CN104356792B - Water-based stone nano-protector and preparation method thereof - Google Patents
Water-based stone nano-protector and preparation method thereof Download PDFInfo
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- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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Abstract
The invention discloses a water-based stone nano-protector. The water-based stone nano-protector is prepared from the following components in parts by weight: 70-80 parts of organic silicon modified polyvinyl alcohol dispersion liquid, 3-5 parts of nano-silicon dioxide, 1-3 parts of nano-titanium dioxide and 5-10 parts of emulsifier. The water-based stone nano-protector is a nano-protection material which is good in effective component penetrating quality and better in adhesive force; the nano-protector is capable of protecting the surface and the interior simultaneously and further improving the interaction of the protector with stone, and therefore, the protection performance is comprehensively improved.
Description
Technical field
The present invention relates to stone protector technical field, be specifically related to a kind of nanometer water stone protectant and preparation method thereof.
Background technology
Stone material, as one of conventional construction material, is widely used in various building, but at sunshine, air slaking and acid-rain corrosion etc.
Under the effect of natural cause, stone material can occur pathological changes, decomposition and fragmentation, has a strong impact on stone appearance, in particular for ornamental stone
The facing color of material.The composition that the destroying of stone material is usually in stone material because of with other chemical reaction, composition is lost to make stone material occur
Losing, loose, destruction and physical property reduce, and the especially marble class performance based on carbonate is the most obvious, modal
Example is that the calcium carbonate in marble reacts with the sulfur dioxide in acid rain, carbon dioxide etc., causes stone material gradually air slaking, not
Break and be taken away by the water, form cavity, groove, crack；Can not be taken away by the water then can form hard cortex, and it is tied with former stone material
Structure is different, final occurs soaked coming off, squamous comes off.
Especially as industrial development, nowadays there is the most serious acid rain, the degree of aggravation stone material etch in Some Domestic area.For
This, prior art utilizes stone protectant to be coated in stone surface, and restriction stone material contacts with polluter, to reach waterproof, anti-
The purposes such as oil, acid and alkali-resistance.The kind of stone surface protective agent is a lot, and classification method is not quite similar, and can be divided into by material property: nothing
Machine surface-protective agent and organic surface-protective agent；Can be divided into according to protection method: semipermanent protection and permanent protection；By making
Can be divided into by mechanism: surface filming type and permeable crystallization type, can be divided into by purposes: surface-protective agent, bottom surface protective agent etc..
Existing stone protectant is high due to production cost, uses inconvenience and has the reasons such as toxic and side effects, is badly in need of providing a kind of stone
Material protective agent can overcome above-mentioned many deficiencies, has formula material low cost, and production technology is simple, and no coupling product does not pollute ring
Border, physical and chemical performance is excellent, has wide range of applications and feature easy to use.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides a kind of nanometer water stone material to prevent
Protect agent and preparation method thereof, form overcoat in the inside of stone material and surface, it is possible to realize the waterproof, weather-proof of stone material and anti-soil.
The present invention solves that the technical scheme that problem set forth above is used is:
A kind of nanometer water stone protectant, counts by weight, and it includes following component: organosilicon-modified polyvinyl disperses
Liquid 70-80 part, nano silicon 3-5 part, nano titanium oxide 1-3 part, emulsifying agent 5-10 part.
By such scheme, described emulsifying agent be the one in Span-60, span-80, Tween-60, tween 80, OP-10 or
Several mixture in any proportion.
By such scheme, the solid content of described organosilicon-modified polyvinyl dispersion liquid is 20-40wt% (in terms of mass content).
By such scheme, described organosilicon-modified polyvinyl dispersion liquid is to use alkoxy silane to poly-second in acidic aqueous solution
Enol is modified obtaining.By alkoxysilane-modified polyvinyl alcohol, obtain a kind of nanodispersion system, have stronger
Penetration, the adhesive force of protective agent is higher, thus improves its weatherability and persistency.
By such scheme, described alkoxy silane is MTMS, vinyltrimethoxy silane, phenyl trimethoxy
One or more in base silane, tetramethoxy-silicane mixture in any proportion.
By such scheme, described polyvinyl alcohol weight average molecular weight (Mw) is 5000-50000.
The preparation method of above-mentioned nanometer water stone protectant, comprises the following steps:
1) it is 1:(4-9 by alkoxy silane and polyvinyl alcohol according to mass ratio) it is dissolved in aqueous solvent, and according to polyvinyl alcohol
The 2-8% of quality adds acid, then heats to 80-100 DEG C, reacts 4-6 hour, obtain organic-silicon-modified under conditions of stirring
Polyvinyl alcohol dispersion liquid；Wherein, the amount of described aqueous solvent is so that obtained organosilicon-modified polyvinyl dispersion liquid solid content is
20-40wt%；
2) count by weight, weigh step 1) organosilicon-modified polyvinyl dispersion liquid 70-80 part of preparing, nanometer two
Silicon oxide 3-5 part, nano titanium oxide 1-3 part and emulsifying agent 5-10 part, by nano silicon, nano titanium oxide, breast
Agent joins in organosilicon-modified polyvinyl dispersion liquid, and under room temperature, 1000-3000r/min stirs 20-40min, obtains nanometer
Aqueous stone protectant.
