CN107974108A - Reactive organic hybrid inorganic nano silica finish and its preparation and application - Google Patents
Reactive organic hybrid inorganic nano silica finish and its preparation and application Download PDFInfo
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- CN107974108A CN107974108A CN201711081144.4A CN201711081144A CN107974108A CN 107974108 A CN107974108 A CN 107974108A CN 201711081144 A CN201711081144 A CN 201711081144A CN 107974108 A CN107974108 A CN 107974108A
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- organic hybrid
- inorganic nano
- hybrid inorganic
- nano 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
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Abstract
The present invention provides a kind of reactive organic hybrid inorganic nano silica finish and its preparation and application.The reactive organic hybrid inorganic nano silica finish, it is characterised in that its raw material includes：Nano silicon dioxide aqueous dispersions 20 80% and silane coupling agent 0.1 8%, wherein, in 7.5 10.5, solids content 5% 50%, the silane coupling agent contains hydrophilic radical for the pH value of the nano silicon dioxide aqueous dispersions.The advantage of the present invention is to form one layer of high-hardness, wearable inorganic silicon dioxide coating connected with covalent intermolecular bond in aqueous double-component polyurethane coating surface; and the finishing coat forms one with double-component polyurethane paint film and ply adhesion problem is not present completely, amplitude peak has played the protective effect of inorganic silicon dioxide coating.
Description
Technical field
, can hydridization processing nano silicon dioxide moisture the present invention relates to a kind of using the silane coupling agent with amino group
Dispersion liquid.Inorganic nano silica particles after hydridization is handled have been grafted the group of the amino containing reactive hydrogen, have formd
The nanometer aqueous dispersions of machine inorganic compounding hybrid silica.The organic-inorganic hybrid nanometer silica dispersions can be used as cover
Finishing coat is coated on dual-component polyurethane Drawing board for children paint surface, plays and improves resistance to scribble, cleaning performance and wear-resisting property, improves double
The service life of component polyurethane Drawing board for children paint.This patent belongs to building material field.
Background technology
Drawing board for children paint, as the term suggests be exactly can allow children's low VOC content water-based watercolor pencil on its film with
The coating of the scribble creation of meaning.Being attached to the person's handwriting of the watercolor pencil of its coating surface can easily clean and wiped clean, and can
Scribble and clean repeatedly.The paint also can be as having indoor wall decoration and the Environmental Protective Water-paint of protective effect.
Drawing board for children paint currently on the market mainly has one-component emulsion paint and double-component waterborne polyurethane two types.It is single
The erasability of the water-based watercolor pencil trace of component-type emulsion paint Drawing board for children paint is poor, after only several scribbles and clean cycle i.e.
Lose due washable property.The paint film property of two-component type aqueous polyurethane Drawing board for children paint is far above one-pack type latex
Paint.Drawing board for children paint can substantially meet the requirement of scribble at initial stage and cleaning, but can after hundreds of pictures and clean cycle
Cleaning can also be deteriorated as film coated surface is constantly cleaned friction destruction.
The content of the invention
The object of the present invention is to provide a kind of reactive organic hybrid inorganic nano silica finish, handled through hydridization
Inorganic nano silica particles afterwards have been grafted amino group containing reactive hydrogen, form organo-mineral complexing hybrid material
Nanometer aqueous dispersions, the finish being configured to the aqueous dispersions can be after the construction of aqueous double-component polyurethane Drawing board for children paint
When 4-6 is small, when drawing board paint film has been done solid work but isocyanate curing agent does not react completely, dual-component polyurethane is coated on
Virgin drawing board coating surface.The inorganic nano silica dioxide granule of the amino group containing reactive hydrogen in finish contacts polyurethane immediately
Drawing board for children paint paint film, amino group containing reactive hydrogen are anti-with the isocyanate groups on polyurethane Drawing board for children paint paint film immediately
Should, inorganic nano silica dioxide granule will pass through organically reaction in the form of covalent bond firmly with polyurethane Drawing board for children paint paint
Film forms an entirety so that polyurethane Drawing board for children paint coating surface, which firmly covers one layer, has material as quartz glass
Heavy seal coat (molecular structure of quartz glass is exactly high-purity silicon dioxide).
In order to achieve the above object, the present invention provides a kind of reactive organic hybrid inorganic nano silica cover
Paint, it is characterised in that its raw material includes：Nano silicon dioxide aqueous dispersions 20-80% and silane coupling agent 0.1-8%, its
In, the pH value of the nano silicon dioxide aqueous dispersions is even in 5%-50%, the silane in 7.5-10.5, solids content
Connection agent contains hydrophilic radical.
