds list
Body is polymerized on nano titanium oxide, obtaining nano titanium oxide-acrylic acid hybridisation resin.And currently in alkyd resin
Hybrid modification is there is not yet open.
The content of the invention
In order to solve the above-mentioned shortcoming and defect mentioned in the prior art, the present invention provides a kind of nanometer of favorable anti-corrosion effect
Silicon dioxide-aqueous alkyd hybrid resin and preparation method thereof.The present invention modifies alkyd resin by KH-560 epoxy ring-openings,
KH-560 modified Nano Ludox is used simultaneously, and hybrid resin is prepared finally by sol-gel process.Due to using while having
The material of the same race (i.e. KH-560) of epoxy radicals and silicon oxygen bond to alkyd resin and silica sol modified, makes both intermiscibilities good respectively,
The technical barrier of nano-powder difficulties in dispersion is solved, the hybrid resin of favorable anti-corrosion effect has been obtained.
The present invention is adopted the following technical scheme that：
A kind of nano silicon-water alcohol acid hybrid resin, its structural formula is：
Further, it is obtained by the raw material of following weight：
Further, it is obtained by the raw material of following weight：
The present invention also provides a kind of preparation method of above-mentioned nano silicon-water alcohol acid hybrid resin, including：
S1, modified silicasol is prepared, specifically included：20-70 parts of water silica sol pH value is adjusted to acidic catalyst first
The scope of 1-5, then 0-25 parts of deionized water and 25-50 parts of KH-560, stirring reaction 6-12h are added thereto to, obtain modified silicon
Colloidal sol, reuses alkali and the pH value of modified silicasol is adjusted into 6-8；
S2, alkyd surface modification, specifically include：98.5-99 parts of aqueous alkide resin is taken, under nitrogen protection, is risen
Temperature is subsequently added 1-1.5 parts of KH-560 and 0.01-0.03 parts of catalyst to 120-140 DEG C, and stirring reaction 1-3h is cooled to room
Wen Hou, adds alkali regulation pH to 6-8；
Prepared by S3, nano silicon-water alcohol acid hybrid resin, specifically include：Under stirring, to modified silicasol
Middle dropwise addition alkyd resin, time for adding is 2-3h, continues thereafter with stirring reaction 6-10h, obtains final product nano silicon-water alcohol acid
Hybrid resin.
Further, in step S1, dioxide-containing silica is 20%-50% in the water silica sol, and particle diameter is 10nm-
100nm, pH are 1-11.
Further, in step S1, the acidic catalyst is selected from the one kind or many in hydrochloric acid, nitric acid, formic acid, acetic acid
Kind.
Further, in step S1 and S2, the alkali is selected from ammoniacal liquor, triethylamine, AMP-95, N, N- dimethylethanolamines
One or more.
Further, in step S2, the solid content of the aqueous alkide resin is 65%-90%, and acid number is 40-
80mgKOH/g。
Further, in step S2, the catalyst is selected from triethylamine, tetrabutylammonium chloride or trimethyl chlorine
Change ammonium one or more.
It is by sol-gel process system the invention provides a kind of nano silicon-water alcohol acid hybrid resin
It is standby, i.e., respectively to aqueous alkide resin and nano silicon dioxide sol surface modification, then by the alkyd tree after surface modification
Fat drips are added in nano silicon, obtain the stabilising dispersions that alkyd resin coats nano silicon dioxide particles.From one kind
There is the coating material KH560 of silicon oxygen bond and epoxy three-membered ring structures simultaneously, wherein, silicon oxygen bond is easily anti-with nano silicon
Should, epoxy three-membered ring structures then easily react with carboxyl structure in aqueous alkide resin.By this dressing agent respectively to resin and
Nano silicon dioxide sol surface modification, makes both compatibilities more preferably, and nano-particle can be dispersed in resin, it is to avoid receives
Ground rice body is difficult the situation disperseed and reunite in resin, therefore improves the antiseptic effect of paint film, when making varnish paint film salt fog
Between can extend 4 times.Nano silicon of the present invention-water alcohol acid hybrid resin, it is adaptable to which the steel construction of specific demand is prevented
Corruption can coordinate rust resisting pigment to prepare Water-based alkyd anti-corrosive paint.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, without having to pay creative labor, can be with root
Other accompanying drawings are obtained according to these accompanying drawings.
