CN104558447B - Inorganic nano composite anti-doodling resin and preparation method thereof - Google Patents
Inorganic nano composite anti-doodling resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an inorganic nano composite anti-doodling resin and a preparation method thereof. Silane-coupling-agent-modified inorganic nanoparticles, fluorine-containing acrylate monomer, alkyl acrylate monomer and hydroxyalkyl acrylate monomer are subjected to free-radical polymerization reaction to obtain the inorganic nano composite anti-doodling resin. The film formed by the inorganic nano composite anti-doodling resin has the advantages of excellent weather resistance, excellent scratch resistance, excellent chemical corrosion resistance, excellent ultraviolet resistance, excellent wear resistance, low surface energy, excellent pollution resistance and excellent anti-doodling performance, thereby implementing the long-term anti-doodling action. The invention relates to the field of an anti-doodling resin and a preparation method thereof.
Description
Technical field
It is the present invention relates to anti-graffiti resin and preparation method thereof field more particularly to a kind of inorganic nano combined anti-graffiti
Resin and preparation method thereof.
Background technology
Malice scribble is the keenly-felt pain of city manager.The expense that various countries are used for removing scribble is huge, and Britain consumes every year
Take 200,000,000 pounds for remove scribble, and the U.S. is then more than 20,000,000,000 pounds.The loss for causing of maliciously scribbling increasingly is subject to
The concern of people.At present, anti-graffiti maximally efficient technology is the coating using anti-graffiti resin formation, is difficult to scribble
Or be easy to remove.One layered low-surface energy nonpolluting coating of body surface is given, attachment and the pollution scribbled can be effectively prevented, and is
Pollution is made also can easily to remove by simple erasing.The minimum compound of the surface energy that is currently known is organic fluoride class, is passed through
Its low-surface-energy characteristic can be given other polymers by modification by copolymerization, and during film forming, fluoro-containing group can be to surface migration
Enrichment so that coating obtains more preferably low-surface-energy effect.
Low-surface-energy characteristic of some producers using fluorocarbon resin is had both at home and abroad, is applied as anti-doodling paint tree
Fat.Chinese patent CN 103360875 discloses the oiliness with fluorocarbon resin, poly- dimethoxysilane as main film forming substance to be prevented
Scribble adhesion resistant paint；German patent DE 102007007999 discloses a kind of fluorinated acrylate monomer, alkyl acrylic acid
Ester monomer and anti-graffiti resin obtained by tetramethylolmethane tetrathio glycolate monomer copolymerization, and it is coating material solidified to be applicable as UV；
Chinese patent CN 102676034 discloses a kind of anti-graffiti coating suitable for outdoor facilities and preparation method thereof, coating master
The mass fraction for wanting component is：Fluorinated acrylate modified soybean oil polyurethane resin 30-65 parts, auxiliary agent 1-10 parts, pigment and
Filler 15-30 parts, water 10-25 parts；These anti-doodling paints antigraffiti effect at short notice is very good, but through many
Secondary scribble is removed and physical abrasion, and its antigraffiti properties drastically can decline, further, since in outdoor prolonged exposure in sunshine,
With the aging of anti-graffiti resin, efflorescence, cracking, the antigraffiti effect of whole coating is lost substantially.
The content of the invention
It is anti-graffiti long-lasting for overcoming the shortcomings of above-mentioned existing fluorine-containing low surface energy coatings, the invention provides a kind of inorganic
Nano combined anti-graffiti resin and preparation method thereof, has excellent weatherability, resistance to marring, chemically-resistant after the resin film forming
Burn into ultraviolet-resistent property and anti-wear performance, while with the low and splendid dirt-resistant of surface energy, antigraffiti properties.
The present invention concrete technical scheme be：A kind of inorganic nano combined anti-graffiti resin, the resin is by silane idol
Connection agent modified inorganic nano-particle, fluorinated acrylate monomer, alkyl acrylate monomer and hydroxyalkyl acrylates monomer
As obtained by free radical solution polymerization, by weight, each component and its consumption for participating in polymerization is as follows：
Silane coupler modified inorganic nano-particle 5-15 parts；
Fluorinated acrylate monomer 10-20 parts；
Alkyl acrylate monomer 20-40 parts；
Hydroxyalkyl acrylates monomer 10-20 parts；
Initiator 0.5-2 parts；
Chain-transferring agent 0.3-1.2 parts；
Organic solvent 30-60 parts.