Preferably, the raw material of the reactive organic hybrid inorganic nano silica finish is by water 10-
78.78%, antifreezing agent 1-10%, nano silicon dioxide aqueous dispersions 20-80%, pH adjusting agent 0.01-1%, silane coupling agent
0.1-8%, defoamer 0.01-0.5% and fungicide 0.1-0.5% are formed.
Preferably, the hydrophilic radical is amino.
Preferably, the silane coupling agent for gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxy diethoxy silane, N- phenyl-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, three ethoxy of 3- (2- aminoethyls)-aminopropyl
Base silane, N- phenylaminomethyls triethoxysilane, double-(γ-trimethoxy silicon propyl group) amine, double (3- triethoxysilylpropyls)
Amine, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane, 3- ureido-propyl trimethoxy silanes, three ethoxy of 3- ureido-propyls
Base silane, vinylbenzylaminoethyl aminopropyl trimethoxysilane, (N, N- dimethyl -3- aminopropyls) trimethoxy silicon
Alkane, 4- amino -3,3- dimethylbutyls trimethoxy silane, γ-divinyl triammonium base propyl trimethoxy silicane, N, N- diethyls
At least one of base -3- aminopropyl trimethoxysilanes and N- (normal-butyl)-γ-aminopropyltrimethoxysilane.
Silane coupling agent citing see the table below in the present invention：
The chemical structural formula of silane coupling agent, which simplifies, is classified as following formula：
Nano silicon dioxide aqueous dispersions in the present invention, translucent liquid, is mainly used for coating, refractory material, weaving
Industry etc., has water-fast, fire resisting, washability, anti-pollution characteristic.Nano silicon dioxide aqueous dispersions are commercially commonly known as silicon
Colloidal sol.The commercially available product for having very more models and specification.As long as pH value all may be used in 7.5-10.5, solids content in 5%-50%
Use.
The middle nanometer silicon dioxide particle chemical structural formula of nano silicon dioxide aqueous dispersions, which simplifies, is illustrated as following formula：
Preferably, the pH adjusting agent be the hydroxide of alkali metal, the carbonate of alkali metal and bicarbonate and
At least one of organic amine compound, organic-silicon-modified pH adjusting agent.
Preferably, the antifreezing agent can be binary or polyalcohol and all can reduce water freezing point material.
Preferably, the defoamer is mineral oil origin and organic silicon type defoamer.
Preferably, the fungicide is water paint in-can preservation agent.
Present invention also offers the preparation method of above-mentioned reactive organic hybrid inorganic nano silica finish, its
It is characterized in that, including：Water, antifreezing agent and nano silicon dioxide moisture is put into successively in reaction vessel under agitation to dissipate
Liquid, input pH adjusting agent adjust pH value to 8.5-10, put into silane coupling agent, and rise temperature is reacted to 65-80 DEG C, is reacted
When maintaining 3-6 small, it is cooled to room temperature, obtains reactive organic hybrid inorganic nano silica finish.
Further, the reaction is carried out in two steps：
The first step：Reaction is hydrolyzed in silane coupling agent, and the by-product methanol for reacting generation exceedes methanol in system temperature
Evaporated after boiling point, reaction system is removed after being collected by condenser；
Second step：The silicone hydroxyl condensation reaction of silane coupling agent and nano-silica surface after hydrolysis, makes inorganic receive
Rice silica surface carries the organic compound ingredient containing reactive hydrogen.Reaction process, which simplifies, is illustrated as following formula：
Present invention also offers the application method of above-mentioned reactive organic hybrid inorganic nano silica finish, its
It is characterized in that, including：Construct first double-component waterborne polyurethane Drawing board for children paint, when dry 4-6 is small under film room temperature；Then will
Reactive organic hybrid inorganic nano silica finish is constructed on previous paint film 2, and twice construction interval time is not
When small more than 1.
Compared with prior art, the beneficial effects of the invention are as follows：
The advantage of the present invention is to form one layer in aqueous double-component polyurethane coating surface to connect with covalent intermolecular bond
High-hardness, wearable inorganic silicon dioxide coating, and the finishing coat formed completely with double-component polyurethane paint film one do not deposit
In ply adhesion problem, amplitude peak has played the protective effect of inorganic silicon dioxide coating.The program is by high-end material at the same time
Material is directly acted on very low organic hybrid inorganic nano silica finish dosage needs high performance film coated surface, tool
There is good cost performance.