A kind of structural formula of nano silicon-water alcohol acid hybrid resin that Fig. 1 is provided for the present invention；
Nano silicon-water alcohol acid hybrid resin scanning electron microscope (SEM) photograph that Fig. 2 is provided for the present invention；
Existing nano silicon scattered scanning electron microscope (SEM) photograph in aqueous alkide resin in Fig. 3.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
With reference to embodiment, the present invention is further described, and specific embodiment (is matched somebody with somebody by following weight portion as shown in table 1
The raw material of ratio is obtained)：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Water silica sol (SiO2Content 20%) | 70 | - | - | - |
| Water silica sol (SiO2Content 30%) | - | 60 | - | |
| Water silica sol (SiO2Content 40%) | - | - | 50 | - |
| Water silica sol (SiO2Content 50%) | - | - | 25 | |
| Deionized water | 5 | 7 | 6 | 25 |
| KH-560 | 26 | 34.5 | 44.5 | 50.8 |
| Aqueous alkide resin | 99 | 98.5 | 99.5 | 99.2 |
The preparation method of embodiment 1 includes：
S1, modified silicasol step is prepared, including first with acidic catalyst hydrochloric acid by SiO270 parts of content 20% are aqueous
Ludox (particle diameter is 10nm) pH value is adjusted to 2 scope, then is added thereto to 5 parts of deionized waters and 25 parts of KH-560, and stirring is anti-
6h is answered, modified silicasol is obtained, triethylamine is reused and the pH value of modified silicasol is adjusted to 6；
S2, alkyd surface modification, including：Take 99 parts of aqueous alkide resin (solid contents of the aqueous alkide resin
It is 65%, acid number is 40mgKOH/g), under nitrogen protection, 120-140 DEG C is warming up to, it is subsequently added 1 part of KH-560 and 0.01
Part tetrabutylammonium chloride, stirring reaction 1h after being cooled to room temperature, adds alkali to adjust pH value to 6；
It is prepared by S3, nano silicon-water alcohol acid hybrid resin, including：It is molten to modified silicon in 2h under stirring
In alkyd resin is slowly added dropwise in glue, stirring reaction 7h is continued thereafter with, obtain nano silicon-water alcohol acid hybrid resin.
The preparation method of embodiment 2 includes：
S1, modified silicasol step is prepared, including first with acidic catalyst nitric acid by SiO260 parts of content 30% are aqueous
Ludox (particle diameter is 50nm) pH value is adjusted to 5 scope, then is added thereto to 7 parts of deionized waters and 33 parts of KH-560, and stirring is anti-
8h is answered, modified silicasol is obtained, ammoniacal liquor is reused and the pH value of modified silicasol is adjusted to 7；
S2, alkyd surface modification, including：(the solid of the aqueous alkide resin contains to take 98.5 parts of aqueous alkide resins
It is 85% to measure, and acid number is 60mgKOH/g), under nitrogen protection, be warming up to 120-140 DEG C, be subsequently added 1.5 parts of KH-560 and
0.02 part of DTAC, stirring reaction 2h after being cooled to room temperature, adds alkali to adjust pH value to 7；
It is prepared by S3, nano silicon-water alcohol acid hybrid resin, including：It is molten to modified silicon in 3h under stirring
In alkyd resin is slowly added dropwise in glue, stirring reaction 10h is continued thereafter with, obtain nano silicon-water alcohol acid hybrid resin.
The preparation method of embodiment 3 includes：
S1, modified silicasol step is prepared, including first with acidic catalyst formic acid by SiO250 parts of content 50% are aqueous
Ludox (particle diameter is 100nm) pH value is adjusted to 6 scope, then is added thereto to 6 parts of deionized waters and 44 parts of KH-560, and stirring is anti-
10h is answered, modified silicasol is obtained, N is reused, the pH value of modified silicasol is adjusted to 7 by N- dimethylethanolamines；
S2, alkyd surface modification, including：(the solid of the aqueous alkide resin contains to take 99.5 parts of aqueous alkide resins
It is 90% to measure, and acid number is 80mgKOH/g), under nitrogen protection, be warming up to 120-140 DEG C, be subsequently added 0.5 part of KH-560 and
0.03 part of tetrabutylammonium chloride, stirring reaction 3h after being cooled to room temperature, adds N, N- dimethylethanolamines regulation pH to 7；
It is prepared by S3, nano silicon-water alcohol acid hybrid resin, including：It is molten to modified silicon in 3h under stirring
In alkyd resin is added dropwise in glue, stirring reaction 9h is continued thereafter with, obtain nano silicon-water alcohol acid hybrid resin.
The preparation method of embodiment 4 includes：
S1, modified silicasol step is prepared, including first with acidic catalyst acetic acid by SiO225 parts of content 50% are aqueous
Ludox (particle diameter is 100nm) pH value is adjusted to 6 scope, then is added thereto to 25 parts of deionized waters and 50 parts of KH-560, stirring
Reaction 12h, obtains modified silicasol, reuses AMP-95 and the pH value of modified silicasol is adjusted into 7；
S2, alkyd surface modification, including：(the solid of the aqueous alkide resin contains to take 99.2 parts of aqueous alkide resins
It is 90% to measure, and acid number is 80mgKOH/g), under nitrogen protection, be warming up to 120-140 DEG C, be subsequently added 0.8 part of KH-560 and
0.03 part of triethylamine, stirring reaction 3h after being cooled to room temperature, adds AMP-95 regulations pH to 7；
It is prepared by S3, nano silicon-water alcohol acid hybrid resin, including：It is molten to modified silicon in 2h under stirring
In alkyd resin is slowly added dropwise in glue, stirring reaction 10h is continued thereafter with, obtain nano silicon-water alcohol acid hybrid resin.