By such scheme, described acid is concentrated sulphuric acid or concentrated hydrochloric acid, and wherein concentrated sulphuric acid concentration is 98%, and concentrated hydrochloric acid concentration is 36-
38%.
Nanometer water stone protectant of the present invention by roller coat, brush, spray or the mode such as immersion is coated in stone material table
Face, infiltrates in stone material micropore or crack, forms protecting film on the surface of stone material and internal capillary top layer, overcomes prior art to exist
Stone surface forms the protecting film of densification, causes the feature blocking stone material micropore, it is ensured that the breathability of stone material.
Compared with prior art, the invention has the beneficial effects as follows:
(1) in the nano stone protectant of the present invention, organosilicon-modified polyvinyl contains hydrophobic alkyl branches, high bond energy, low table
The silicon-oxygen backbone of face energy, it is thus possible to ensure waterproof, weather-proof (acidproof, alkaline-resisting, uvioresistant) performance of anti-dose of stone material, Yi Jikang
Dirt.It addition, the organosilicon modifier alkoxy silane selected by the present invention is polyfunctionality monomer so that organic-silicon-modified poly-second
Enol has more terminal hydroxy group, makes gained nanometer water stone protectant energy preferably and the silicone hydroxyl effect of stone surface, from
And formed and combine higher protecting film.
(2) nano stone protectant of the present invention utilizes the polyvinyl alcohol that good water solubility, solution viscosity are big to react with alkoxy silane,
Obtain the protective agent of aqueous, environmental protective, and organic principle in stone protectant system, inorganic filler (nanometer titanium dioxide can also be improved
Titanium and nano silicon) dispersion stabilization.
(3) intensity after the nano silicon in the stone protectant of the present invention can improve protective agent film forming and toughness；Nano-silica
Change titanium and can effectively suppress the growth of antibacterial under conditions of illumination.
(4) stone protectant of the present invention is nano protecting material, and effective ingredient permeance property is good, adhesive force is higher, can exist simultaneously
Top layer and be internally formed protection, improves protective agent further and interacts with stone material, comprehensively improve barrier propterty.
Detailed description of the invention
Describing the present invention below in conjunction with specific embodiment, the description of this part is only exemplary and explanatory, should not
Protection scope of the present invention is had any restriction effect.
Embodiment 1
A kind of nanometer water stone protectant, counts by weight, and it includes following component: solid content is the organosilicon of 20wt%
Modified polyvinylalcohol dispersion liquid 70 parts, nano silicon 3 parts, nano titanium oxide 1 part, emulsifying agent Span-605 parts.
The preparation method of nanometer water stone protectant described in the present embodiment, comprises the following steps:
1) 10g MTMS and 40g polyvinyl alcohol (Mw=5000) are dissolved in 200g water, add 0.8g
98% concentrated sulphuric acid is also warming up to 80 DEG C, reacts 4h, be cooled to room temperature and obtain the organosilicon that solid content is 20wt% under stirring condition
Modified polyvinylalcohol dispersion liquid；
2) step 1 is weighed) the organosilicon-modified polyvinyl dispersion liquid 70g for preparing, add 3g nano silicon, 1g receives
Rice titanium dioxide, 5g Span-60, at room temperature 1000r/min stirs 20min, obtains nanometer water stone protectant.
Embodiment 2
A kind of nanometer water stone protectant, counts by weight, and it includes following component: solid content is the organosilicon of 40wt%
Modified polyvinylalcohol dispersion liquid 80 parts, nano silicon 5 parts, nano titanium oxide 3 parts, emulsifier op-10 5 parts,
Emulsifying agent Span-605 parts.
The preparation method of nanometer water stone protectant described in the present embodiment, comprises the following steps:
1) 5g MTMS, 5g tetramethoxy-silicane and 90g polyvinyl alcohol (Mw=50000) are dissolved in 150g
In water, add 7.2g 38% concentrated hydrochloric acid and be warming up to 100 DEG C, reacting 6h under stirring condition, be cooled to room temperature and obtain solid content about
Organosilicon-modified polyvinyl dispersion liquid for 40wt%；
2) step 1 is weighed) the organosilicon-modified polyvinyl dispersion liquid 80g for preparing, add 5g nano silicon, 3g receives
Rice titanium dioxide, 5g Span-60 and 5gOP-10, stir 40min under the conditions of room temperature 3000r/min, obtain nanometer water
Stone protectant.