Brief description of the drawings
Fig. 1 is reactive organic hybrid inorganic nano silica finish reaction equation.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Each percentage in the present invention, unless otherwise specified, is weight percentage.
Each ratio in the present invention, is weight ratio unless otherwise specified.
Embodiment 1
A kind of reactivity organic hybrid inorganic nano silica finish, its raw material is by water 78.78%, antifreezing agent 1%,
Nano silicon dioxide aqueous dispersions 20%, pH adjusting agent 0.01%, silane coupling agent 0.1%, defoamer 0.01% and sterilization
Agent 0.1% forms.
The silane coupling agent uses N- β-(aminoethyl)-γ-aminopropyl trimethoxy of Dow corning company production
Base silane coupling agent.Nano silicon dioxide aqueous dispersions dissipate for the NALCO1030 nano silicon dioxide moisture of NALCO companies of the U.S.
Liquid, pH value 8.5, solids content are 30 ± 1%.Antifreezing agent is propane diols, pH adjusting agent is BS-198 (Wacker), defoamer
It is Dow 631 for BYK 028 and fungicide.
The preparation method of above-mentioned reactive organic hybrid inorganic nano silica finish, concretely comprises the following steps：
Put into water, antifreezing agent and nano silicon dioxide aqueous dispersions successively in reaction vessel under agitation, put into
PH adjusting agent adjusts pH value to 8.5, puts into silane coupling agent, and rise temperature is reacted to 70 DEG C, reaction maintain 2 it is small when, it is cold
But to room temperature, put into defoamer and fungicide obtains reactive organic hybrid inorganic nano silica finish.
The application process of reactive organic hybrid inorganic nano silica finish is：
Construct double-component waterborne polyurethane Drawing board for children paint (German crocodile paint Drawing board for children paint), done under film room temperature first
When dry 4-6 is small.The film of double-component waterborne polyurethane Drawing board for children paint has had certain intensity at this time while coating surface is also
Possess substantial amounts of unreacted NCO isocyanate groups.
Then reactive organic hybrid inorganic nano silica finish is constructed on previous paint film 2, twice
When construction interval time is small no more than 1.Since the reaction speed of NH groups and NCO group is very fast, paint film during finish surface drying
The reaction on surface has been completed, and reaction equation is as shown in Figure 1.
Coating surface pencil hardness is H after final paint film conserves 7 days, and without the former coating surface of product cover of the present invention
Pencil hardness is F.
Embodiment 2
Similar to embodiment 1, difference lies in the raw material of reactive organic hybrid inorganic nano silica finish is by water
30%, antifreezing agent 10%, nano silicon dioxide aqueous dispersions 50%, pH adjusting agent 1%, silane coupling agent 8%, defoamer
0.5% and fungicide 0.5% form.
Cover is only needed to can reach the performance of example 1 together.
Claims (8)
1. a kind of reactivity organic hybrid inorganic nano silica finish, it is characterised in that its raw material is by water 10-
78.78%, antifreezing agent 1-10%, nano silicon dioxide aqueous dispersions 20-80%, pH adjusting agent 0.01-1%, silane coupling agent
0.1-8%, defoamer 0.01-0.5% and fungicide 0.1-0.5% are formed, wherein, the nano silicon dioxide moisture dissipates
The pH value of liquid contains hydrophilic radical in 7.5-10.5, solids content in 5%-50%, the silane coupling agent.
2. reactivity organic hybrid inorganic nano silica finish as claimed in claim 1, it is characterised in that described
Silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy
Silane, N- phenyl-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- β-
(aminoethyl)-γ-aminopropyltrimethoxysilane, 3- (2- aminoethyls)-aminopropyl triethoxysilane, N- phenylaminomethyls three
Ethoxysilane, double-(γ-trimethoxy silicon propyl group) amine, double (3- triethoxysilylpropyls) amine, N- cyclohexyl-γ-aminopropyl
Methyl dimethoxysilane, 3- ureido-propyl trimethoxy silanes, 3- ureidopropyltriethoxysilanes, vinyl-benzylamino
Ethylaminopropyl trimethoxy silane, (N, N- dimethyl -3- aminopropyls) trimethoxy silane, 4- amino -3,3- dimethyl butyrates
Base trimethoxy silane, γ-divinyl triammonium base propyl trimethoxy silicane, N, N- diethyl -3- aminopropyl trimethoxy silicon
Alkane and N- (normal-butyl)-γ-aminopropyltrimethoxysilane.
3. reactivity organic hybrid inorganic nano silica finish as claimed in claim 1, it is characterised in that described
PH adjusting agent is the hydroxide of alkali metal, at least one in the carbonate of alkali metal and bicarbonate and organic amine compound
Kind.