Preferably, described fluorinated acrylate monomer is selected from short fluorocarbon chain environmental protection monomer：Acrylic acid [N- methyl perfluoros
Hexane sulfoamido] ethyl ester, methacrylic acid [N- methyl perfluoro hexane sulfoamidos] ethyl ester, acrylic acid [N- methyl perfluoro fourths
Alkyl sulfonamide base] ethyl ester, methacrylic acid [N- methyl perfluoro butane sulfoamidos] ethyl ester.
Preferably, described alkyl acrylate monomer is selected from acrylic acid methyl ester., methyl methacrylate, acrylic acid
Ethyl ester, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, propylene
Sour pentyl ester, pentylmethacrylate, Hexyl 2-propenoate, N-Hexyl methacrylate, n-octyl, methacrylic acid are just pungent
Ester, Isooctyl acrylate monomer, 2-Propenoic acid, 2-methyl-, isooctyl ester, octadecyl acrylate, octadecyl methacrylate.
Preferably, the hydroxyalkyl acrylates monomer is selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, propylene
Sour hydroxypropyl acrylate, Hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate.
Preferably, described initiator is selected from 2,2 '-azodiisobutyronitrile, benzoyl peroxide.
Preferably, the described chain-transferring agent is selected from lauryl mercaptan, Stearyl mercaptan.
Preferably, described organic solvent by one or more in esters, ketone and solvent of ether ester type by arbitrarily matching somebody with somebody
Than mixing composition.Described esters solvent is selected from butyl acetate, ethyl acetate；Described ketones solvent is selected from acetone, methyl second
Base ketone；Described solvent of ether ester type selected from ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol methyl ether acetate,
Propandiol butyl ether acetate.
A kind of preparation method of inorganic nano combined anti-graffiti resin, comprises the steps：
(1) by nano silicon, ethanol, water and γ-methacryloxypropyl trimethoxy silane in mass ratio
1:20-60:5-15:0.5-4.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 8-24h, reaction is cooled to room temperature after stopping, and produces
Thing obtains the silane coupler modified inorganic nano-particle of C=C modifications through centrifugation and washing.
(2) initiator for accounting for initiator total amount 30wt% is dissolved in the organic solvent for accounting for organic solvent total amount 30wt%,
60 DEG C -90 DEG C are preheated to, the first solution is obtained.
(3) will whole silane coupler modified inorganic nano-particles, fluorinated acrylate monomer, alkyl acrylate list
The initiator of body, hydroxyalkyl acrylates monomer, chain-transferring agent and the 60wt% for accounting for initiator total amount is dissolved in that to account for organic solvent total
In the organic solvent of amount 60wt%, the second solution is obtained.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in the 2-4 hours；After adding, protect
Warm 4-6 hours, add remaining initiator and organic solvent, are warming up to 70-100 DEG C, continue insulation 4-24 hours, obtain resin
Solution, adds volume polymeric reaction product to settle out for the precipitant of 5-20 times of resin solution, is centrifuged, and vacuum drying obtains
Inorganic nano combined anti-graffiti resin.
Preferably, the particle diameter of described nano silicon is in 10-100nm.
Preferably, described precipitant is selected from methanol, normal hexane, petroleum ether, dichloromethane.
It is compared with the prior art, the invention has the beneficial effects as follows：
1st, the present invention passes through silane coupler to nano-silicon dioxide modified so as to can adopt with acrylate monomer copolymerization
Nano silicon, Organic fluoride and hydroxyalkyl are incorporated on acrylic resin with radical polymerization, obtain a kind of inorganic nano
Compound anti-graffiti resin, it is modified after nano silicon directly participate in polymerization, being evenly distributed in resin, to propylene
The modified effect of acid resin more preferably, can greatly improve the weatherability after resin film forming, resistance to marring, resistance to chemical attack, anti-purple
Outer property and anti-wear performance, while retain the low and splendid dirt-resistant of the surface energy that has of fluorine resin, antigraffiti properties, so as to reality
Now anti-graffiti coatings is long-lasting.
2nd, the fluorocarbon chain acrylate monomer used in the present invention is short fluorocarbon chain environmental protection monomer, does not contain and does not produce
Environmentally harmful PFOA and PFOS of life etc., environmental protection.
3rd, after inorganic nano combined anti-graffiti resin film forming prepared by the present invention, Jing is determined, and Static water contact angles are at 100 °
More than, illustrate that resin is provided with low-surface-energy；On film, Jing is infected with repeatedly oil-dirt for 100 times and cleans noresidue, illustrates resin
It is provided with stronger anti-graffiti property.
