CN101024751B - Coating material containing POSS acrylate copolymer and preparing method - Google Patents
Coating material containing POSS acrylate copolymer and preparing method Download PDFInfo
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- CN101024751B CN101024751B CN200710008684XA CN200710008684A CN101024751B CN 101024751 B CN101024751 B CN 101024751B CN 200710008684X A CN200710008684X A CN 200710008684XA CN 200710008684 A CN200710008684 A CN 200710008684A CN 101024751 B CN101024751 B CN 101024751B
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Abstract
The invention relates to a manufacturing method for coat material containing POSS acrylate copolymer. It takes free radical copolymerized to acr monomer and other acr monomer, and uses as modifier adding into the base compounding of UV coat, after taking UV solidification the coat material of high rigidity would be gained. The constituent includes 40-55% light-cured resin, 5-20% active modifier, 20-45% spike, 1-10% photoinitiator, 2-10% anti-foam additive. The rigidity of coat could reach to 6H, and the shrinkage ratio could reach 2%.
Description
Technical field
The present invention relates to a kind of preparation of coating, especially the coated material of constructing based on nanometer that contains acrylate copolymer.
Background technology
UV-light (UV) curing technology is since the sixties in 20th century, and as a kind of " green technology ", characteristics cause people's extensive concern so that its fast setting, low or solvent-free release, solidification value be low etc.The UV curing technology is to form free radical or positively charged ion by the UV-irradiation light trigger, causes low-molecular-weight oligomer and reactive thinner (monomer) with unsaturated double-bond, forms the macromolecules cross-linking system, thereby obtains the solidified three dimensional structure.UV is coating material solidified as one of product the most commonly used in the UV solidify material, has " 4E " promptly economic (Economy), energy-conservation (Energy), ecological (Ecology), efficient (Efficiency).Be in particular in: single component, easy to use; Curing speed is fast, can finish curing in general several seconds to tens of seconds, helps realizing automatic production, raises labour productivity; Solidification value is low, and room temperature is promptly curable, and energy consumption is low.Simultaneously UV is coating material solidified also has a shortcoming that is difficult to overcome: 1, UV solidifies because set time is short, and the situation of unrelieved stress is more outstanding, and there is defective in mechanical property; 2, the situation of volumetric shrinkage is more outstanding; 3, surface hardness is big inadequately, and wear resisting property is good inadequately.
The interpolation inorganics not only can improve the hardness of coating, and control is convenient, and to improving ADHESION OF PAINTS power positive effect is arranged, thereby is widely adopted.The strong grade of old usefulness (Chen Yonglie, Deng. radiation curing material and application thereof, the 1st edition, Beijing: mention hardness and wear resistance that mineral fillers such as using aerosil, silicon powder, talcum powder can improve coating Chemical Industry Press), but the flexibility of coating descends.Along with the development of inorganic nano material, add inorganic nano-filler and become a new developing direction.Nano material is meant that having one dimension in the three dimension scale at least is material in the nanoscale scope.(Zhang Lide such as Zhang Lide, Mu Limei. nano material and nanostructure. the 1st edition. Beijing: Science Press, 2001) think since the yardstick of nano material between atom and macroscopical crystal, thereby the small-size effect of demonstrating, surface and interfacial effect, quantum effect etc., and the characteristic that derivative various macroscopical crystal do not have on this basis.Because the advantageous characteristic of nano material is added it in UV cured resin system to as fillers dispersed, in the hope of playing a positive role at aspects such as improving hardness and wear resistance and reduction shrinking percentage.The current Nano filling system of using mainly contains:
1, nano silicon system.This system also is one of maximum system of research.Liu Changli etc. (Liu Changli, etc. material engineering, 2006, supplementary issue 1:75-78) adopt ultrasonic dispersion with nanometer SiO
2Powder is dispersed in photosensitivity silicone resin PSUA, and test shows at nanometer SiO
2Content is 4% o'clock, its pencil hardness the highest (reaching 6H), but reduced photocuring speed.(Kim B.S. such as Kim, Park S.H., Kim B.K., Colloid and Polymer Science, 2006,284 (9): 1067-1072) carried out hydrophilic respectively and the hydrophobic processing, be filled into then in the UV solidified polyimide, found also to improve along with its intensity of increase and the wear resistance of silica volume to silica sphere.