4. reactivity organic hybrid inorganic nano silica finish as claimed in claim 1, it is characterised in that described
Antifreezing agent is binary or polyalcohol and the material of other freezing points for reducing water.
5. reactivity organic hybrid inorganic nano silica finish as claimed in claim 1, it is characterised in that described
Defoamer is mineral oil origin and organic silicon type defoamer.
6. reactivity organic hybrid inorganic nano silica finish as claimed in claim 1, it is characterised in that described
Fungicide is water paint in-can preservation agent.
7. the preparation side of the reactive organic hybrid inorganic nano silica finish any one of claim 1-6
Method, it is characterised in that including：Put into water, antifreezing agent and nano silicon dioxide water successively in reaction vessel under agitation
Dispersion liquid, input pH adjusting agent adjust pH value to 8.5-10, put into silane coupling agent, and rise temperature is reacted to 65-80 DEG C,
When reaction maintains 3-6 small, it is cooled to room temperature, puts into defoamer and fungicide obtains reactive organic hybrid inorganic nano titanium dioxide
Silicone mask finishing coat.
8. the user of the reactive organic hybrid inorganic nano silica finish any one of claim 1-6
Method, it is characterised in that including：Construct first double-component waterborne polyurethane Drawing board for children paint, when dry 4-6 is small under film room temperature；
Then reactive organic hybrid inorganic nano silica finish is constructed on previous paint film 2, twice construction is spaced
When time is small no more than 1.
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| CN201711081144.4A CN107974108A (en) | 2017-11-06 | 2017-11-06 | Reactive organic hybrid inorganic nano silica finish and its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711081144.4A CN107974108A (en) | 2017-11-06 | 2017-11-06 | Reactive organic hybrid inorganic nano silica finish and its preparation and application |
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| CN107974108A true CN107974108A (en) | 2018-05-01 |
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| CN201711081144.4A Pending CN107974108A (en) | 2017-11-06 | 2017-11-06 | Reactive organic hybrid inorganic nano silica finish and its preparation and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110746824A (en) * | 2019-09-17 | 2020-02-04 | 鳄鱼制漆(上海)有限公司 | Inorganic nano-silica hybrid bio-based acrylic acid exterior wall coating and preparation method and application thereof |
| CN110746825A (en) * | 2019-09-17 | 2020-02-04 | 鳄鱼制漆(上海)有限公司 | Inorganic nano silicon dioxide hybrid bio-based acrylic emulsion finish paint and preparation method and application thereof |
| CN113372814A (en) * | 2021-05-27 | 2021-09-10 | 广州一新科技有限公司 | Cage-shaped polysilsesquioxane-based super-hydrophilic functional coating and preparation method thereof |
| CN114350262A (en) * | 2022-03-21 | 2022-04-15 | 广东简一(集团)陶瓷有限公司 | Bactericidal and antiviral super-wear-resistant organic silicon coating liquid and preparation method thereof, and organic silicon coating and preparation method thereof |
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Patent Citations (1)
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| CN106398333A (en) * | 2016-09-10 | 2017-02-15 | 上海大学 | Preparation method of nano sol hybrid polysiloxane magnesium alloy surface preservative |
Non-Patent Citations (1)
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| 包彦堃等: "《熔模精密铸造技术》", 31 August 2012, 浙江大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746824A (en) * | 2019-09-17 | 2020-02-04 | 鳄鱼制漆(上海)有限公司 | Inorganic nano-silica hybrid bio-based acrylic acid exterior wall coating and preparation method and application thereof |
| CN110746825A (en) * | 2019-09-17 | 2020-02-04 | 鳄鱼制漆(上海)有限公司 | Inorganic nano silicon dioxide hybrid bio-based acrylic emulsion finish paint and preparation method and application thereof |
| CN113372814A (en) * | 2021-05-27 | 2021-09-10 | 广州一新科技有限公司 | Cage-shaped polysilsesquioxane-based super-hydrophilic functional coating and preparation method thereof |
| CN114350262A (en) * | 2022-03-21 | 2022-04-15 | 广东简一(集团)陶瓷有限公司 | Bactericidal and antiviral super-wear-resistant organic silicon coating liquid and preparation method thereof, and organic silicon coating and preparation method thereof |
| CN114350262B (en) * | 2022-03-21 | 2022-05-17 | 广东简一(集团)陶瓷有限公司 | Bactericidal and antiviral super-wear-resistant organic silicon coating liquid and preparation method thereof, and organic silicon coating and preparation method thereof |
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