4th, this coating resin environmental friendliness, synthetic method is simple, convenient, reaction conversion ratio is high, product film forming is fast, weather-proof
Property, chemical reagent resistance and wearability are good, good with coating substrate adhesive force, can be many in glass, PVC board and sheet metal etc.
Plant surface to use.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
(1) by particle diameter be the nano silicon of 10nm, ethanol, water and γ-methacryloxypropyl trimethoxy
Silane in mass ratio 1:20:5:0.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 8h, reaction is cooled to room temperature, product after stopping
Through centrifugation and washing, the silane coupler modified inorganic nano-particle of C=C modifications is obtained.
(2) by the 2 of 0.15 part, 2 '-azodiisobutyronitrile is dissolved in 9 parts of butyl acetate, is preheated to 60 DEG C, is obtained first molten
Liquid.
(3) by 5 parts of silane coupler modified inorganic nano-particle, 10 parts of methacrylic acid [N- methyl perfluoro hexanes
Sulfoamido] ethyl ester, 20 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 0.3 part of dodecyl
The 2 of mercaptan and 0.3 part, 2 '-azodiisobutyronitrile is dissolved in 18 parts of butyl acetate, obtains the second solution.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in 2 hours；After adding, insulation
4 hours, the 2 of 0.05 part are added, the butyl acetate of 2 '-azodiisobutyronitrile and 3 parts is warming up to 70 DEG C, continues insulation 4 hours,
Resin solution is obtained, is added volume polymeric reaction product to settle out for the normal hexane of 5 times of resin solution, is centrifuged, vacuum drying, i.e.,
Obtain inorganic nano combined anti-graffiti resin.
Embodiment 2
(1) by particle diameter be the nano silicon of 50nm, ethanol, water and γ-methacryloxypropyl trimethoxy
Silane in mass ratio 1:40:10:2.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 12h, reaction is cooled to room temperature after stopping, and produces
Thing obtains the silane coupler modified inorganic nano-particle of C=C modifications through centrifugation and washing.
(2) by the 2 of 0.15 part, 2 '-azodiisobutyronitrile is dissolved in 9 parts of ethylene glycol ether acetate, is preheated to 60 DEG C,
Obtain the first solution.
(3) by 5 parts of silane coupler modified inorganic nano-particle, 10 parts of methacrylic acid [N- methyl perfluoro butane
Sulfoamido] ethyl ester, 20 parts of acrylic acid methyl ester., 10 parts of glycidyl methacrylate, 0.3 part of lauryl mercaptan
With the 2 of 0.3 part, 2 '-azodiisobutyronitrile is dissolved in 18 parts of ethylene glycol ether acetate, obtains the second solution.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in 3 hours；After adding, insulation
5 hours, the 2 of 0.05 part are added, the ethylene glycol ether acetate of 2 '-azodiisobutyronitrile and 3 parts is warming up to 70 DEG C, continues to protect
Temperature 12 hours, obtains resin solution, adds volume polymeric reaction product to settle out for the petroleum ether of 10 times of resin solution, is centrifuged,
Vacuum drying, that is, obtain inorganic nano combined anti-graffiti resin.
Embodiment 3
(1) by particle diameter be the nano silicon of 100nm, ethanol, water and γ-methacryloxypropyl trimethoxy
Silane in mass ratio 1:50:12:3.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 16h, reaction is cooled to room temperature after stopping, and produces
Thing obtains the silane coupler modified inorganic nano-particle of C=C modifications through centrifugation and washing.
(2) 0.3 part of benzoyl peroxide is dissolved in 12 parts of methyl ethyl ketone, is preheated to 75 DEG C, obtain the first solution.
(3) by 10 parts of silane coupler modified inorganic nano-particle, 20 parts of acrylic acid [N- methyl perfluoro hexane sulphonyl
Amido] ethyl ester, 40 parts of octadecyl acrylate, 20 parts of glycidyl acrylate, 0.8 part of Stearyl mercaptan and 0.6
The benzoyl peroxide of part is dissolved in 24 parts of methyl ethyl ketone, obtains the second solution.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in 4 hours；After adding, insulation
6 hours, 0.1 part of benzoyl peroxide and 4 parts of methyl ethyl ketone is added, 85 DEG C are warming up to, is continued insulation 24 hours, is obtained
Resin solution, adds volume polymeric reaction product to settle out for the methanol of 20 times of resin solution, is centrifuged, and vacuum drying obtains
Inorganic nano combined anti-graffiti resin.
