CN106749856A - Ludox and preparation method thereof, acrylic resin, acrylic acid double-component polyurethane coating - Google Patents
Ludox and preparation method thereof, acrylic resin, acrylic acid double-component polyurethane coating Download PDFInfo
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- CN106749856A CN106749856A CN201611205658.1A CN201611205658A CN106749856A CN 106749856 A CN106749856 A CN 106749856A CN 201611205658 A CN201611205658 A CN 201611205658A CN 106749856 A CN106749856 A CN 106749856A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- 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
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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
- 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
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Abstract
The present invention provides a kind of Ludox and preparation method thereof, acrylic resin, acrylic acid dual-component polyurethane and applies.For solving the problems, such as the aspect poor performances such as hardness, wearability, impact resistance, adhesive force that existing acrylic acid double-component polyurethane coating is present, the present invention provides a kind of Ludox and preparation method thereof, comprises the following steps：Step 1) tetraethyl orthosilicate and absolute ethyl alcohol are reacted in acid condition, form intermediate reaction liquid；Step 2) by absolute ethyl alcohol and silane coupler, (γ (methacryloxypropyl) propyl trimethoxy silicane is reacted in adding described intermediate reaction liquid, and ageing obtains Ludox.And above-mentioned Ludox is used for the modified of acrylic resin, and modified acrylic resin is applied to acrylic acid double-component polyurethane coating, obtain in the excellent acrylic acid double-component polyurethane coating containing silica sol modified acrylic resin of hardness, wearability, impact resistance, adhesion performance.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of Ludox and preparation method thereof, acrylic resin, third
Olefin(e) acid double-component polyurethane coating.
Background technology
Acrylic resin is the macromolecular material that a kind of cementability is strong, film forming is high, with excellent film forming, good
Oil resistivity and weatherability, excellent adhesiveness, very strong adhesive force is respectively provided with to polarity and apolar surfaces, with normal temperature self-drying
The characteristics of, and raw material sources are abundant, produce easy to implement.But acrylic resin structure is generally chain linear structure, to temperature
Degree is extremely sensitive, just can gradually soften as temperature rises, become sticky；In addition, film formed by acrylic resin is intolerant to organic molten
The effect of agent, film can occur Swelling in the presence of organic solvent, cause coating shedding.Acrylic resin is changed
Property, its main purpose is the shortcoming for overcoming acrylic resin " hot sticky cold crisp ", not organic solvent-resistant, improves its vitrifying temperature
Degree.
By polysiloxanes and acrylic ester grafted copolymerization, can significantly reduce the cruel surface tension of polyacrylic acid, water imbibition,
Resistance to soiling, and improve its resistant of high or low temperature.It is direct using double bond containing organosilicon polysiloxane monomer and acrylic ester monomer
Carry out combined polymerization, on main polymer chain introduce siloxanes be obtained Stability Analysis of Structures can ambient cross-linking organosilicon acrylic resin.Organosilicon changes
Property acrylic resin modification by copolymerization, be substantially introducing silicon side chain in carbochain, form grafting, block or interpenetrating network system, reach
To the new material with the two excellent properties.Silica sol modified acrylic resin can be effectively combined organosilicon polymer
With the respective advantage of acrylic resin, its product has been widely used in the industries such as coating, adhesive, leather, weaving, papermaking.
In the research that polyfunctional group organosilicon function monomer is extremely modified to acrylic acid, mainly use containing vinyl
The organosilicon function monomer or performed polymer of functional group carry out emulsion copolymerization with acrylic ester monomer.Come from domestic and international present Research
See, remain in some problems:Such as due to the presence for having water in emulsion polymerization, there is the hydrolysis-condensation reaction of alkoxy, serious shadow
The stabilization for ringing emulsion polymerization is carried out；Because there is huge difference on molecular structure and polarity in organosiloxane and acrylate
Away from, can occur different degrees of phase separation because of consistency problem, the selection to comonomer is relatively difficult etc..
Acrylic resin has the advantages that color is shallow, transparency is high, gloss retention good, corrosion resistance, adhesive force are strong, tough and tensile.But
It is, due to temperature tolerance, water resistance, the poor air permeability of acrylic resin, to limit its application.
The content of the invention
The used technical scheme that solves the above problems is a kind of Ludox and preparation method thereof, acrylic resin, propylene
Sour double-component polyurethane coating.
The present invention provides a kind of preparation method of Ludox, comprises the following steps：
Step 1) tetraethyl orthosilicate and absolute ethyl alcohol are reacted in acid condition, form intermediate reaction liquid；
Step 2) by absolute ethyl alcohol and silane coupler, (γ-(methacryloxypropyl) propyl trimethoxy silicane adds institute
Reacted in the intermediate reaction liquid stated, ageing obtains Ludox.