2, utilize flaky organic modified nano clay systems to carry out modification.(Wang Huimin such as Wang Huimin, Deng. the Materials Science and Engineering journal, 2004,22 (6): it is coating material solidified 906-908) polynite, Resins, epoxy and vinylformic acid to be made UV, and the result shows that the content of polynite is that its intensity of epoxy acrylate/montmorillonite composite material of 1.0%～2.0% has improvement.(UhlFawn M. such as Uhl, Webster Dean C., Davuluri Siva Prashanth, Wong Shing-Chung, European PolymerJournal, 2006,42 (10): 2596-2605) utilize imvite modified epoxy acrylate, contrast two kinds of polynite and unmodified polynites that process is organically-modified, the polynite of finding non-modified to the improvement of its mechanical property than the polynite of modification come effectively.
3, other mineral filler systems.(Zhang Xiahong such as Zhang Xiahong, Deng. the polymer journal, 2006,6:750-755) utilize titanium dioxide nano-particle, prepare UV coating with epoxy acrylic oligopolymer/thinner/tween 80 (Tween 80)/light trigger, hardness is up to 6H (massfraction of nano titanium oxide is 2%).Li Yanqing etc. (Chinese patent CN1709965) utilize nano indium oxide, stannic oxide, weisspiessglanz, zinc oxide, titanium oxide and composition thereof to obtain the UV solidify material of high hardness wear-resisting.
The current main method of utilizing the nano-powder filled polymer has more than been described, though these methods have certain effect to improving hardness and wear resistance, but the shortcoming that exists mainly contains: 1, nano inoganic particle is owing to occur incompatible with matrix reunites, though passing through surface modification or be coated with to be beneficial to reduce, nanoparticle reunites, yet operation is numerous and diverse, the industrialization difficulty is big, and nanoparticle surface can be big, and the trend of reunion is difficult to avoid; 2, the adding of inorganic nano-particle often is accompanied by the reduction of curing speed; 3, the reunion of nanoparticle becomes the source of collective's defective, and the situation that resistance to impact shock is descended happens occasionally.Therefore how on the basis of nanometer organic inorganic hybridization, improve the dispersing property of inorganic particulate, do not reduce its mechanics and dynamic performance again simultaneously, become the key of preparation high rigidity and high-wearing feature coating.
Summary of the invention
Purpose of the present invention aims to provide coated material of a kind of (methyl) acrylic ester monomer (POSS) acrylate copolymer that contains polyhedral oligomeric silsesquioxane and preparation method thereof.
Technical scheme of the present invention is carried out free-radical polymerized then joining in the basic components of UV coating as properties-correcting agent with containing polyhedral oligomeric silsesquioxane (methyl) acrylic ester monomer (POSS) (methyl) acrylic ester monomer with other, solidify through UV, obtain the coated material of the coating with high rigidity of constructing based on nanometer.
The coated material of a kind of (methyl) acrylic ester monomer (POSS) acrylate copolymer that contains polyhedral oligomeric silsesquioxane of the present invention consist of (massfraction) 40%～55% light-cured resin, 20%～45% thinner, 1%～10% light trigger, 2%～10% defoamer, 5%～20% active modifier.
Described light-cured resin is the epoxy acrylic oligopolymer.Described thinner is hexanediyl ester and pentaerythritol triacrylate, by quality than hexanediyl ester: pentaerythritol triacrylate is 4: 3.Described light trigger is 2-hydroxy-2-methyl-1-Propiophenone (HMPP).Described defoamer is Dow Corning 163 siloxanes.Described active modifier is polyhedral oligomeric silsesquioxane (methyl) acrylic ester monomer (POSS) and other (methyl) acrylic ester monomer carries out polymkeric substance after free-radical polymerized, and the structural formula of (methyl) acrylic ester monomer (POSS) of polyhedral oligomeric silsesquioxane is as follows:
Wherein: R=-CH
3,-n-C
6H
11,-n-C
4H
9,-n-C
8H
17,-C
6H
5N=1～6; Y=-H ,-CH
3, described other (methyl) acrylic ester monomer is methyl methacrylate, butyl acrylate, methyl acrylate and glycidyl methacrylate mix monomer.