Embodiment 4
(1) by particle diameter be the nano silicon of 100nm, ethanol, water and γ-methacryloxypropyl trimethoxy
Silane in mass ratio 1:60:15:4.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 24h, reaction is cooled to room temperature after stopping, and produces
Thing obtains the silane coupler modified inorganic nano-particle of C=C modifications through centrifugation and washing.
(2) by the 2 of 0.6 part, 2 '-azodiisobutyronitrile is dissolved in 18 parts of ethyl acetate, is preheated to 60 DEG C, is obtained first molten
Liquid.
(3) by 10 parts of silane coupler modified inorganic nano-particle, 20 parts of the third acrylic acid [N- methyl perfluoro butane sulphurs
Amide groups] ethyl ester, 40 parts of methyl methacrylate, 20 parts of hydroxyethyl methylacrylate, 1.2 parts of lauryl mercaptan and
The 2 of 1.2 parts, 2 '-azodiisobutyronitrile are dissolved in 36 parts of ethyl acetate, obtain the second solution.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in 4 hours；After adding, insulation
6 hours, the 2 of 0.2 part are added, the ethyl acetate of 2 '-azodiisobutyronitrile and 6 parts is warming up to 85 DEG C, continues insulation 24 hours,
Resin solution is obtained, is added volume polymeric reaction product to settle out for the dichloromethane of 10 times of resin solution, is centrifuged, vacuum is done
It is dry, that is, obtain inorganic nano combined anti-graffiti resin.
Embodiment 5
(1) by particle diameter be the nano silicon of 100nm, ethanol, water and γ-methacryloxypropyl trimethoxy
Silane in mass ratio 1:20:5:0.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 12h, reaction is cooled to room temperature after stopping, and produces
Thing obtains the silane coupler modified inorganic nano-particle of C=C modifications through centrifugation and washing.
(2) 0.3 part of benzoyl peroxide is dissolved in 12 parts of propylene glycol methyl ether acetate, is preheated to 90 DEG C, obtain
One solution.
(3) by 15 parts of silane coupler modified inorganic nano-particle, 15 parts of acrylic acid [N- methyl perfluoro hexane sulphonyl
Amido] ethyl ester, 30 parts of butyl methacrylate, 15 parts of Hydroxypropyl acrylate, 0.8 part of Stearyl mercaptan and 0.6 part
Benzoyl peroxide be dissolved in 24 parts of propylene glycol methyl ether acetate, obtain the second solution.
(4) the second solution that step (3) is obtained being added in the first solution at the uniform velocity in 4 hours；After adding, insulation
6 hours, 0.1 part of benzoyl peroxide and 4 parts of propylene glycol methyl ether acetate is added, 100 DEG C are warming up to, continues insulation 24 little
When, resin solution being obtained, is added volume polymeric reaction product to settle out for the petroleum ether of 20 times of resin solution, is centrifuged, vacuum is done
It is dry, that is, obtain inorganic nano combined anti-graffiti resin.
Performance test is contrasted
It is prepared by anti-graffiti resin coating film：It is by the inorganic nano combined anti-graffiti resins dilute for preparing to 5wt%, uniform to apply
In clean glass sheet, the then spin coating on spin coater, the film-forming at room temperature of Jing 24 hours obtain smooth copolymer thin
Film supplies performance test.
Contact angle method of testing：CAM200 type surface tension and contact angle survey of the contact angle using the production of KSV companies of Finland
Amount instrument, during measurement Static water contact angles, droplet size is 3 μ L, and the contact angular data of gained is based on three differences of sample surfaces
Contact angle meansigma methodss.
Antigraffiti properties are tested：Scribble in anti-graffiti resin coating film topical oil pen, removed with ethanol, scribble repeatedly,
Erasing 100 times.
Test result：
Inorganic nano combined anti-graffiti resin coating film Static water contact angles test result such as table 1：
Table 1：The Static water contact angles test result of inorganic nano combined anti-graffiti resin coating film
After the inorganic nano combined anti-graffiti resin film forming for synthesizing as seen from the above table, Jing is determined, and Static water contact angles exist
More than 100 °,
Illustrate to be provided with low-surface-energy；On film, Jing is infected with repeatedly oil pen's spot for 100 times and cleans noresidue, illustrates resin
It is provided with stronger anti-graffiti property.