Preferably, the step 1) in, the mass ratio of tetraethyl orthosilicate and absolute ethyl alcohol is 1：(1-1.28).
Preferably, the step 1) in reaction temperature be 30-40 DEG C, the reaction time be 1-1.5 hours.
Preferably, the step 2) in, absolute ethyl alcohol and silane coupler (γ-(methacryloxypropyl) propyl group trimethoxy
The mass ratio of base silane is (0.29-0.37)：1.
Preferably, the step 2) in the silane coupler (addition of γ-(methacryloxypropyl) propyl trimethoxy silicane
To be added dropwise, time for adding is 30-40min to mode.
Preferably, the step 2) in reaction temperature be 50-60 DEG C, the reaction time be 3-4 hours；Digestion time is 3-4
My god.
The present invention also provides a kind of Ludox, is prepared using the preparation method of above-mentioned Ludox.
The present invention also provides a kind of acrylic resin, is to use for raw material monomer and Ludox to carry out mixed and modified preparation
, wherein, the Ludox accounts for the 10-12% of described raw material monomer quality by percentage to the quality.
The present invention also provides a kind of acrylic acid double-component polyurethane coating, including above-mentioned acrylic resin.
The present invention provides a kind of Ludox and preparation method thereof, acrylic resin, acrylic acid double-component polyurethane coating, bag
Acrylic acid double-component polyurethane coating containing silica sol modified acrylic resin is in hardness, wearability, impact resistance, attachment
Power aspect is all more excellent, has reached the requirement of national standard；Meanwhile, some aspect of performances are better than not containing silica sol modified
The acrylic acid double-component polyurethane coating of acrylic resin.
Be introduced into inorganic silica sol in organic solution by the present invention, improves the coating performance of coating, olefin(e) acid of the invention
Double-component polyurethane coating has that mixing is easy, and easy construction, comprehensive physical mechanical performance is excellent, with prominent extra-weather-proof
Property, wearability, temperature tolerance, water resistance, oil resistivity and resistant to chemical media, improve production efficiency.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, with reference to specific embodiment to this
Invention is described in further detail.
Embodiment 1
182g tetraethyl orthosilicates (TEOS), 146g absolute ethyl alcohols are added in there-necked flask, 35 DEG C of oil bath stirs,
A drop hydrochloric acid is added, 1h is reacted, is further continued for adding 73g absolute ethyl alcohols, 218g silane couplers (γ-(methyl is then added dropwise
Acryloyl-oxy) propyl trimethoxy silicane, KH570), time for adding 35min is warmed up to 50 DEG C of back flow reaction 3h, most after dripping off
Room temperature is aged 3 days afterwards, obtains final product Ludox.
Embodiment 2
189g tetraethyl orthosilicates (TEOS), 180g absolute ethyl alcohols are added in there-necked flask, 40 DEG C of oil bath stirs,
A drop hydrochloric acid is added, 1.5h is reacted, is further continued for adding 90g absolute ethyl alcohols, 240g silane couplers (γ-(methyl is then added dropwise
Acryloyl-oxy) propyl trimethoxy silicane, KH570), time for adding 35min is warmed up to 60 DEG C of back flow reaction 3.5h after dripping off,
Last room temperature is aged 4 days, obtains final product Ludox.
Embodiment 3
218g tetraethyl orthosilicates (TEOS), 170g absolute ethyl alcohols are added in there-necked flask, 35 DEG C of oil bath stirs,
A drop hydrochloric acid is added, 1h is reacted, is further continued for adding 85g absolute ethyl alcohols, 290g silane couplers (γ-(methyl-prop is then added dropwise
Alkene acyl-oxygen) propyl trimethoxy silicane, KH570), time for adding 40min is warmed up to 55 DEG C of back flow reaction 4h, finally after dripping off
Room temperature is aged 3.5 days, obtains final product Ludox.
Embodiment 4：
The present embodiment provides a kind of acrylic resin and preparation method thereof, comprises the following steps：
1. neodecanoic acid is added being equipped with the four-hole boiling flask of reflux condensing tube, addition funnel, agitator, temperature sensor
Ethylene oxidic ester 20g and acetic acid fourth vinegar 5g, is passed through nitrogen, is heated to 140 DEG C or so, and 10 points are incubated at a reflux temperature
Clock, by t-amyl peroxy compound (DTAP) 1.5g of part initiator two and chain-transferring agent (3- thiohydracrylic acid -2- hydroxyl ethyl esters) 2.0g
It is well mixed, it is fitted into four-hole boiling flask.
2. by whole monomers (acrylic acid (AA) 2g, methyl methacrylate (MMA) 30g, hydroxy propyl methacrylate
(HPMA) 5g, isobornyl methacrylate (IBOMA) 10g, styrene (ST) 15g, butyl methacrylate (BMA) 18g, third
Olefin(e) acid butyl ester (BA) 20g), initiator two t-amyl peroxy compound (DTAP) 0.5g stirring mixing after be placed in separatory funnel, to
It is added dropwise in four-hole boiling flask.