Embodiment 3
A kind of nanometer water stone protectant, counts by weight, and it includes following component: solid content is the organosilicon of 30wt%
Modified polyvinylalcohol dispersion liquid 75 parts, nano silicon 4 parts, nano titanium oxide 2 parts, emulsifying agent span-80 6 parts.
The preparation method of nanometer water stone protectant described in the present embodiment, comprises the following steps:
1) 10g vinyltrimethoxy silane and 50g polyvinyl alcohol (Mw=50000) are dissolved in 140g water, add
2.5g36% concentrated hydrochloric acid is also warming up to 90 DEG C, reacts 6h, be cooled to room temperature and obtain having of solid content about 30% under stirring condition
Machine Si modification polyvinyl alcohol dispersion liquid；
2) step 1 is weighed) the organosilicon-modified polyvinyl dispersion liquid 75g for preparing, add 4g nano silicon, 2g receives
Rice titanium dioxide and 6g span-80, stir 30min under the conditions of room temperature 2000r/min, obtain nanometer water stone protector
Agent.
Embodiment 4
A kind of nanometer water stone protectant, counts by weight, and it includes following component: solid content is the organosilicon of 20wt%
Modified polyvinylalcohol dispersion liquid 70 parts, nano silicon 4 parts, nano titanium oxide 2 parts, emulsifier tween-608 parts.
The preparation method of nanometer water stone protectant described in the present embodiment, comprises the following steps:
1) 10g phenyltrimethoxysila,e and 50g polyvinyl alcohol (Mw=5000) are dissolved in 240g water, add
2.5g98% concentrated sulphuric acid is also warming up to 90 DEG C, under stirring condition react 4h, be cooled to room temperature obtain solid content be 20% organic
Si modification polyvinyl alcohol dispersion liquid；
2) step 1 is weighed) the organosilicon-modified polyvinyl dispersion liquid 70g for preparing, add 4g nano silicon, 2g receives
Rice titanium dioxide and 8g Tween-60, stir 30min under the conditions of room temperature 2000r/min, obtain nanometer water stone protector
Agent.
Embodiment 5
A kind of nanometer water stone protectant, counts by weight, and it includes following component: solid content is the organosilicon of 40wt%
Modified polyvinylalcohol dispersion liquid 80 parts, nano silicon 5 parts, nano titanium oxide 1 part, emulsifier tween-808 parts.
The preparation method of nanometer water stone protectant described in the present embodiment, comprises the following steps:
1) 10g tetramethoxy-silicane and 70g polyvinyl alcohol (Mw=5000) are dissolved in 120g water, add 3.5g98% dense
Sulphuric acid is also warming up to 80 DEG C, reacts 6h, be cooled to room temperature and obtain the organic-silicon-modified poly-second that solid content is 40% under stirring condition
Enol dispersion liquid；
2) step 1 is weighed) the organosilicon-modified polyvinyl dispersion liquid 80g for preparing, add 5g nano silicon, 1g receives
Rice titanium dioxide and 8g tween 80, stir 30min under the conditions of room temperature 2000r/min, obtain nanometer water stone protector
Agent.
The droplet measurement of the nanometer water stone protectant that 1, prepared by embodiment of the present invention 1-6
The nanometer water stone protectant Britain Malvern nanometer laser particle size analyzer preparing embodiment carries out testing graininess, detection
Result see table 1.
Table 1. testing graininess result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Granularity (nm) | 64 | 88 | 75 | 69 | 80 |
From upper table 1 testing result, the particle diameter of the nanometer water stone protectant of embodiment gained all between 60-90nm,
Belong to nano material, there is good permeability and adhesive force, can guarantee that the silicone ingredients of weather-proof anti-soil and inorganic filler (are received
Rice silicon dioxide, nano titanium oxide) effectively penetrate into inside stone material space, improve the phase interaction between protective agent with stone material
With, simultaneously at stone surface be internally formed compact protective layer.
The barrier propterty application test of the nanometer water stone protectant that 2, prepared by embodiment of the present invention 1-6:
Above-described embodiment gained nanometer water protective agent is respectively coated with on marble, and consumption is that every square metre of marble uniformly coats
50g, according to JC/T 973-2005 " architectural decoration lithotome protective agent " standard detection barrier propterty, detects knot in detail
Fruit see table 2.
Table 2. barrier propterty testing result
From upper table 2 testing result, the nanometer water stone protectant of embodiment gained complies fully with building materials rower JC/T 973-
The requirement of the property indices of defined in 2005 " architectural decoration lithotome protective agents ", and water proofing property and anti-pollution
Property belongs to high-class product.It addition, the present invention has been simultaneously introduced alkoxy silane and the nano silicon of high bond energy, thus have
The most acidproof, alkali resistance；The introducing of nano titanium oxide can absorb the growth of the Energy suppression antibacterial of ultraviolet light, thus carries
High ultra-violet resistance；The stone protectant of the present invention is aqueous, introduce water miscible polyvinyl alcohol improve organic principle, filler point
Scattered stability, thus the problem that there is not layering, floating oil, precipitation.