The performance comparison of above-mentioned 4 embodiment and aqueous alkide resin is as shown in table 2：
Table 2
Be can be seen that from upper table, the water proofing property of nano silicon of the invention-more existing resin of water alcohol acid hybrid resin
Energy, salt spray resistance are greatly improved.The present invention by solving nano material scattering problem in aqueous coating system, preferably
To solve water paint film forming uneven, the problems such as to corrosive medium shielding difference.The nano-silica that Fig. 2 is provided for the present invention
SiClx-water alcohol acid hybrid resin scanning electron microscope (SEM) photograph, nano silicon is scattered in aqueous alkide resin in comparison diagram 3 sweeps
Electron microscope (there is obvious agglomeration) is retouched, the fact that nano silicon is uniformly dispersed in resin has been also further demonstrated that.
Finally it should be noted that various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
Pipe has been described in detail with reference to foregoing embodiments to the present invention, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of nano silicon-water alcohol acid hybrid resin, it is characterised in that its structural formula is：
2. nano silicon according to claim 1-water alcohol acid hybrid resin, it is characterised in that by following weight
The raw material of part proportioning is obtained：
3. nano silicon according to claim 2-water alcohol acid hybrid resin, it is characterised in that by following weight
The raw material of part proportioning is obtained：
4. the preparation method of the nano silicon described in a kind of claim 2-water alcohol acid hybrid resin, it is characterised in that
Including：
S1, modified silicasol is prepared, specifically included：20-70 parts of water silica sol pH value is first adjusted to 1-5's with acidic catalyst
Scope, then 0-25 parts of deionized water and 25-50 parts of KH-560, stirring reaction 6-12h are added thereto to, modified silicasol is obtained,
Reuse alkali and the pH value of modified silicasol is adjusted to 6-8；
S2, alkyd surface modification, specifically include：98.5-99 parts of aqueous alkide resin is taken, under nitrogen protection, is warming up to
120-140 DEG C, it is subsequently added 1-1.5 parts of KH-560 and 0.01-0.03 parts of catalyst, stirring reaction 1-3h, after being cooled to room temperature,
Add alkali regulation pH to 6-8；
Prepared by S3, nano silicon-water alcohol acid hybrid resin, specifically include：Under stirring, dripped in modified silicasol
Plus alkyd resin, time for adding is 2-3h, continues thereafter with stirring reaction 6-10h, obtains final product nano silicon-water alcohol acid hydridization
Resin.
5. preparation method according to claim 4, it is characterised in that in step S1, titanium dioxide in the water silica sol
Silicone content is 20%-50%, and particle diameter is 10nm-100nm, and pH is 1-11.
6. preparation method according to claim 4, it is characterised in that in step S1, the acidic catalyst be selected from hydrochloric acid,
One or more in nitric acid, formic acid, acetic acid.
7. preparation method according to claim 4, it is characterised in that in step S1 and S2, the alkali is selected from ammoniacal liquor, three second
Amine, AMP-95, N, one or more of N- dimethylethanolamines.
8. preparation method according to claim 4, it is characterised in that in step S2, the solid of the aqueous alkide resin contains
It is 65%-90% to measure, and acid number is 40-80mgKOH/g.
9. preparation method according to claim 4, it is characterised in that in step S2, the catalyst is selected from triethylamine, four
One or more of butyl ammonium chloride or DTAC.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020056628A1 (en) * | 2018-09-18 | 2020-03-26 | 周连惠 | Aqueous nano porcelain imitating coating and preparation method therefor |
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| CN102989652A (en) * | 2012-11-16 | 2013-03-27 | 国家电网公司 | Method for manufacturing high-corrosion high-strength power transmission tower steel plate |
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2016
- 2016-12-14 CN CN201611152513.XA patent/CN106750355A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989652A (en) * | 2012-11-16 | 2013-03-27 | 国家电网公司 | Method for manufacturing high-corrosion high-strength power transmission tower steel plate |
Non-Patent Citations (2)
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| 周志文: "硅溶胶改性环氧树脂复合乳液的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王华林，等: "疏水型醇酸树脂/SiO2有机无机杂化材料的制备与性能", 《高分子材料科学与工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020056628A1 (en) * | 2018-09-18 | 2020-03-26 | 周连惠 | Aqueous nano porcelain imitating coating and preparation method therefor |
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