The above, is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, every according to the present invention
Any simple modification, change and equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (7)
1. a kind of inorganic nano combined anti-graffiti resin, it is characterised in that：The resin inorganic is received by silane coupler modified
Rice corpuscles, fluorinated acrylate monomer, alkyl acrylate monomer and hydroxyalkyl acrylates monomer pass through free-atom aqueous solution
Polymerization gained, by weight, each component and its consumption for participating in polymerization is as follows：
Silane coupler modified inorganic nano-particle 5-15 parts；
Fluorinated acrylate monomer 10-20 parts；
Alkyl acrylate monomer 20-40 parts；
Hydroxyalkyl acrylates monomer 10-20 parts；
Initiator 0.5-2 parts；
Chain-transferring agent 0.3-1.2 parts；
Organic solvent 30-60 parts；
The preparation method of the inorganic nano combined anti-graffiti resin, comprises the steps：
（1）By nano silicon, ethanol, water and γ-methacryloxypropyl trimethoxy silane in mass ratio 1:20-
60:5-15:0.5-4.5 mix homogeneously, in 55 DEG C of water-bath back flow reaction 8-24h, reaction is cooled to room temperature after stopping, and product is passed through
Centrifugation and washing, obtain the silane coupler modified inorganic nano-particle of C=C modifications；
（2）The initiator for accounting for initiator total amount 30wt% is dissolved in the organic solvent for accounting for organic solvent total amount 30wt%, is preheated to
60 DEG C -90 DEG C, obtain the first solution；
（3）Will all silane coupler modified inorganic nano-particles, fluorinated acrylate monomer, alkyl acrylate monomer,
The initiator of hydroxyalkyl acrylates monomer, chain-transferring agent and the 60wt% for accounting for initiator total amount is dissolved in and accounts for organic solvent total amount
In the organic solvent of 60wt%, the second solution is obtained；
（4）By step（3）The second solution for obtaining being added in the first solution at the uniform velocity in the 2-4 hours；After adding, 4- is incubated
6 hours, remaining initiator and organic solvent is added, 70-100 DEG C is warming up to, continued insulation 4-24 hours, obtain resin molten
Liquid, adds volume polymeric reaction product to settle out for the precipitant of 5-20 times of resin solution, is centrifuged, and vacuum drying obtains nothing
The nano combined anti-graffiti resin of machine.
2. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that described fluorinated acrylate
Monomer is selected from short fluorocarbon chain environmental protection monomer：Acrylic acid [N- methyl perfluoro hexane sulfoamidos] ethyl ester, methacrylic acid [N- methyl
Perflexane sulfoamido] ethyl ester, acrylic acid [N- methyl perfluoro butane sulfoamidos] ethyl ester, [N- methyl is complete for methacrylic acid
Fluorine butane sulfoamido] ethyl ester；
Described alkyl acrylate monomer is selected from acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, metering system
Acetoacetic ester, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, amyl acrylate, methyl-prop
Olefin(e) acid pentyl ester, Hexyl 2-propenoate, N-Hexyl methacrylate, n-octyl, n octyl methacrylate, acrylic acid are different pungent
Ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, octadecyl acrylate, octadecyl methacrylate；
The hydroxyalkyl acrylates monomer is selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate, methyl
Hydroxypropyl acrylate.
3. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that described initiator is selected from 2,
2 '-azodiisobutyronitrile, benzoyl peroxide.
4. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that the described chain-transferring agent
Selected from lauryl mercaptan, Stearyl mercaptan.
5. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that described organic solvent is by ester
One or more in class, ketone and solvent of ether ester type is by any proportioning mixing composition；
Described esters solvent is selected from butyl acetate, ethyl acetate；
Described ketones solvent is selected from acetone, methyl ethyl ketone；
Described solvent of ether ester type selected from ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol methyl ether acetate, third
Glycol monobutyl ether acetate.
6. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that described nano silicon
Particle diameter in 10-100nm.
7. inorganic nano combined anti-graffiti resin as claimed in claim 1, it is characterised in that described precipitant is selected from first
Alcohol, normal hexane, petroleum ether, dichloromethane.
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| CN102677541A (en) * | 2011-11-28 | 2012-09-19 | 泉州市思康新材料发展有限公司 | Fluorine-containing paper oil-proof agent and its preparation method |
| CN103305112A (en) * | 2013-06-27 | 2013-09-18 | 浙江大学 | Environment-friendly coating with anti-icing function and preparation method thereof |
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