3. 140 DEG C or so are kept, after being added dropwise about 60 minutes, Ludox 12.0g (Ludox accounts for the 12% of total monomer quality)
Loaded on being added dropwise in four-hole boiling flask in another constant pressure separatory funnel, rate of addition is controlled, two points of liquid are dripped with about 3h
Solution in funnel.
4., by initiator two t-amyl peroxy compound (DTAP) 0.5g addition four-hole boiling flasks after dripping, temperature is controlled
140 DEG C or so, uniform stirring is incubated 2 hours, is subsequently cooled within 50 DEG C, and cooling adds acetic acid fourth vinegar 5g, and stir drop
Filter standby to room temperature.Obtain final product acrylic resin.
Embodiment 5：
The present embodiment provides a kind of acrylic resin and preparation method thereof, comprises the following steps：
Specific steps are with embodiment 4, the difference is that Ludox accounts for the 10% of total monomer quality, i.e. 10.0g.
Embodiment 6：
The present embodiment provides a kind of acrylic resin and preparation method thereof, comprises the following steps：
Specific steps are with embodiment 4, the difference is that Ludox accounts for the 11% of total monomer quality, i.e. 11.0g.
Embodiment 7：
The present embodiment provides a kind of acrylic acid bi-component polyurethane coating and preparation method thereof.
Acrylic acid bi-component polyurethane coating preparation process is as follows：
Weight portion (its of solvent mixture 23.8 is added in the weight portion of acrylic resin 100 prepared by above-described embodiment 4
In：8 parts of butyl acetate, 260-E solvents, 12.3 parts, 3.5 parts of hexone, the weight portion of auxiliary agent 2 is (wherein：Dispersant
Dispers700,0.2 part, wetting agent Dispers610s, 0.3 part, smooth agent ClideB148,41 parts), the weight of color stuffing 24.2
Part is (wherein：20 parts of anatase thpe white powder, 0.2 part of carbon black, mica powder 2,1 part of blanc fixe, 1 part of glass dust) it is sufficiently stirred for point
Dissipate uniform through milling, fineness reaches less than 30 μm, adds curing agent polyisocyanates MR-200 to stir after filtering, as
Acrylic acid bi-component polyurethane coating.
Embodiment 8：
The present embodiment provides a kind of acrylic acid bi-component polyurethane coating and preparation method thereof.
Acrylic acid bi-component polyurethane coating preparation process is as follows：
Weight portion (its of solvent mixture 23.8 is added in the weight portion of acrylic resin 100 prepared by above-described embodiment 5
In：8 parts of butyl acetate, 260-E solvents, 12.3 parts, 3.5 parts of hexone, the weight portion of auxiliary agent 2 is (wherein：Dispersant
Dispers700,0.2 part, wetting agent Dispers610s, 0.3 part, smooth agent ClideB148,41 parts), the weight of color stuffing 24.2
Part is (wherein：20 parts of anatase thpe white powder, 0.2 part of carbon black, mica powder 2,1 part of blanc fixe, 1 part of glass dust) it is sufficiently stirred for point
Dissipate uniform through milling, fineness reaches less than 30 μm, adds curing agent polyisocyanates MR-200 to stir after filtering, as
Acrylic acid bi-component polyurethane coating.
Embodiment 9：
The present embodiment provides a kind of acrylic acid bi-component polyurethane coating and preparation method thereof.
Acrylic acid bi-component polyurethane coating preparation process is as follows：
Weight portion (its of solvent mixture 23.8 is added in the weight portion of acrylic resin 100 prepared by above-described embodiment 6
In：8 parts of butyl acetate, 260-E solvents, 12.3 parts, 3.5 parts of hexone, the weight portion of auxiliary agent 2 is (wherein：Dispersant
Dispers700,0.2 part, wetting agent Dispers610s, 0.3 part, smooth agent ClideB148,41 parts), the weight of color stuffing 24.2
Part is (wherein：20 parts of anatase thpe white powder, 0.2 part of carbon black, mica powder 2,1 part of blanc fixe, 1 part of glass dust) it is sufficiently stirred for point
Dissipate uniform through milling, fineness reaches less than 30 μm, adds curing agent polyisocyanates MR-200 to stir after filtering, as
Acrylic acid bi-component polyurethane coating.