Especially, embodiment 2 water proofing property is high-class product (95%), stain resistance 0 grade, weatherability (ultraviolet acidproof, alkaline-resisting, resistance to)
Preferably, excellent combination property, for preferred embodiment.Relative to other embodiments, the reason of embodiment excellent combination property
It is: the mixture that alkoxy silane is MTMS and tetramethoxy-silicane selected in (1) embodiment 2,
Having hydrophobic alkyl and the monomer of four degrees of functionality, after reaction, the end group of organosilicon-modified polyvinyl is more, energy simultaneously
Preferably and the hydroxyl effect of stone surface, obtain combining the most waterproof, weather-proof, anti-soil overcoat；(2) embodiment 2
Polyvinyl alcohol molecule amount selected by is bigger, ratio is higher so that the dispersion stabilization of the aqueous stone protectant of the present invention is more
Good；(3) mixture that emulsifying agent is Span-60 and OP-10 selected in embodiment 2, dispersion effect is more preferable, can improve product
The dispersing uniformity of inorganic filler and the dispersion stabilization of product in product；(4) the consolidating of organosilicon-modified polyvinyl in embodiment 2
Content, activeness and quietness nano silicon, the antibacterial nano titanium oxide of extinction consumption higher, but for nanometer water stone material prevent
For protecting agent, be not that total effective ingredient is the highest more good, also need to ensure simultaneously its particle diameter in nanometer range, if particle diameter surpasses
Going out the scope (1-100nm) of nano material, will affect the permeance property of product, particle diameter is the least to be easily adsorbed in micropore
Portion, is unfavorable for again polymer film forming, and the particle diameter of embodiment 2 gained nano stone protectant is 88nm, real relative to other
Executing example particle diameter bigger, it is easier to form protecting film, belong to again nano material scope simultaneously, permeability is strong.
Below it is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as the present invention
Protection domain.
Claims (5)
1. a nanometer water stone protectant, it is characterised in that count by weight, it includes following component: organosilicon-modified polyvinyl dispersion liquid 70-80 part, nano silicon 3-5 part, nano titanium oxide 1-3 part, emulsifying agent 5-10 part；
The solid content of described organosilicon-modified polyvinyl dispersion liquid is 20-40wt%, alkoxy silane is used to be modified obtaining to polyvinyl alcohol in acidic aqueous solution, it is 1:(4-9 by alkoxy silane and polyvinyl alcohol according to mass ratio) it is dissolved in aqueous solvent, and add acid according to the 2-8% of polyvinyl alcohol quality, then heat to 80-100 DEG C, react 4-6 hour under conditions of stirring, obtain organosilicon-modified polyvinyl dispersion liquid；Wherein, described polyvinyl alcohol weight average molecular weight is 5000-50000, and described acid is concentrated sulphuric acid or concentrated hydrochloric acid.
A kind of nanometer water stone protectant the most according to claim 1, it is characterised in that described emulsifying agent is the mixture in any proportion of one or more in Span-60, span-80, Tween-60, tween 80, OP-10.
A kind of nanometer water stone protectant the most according to claim 1, it is characterised in that described alkoxy silane is the mixture in any proportion of one or more in MTMS, vinyltrimethoxy silane, phenyltrimethoxysila,e, tetramethoxy-silicane.
4. the preparation method of the nanometer water stone protectant described in claim 1, it is characterised in that it comprises the following steps:
1) it is 1:(4-9 by alkoxy silane and polyvinyl alcohol according to mass ratio) it is dissolved in aqueous solvent, and add acid according to the 2-8% of polyvinyl alcohol quality, then heat to 80-100 DEG C, react 4-6 hour under conditions of stirring, obtain organosilicon-modified polyvinyl dispersion liquid；Wherein, the amount of described aqueous solvent is so that obtained organosilicon-modified polyvinyl dispersion liquid solid content is 20-40wt%；
2) count by weight, weigh organosilicon-modified polyvinyl dispersion liquid 70-80 part, nano silicon 3-5 part, nano titanium oxide 1-3 part and emulsifying agent 5-10 part prepared by step 1), nano silicon, nano titanium oxide, emulsifying agent are joined in organosilicon-modified polyvinyl dispersion liquid, under room temperature, 1000-3000r/min stirs 20-40min, obtains nanometer water stone protectant.
The preparation method of nanometer water stone protectant the most according to claim 4, it is characterised in that described acid is concentrated sulphuric acid or concentrated hydrochloric acid, wherein concentrated sulphuric acid concentration is 98%, and concentrated hydrochloric acid concentration is 36-38%.
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