Comparative example：
The present embodiment provides a kind of acrylic acid bi-component polyurethane coating and preparation method thereof,
Acrylic acid bi-component polyurethane coating preparation process is as follows：
In acrylic resin (not having the 3rd step in being free of Ludox, that is, embodiment 4 in acrylic resin) 100 weight
The weight portion of solvent mixture 23.8 is added in part (wherein：8 parts of butyl acetate, 260-E solvents, 12.3 parts, hexone
3.5 parts, the weight portion of auxiliary agent 2 is (wherein：Dispersant Dispers700,0.2 part, wetting agent Dispers610s, 0.3 part, smooth agent
ClideB148,41 parts), the weight portion of color stuffing 24.2 is (wherein：It is 20 parts of anatase thpe white powder, 0.2 part of carbon black, 2 parts of mica powder, heavy
1 part of shallow lake barium sulfate, 1 part of glass dust) it is sufficiently stirred for being uniformly dispersed through milling, fineness reaches less than 30 μm, adds after filtering admittedly
Agent polyisocyanates MR-200 stirs, as acrylic acid bi-component polyurethane coating.
The acrylic acid bi-component polyurethane coating performance comparison table of table 1
Note：Above-mentioned method of testing is carried out by GB/T 22374-2008 terrace coating material national standard standards.
As seen from Table 1, it is better than in some aspects by the performance of silica sol modified acrylic acid bi-component polyurethane coating
Not over silica sol modified acrylic acid bi-component polyurethane coating performance or reached the requirement of GB.
It is understood that the embodiment of above principle being intended to be merely illustrative of the present and the exemplary implementation for using
Mode, but the invention is not limited in this.For those skilled in the art, essence of the invention is not being departed from
In the case of god and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Ludox, it is characterised in that comprise the following steps：
Step 1) tetraethyl orthosilicate and absolute ethyl alcohol are reacted in acid condition, form intermediate reaction liquid；
Step 2) by absolute ethyl alcohol and silane coupler, (γ-(methacryloxypropyl) propyl trimethoxy silicane adds described
Reacted in intermediate reaction liquid, ageing obtains Ludox.
2. the preparation method of Ludox as claimed in claim 1, it is characterised in that
The step 1) in, the mass ratio of tetraethyl orthosilicate and absolute ethyl alcohol is 1：(1-1.28).
3. the preparation method of Ludox as claimed in claim 1, it is characterised in that
The step 1) in reaction temperature be 30-40 DEG C, the reaction time be 1-1.5 hours.
4. the preparation method of Ludox as claimed in claim 1, it is characterised in that
The step 2) in, absolute ethyl alcohol and the silane coupler (quality of γ-(methacryloxypropyl) propyl trimethoxy silicane
Than being (0.29-0.37)：1.
5. the preparation method of Ludox as claimed in claim 1, it is characterised in that
The step 2) in silane coupler (feed postition of γ-(methacryloxypropyl) propyl trimethoxy silicane for be added dropwise,
Time for adding is 30-40min.
6. the preparation method of Ludox as claimed in claim 1, it is characterised in that the step 2) in reaction temperature be 50-
60 DEG C, the reaction time is 3-4 hours；Digestion time is 3-4 days.
7. a kind of Ludox, it is characterised in that be the preparation method using the Ludox as any one of claim 1-6
Prepare.
8. a kind of acrylic resin, it is characterised in that be using raw material monomer and Ludox are carried out into mixed and modified preparation, its
In, the Ludox accounts for the 10-12% of described raw material monomer quality by percentage to the quality.
9. a kind of acrylic acid double-component polyurethane coating, it is characterised in that including acrylic resin as claimed in claim 8.
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Cited By (9)
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| CN108586812A (en) * | 2018-05-02 | 2018-09-28 | 太仓美克斯机械设备有限公司 | A kind of preparation method and applications of sol dispersion |
| CN108658473A (en) * | 2018-05-31 | 2018-10-16 | 厦门大学 | A kind of cover-plate glass and its preparation method and application |
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| CN109868047A (en) * | 2019-03-15 | 2019-06-11 | 常州穗时新材料有限公司 | A kind of middle low-temperature setting organosilicon-modified acrylic polyurethane water-based paint and preparation method thereof |
| CN111019465A (en) * | 2019-12-27 | 2020-04-17 | 海安常州大学高新技术研发中心 | Preparation process of organic-inorganic composite water-based acrylic acid anticorrosive paint |
| CN111826073A (en) * | 2020-08-20 | 2020-10-27 | 河南朗迪新材料科技有限公司 | Preparation method of waterproof coating |
| CN112094509A (en) * | 2020-09-24 | 2020-12-18 | 蚌埠学院 | Organic silicon modified high-stability acidic silica sol and preparation method thereof |
| CN114163926A (en) * | 2021-12-20 | 2022-03-11 | 江苏三木化工股份有限公司 | Organic silicon resin for air-drying high-performance solar panel and fan blade paint and preparation method thereof |
| CN116769337A (en) * | 2023-07-04 | 2023-09-19 | 佛山市顺德区荷叶化工有限公司 | Inorganic floor coating suitable for large heavy logistics warehouse and manufacturing method thereof |
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