The preparation method of the coated material of a kind of (methyl) acrylic ester monomer (POSS) acrylate copolymer that contains polyhedral oligomeric silsesquioxane of the present invention is as follows:
1) active modifier is synthetic: in reaction vessel; with dimethylbenzene as solvent; under the nitrogen protection; 80～130 ℃ of control reaction temperature; add (methyl) acrylic ester monomer (POSS) and the 10～20g/L dicumyl peroxide that 20～100g/L contains polyhedral oligomeric silsesquioxane successively according to the xylene solvent amount then; react 1h earlier; drip 600～800g/L methyl methacrylate then; 20～200g/L butyl acrylate; 20～200g/L methyl acrylate; 40～200g/L glycidyl methacrylate mix monomer and the different monooctyl ester of 0～2g/L chain-transfer agent 3-thiohydracrylic acid; reaction 8～16h; after being cooled to room temperature; add 5～20g/L Resorcinol and with the volume ratio of dimethylbenzene be (0.4～0.8): 1 N; dinethylformamide (DMF) and with the vinylformic acid of glycidyl methacrylate equivalent; be warming up to 60～120 ℃; react 4～12h again, add ethanol multipolymer is precipitated, filter; use hot wash, and the back is standby for several times with methyl alcohol drip washing.
2) be 5%～20% active modifier and 40%～55% light-cured resin by the composition component of coated material with step 1 synthetic massfraction, 20%～45% thinner, 2%～10% defoamer, allotment is even down at 30～50 ℃, promptly obtains based on organic-inorganic hybrid nanometer bunch acrylate paint.
This coating is coated on the matrix, and thickness is 0.2～0.3mm, and then with the 1000W high voltage mercury lamp radiation, film-forming, radiation length are 15cm.Radiated time is 40～120s, detects the hardness of coating with pencil hardness method.
The present invention is owing to introduce copolymer-modified dose of hybrid inorganic-organic with nanostructure in the UV cured resin, it endorses the microfacies district that forms nano inorganic by the inorganic cage shape that silica constituted, and avoids the reunion of inorganic particulate; Contained unsaturated carbon-carbon double bond can participate in curing reaction, can improve the cross-linking density that solidifies the back system; And, play the enhanced effect of filling, thereby improve the coating material solidified surface hardness of UV because polyhedral oligomeric silsesquioxane has the trend to surface enrichment.The formed coating hardness of this coating is up to pencil hardness 6H.At UV matrix resin solidified simultaneously, the hybrid inorganic-organic properties-correcting agent of introducing can form interpenetrating(polymer)networks with matrix, can be when improving hardness, and the shrinking percentage when reducing the UV resin solidification.Use ASTM D 2566 standards, the shrinking percentage of testing coating is minimum to be 2%, less than the shrinking percentage more than 8% of common UV resin.Prepared coating can be applicable to the top layer application of woodenware such as the timber floor of high surface strength, the external coating of hardware equipment such as automobile and motorcycle device, and optical fiber surface, building material surface, the high rigidity application of optical storage equipment surface.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1:
Step 1, in the 100ml three-necked bottle, add dimethylbenzene 50ml, feed nitrogen, under agitation be heated to and add the methyl acrylic ester monomer (R=-CH wherein that 5.0g contains polyhedral oligomeric silsesquioxane after 120 ℃ respectively
3, n=1, Y=-CH
3) and initiator dicumyl peroxide 0.7g, reaction 1h earlier.
Step 2, will be by methyl methacrylate 30.0g, butyl acrylate 5.0g, mix monomer and chain that methyl acrylate 1.0g, glycidyl methacrylate 8.0g form move the different monooctyl ester 0.5g of agent 3-thiohydracrylic acid, are added drop-wise in the three-necked bottle, continue reaction 8h.
Step 3, be cooled to room temperature after, add Resorcinol 0.5g, DMF20ml and with the vinylformic acid of glycidyl methacrylate equivalent, be warming up to 80 ℃, reaction 7h.
Step 4, be cooled to room temperature after, add ethanol 300ml multipolymer precipitated, filter, with hot water agitator treating suction filtration, be used to remove hydroquinone of polymerization retarder, and, be used to take out anhydrate branch and unreacted monomer with methyl alcohol drip washing several.Final drying obtains properties-correcting agent to constant weight.
Step 5, with epoxy acrylate oligomer 55g, (methyl) acrylic acid esters co-polymer active modifier 15g that contains polyhedral oligomeric silsesquioxane, hexanediyl ester 20g and pentaerythritol diacrylate 15g, light trigger 2-hydroxy-2-methyl-1-Propiophenone (HMPP) 5g, Dow Corning 163 silicone antifoam agent 5g, under 40 ℃, stir, promptly obtain based on organic-inorganic hybrid nanometer bunch acrylate paint.
Step 6, coating is evenly coated on 5.0 * 12.0 the sheet glass, shines 80s under the 1000W high voltage mercury lamp, radiation length is 15cm.Detect the hardness of this coating up to 6H with pencil hardness method.Use ASTM D 2566 standards, the shrinking percentage of testing coating is 5.5%.
Embodiment 2:
Step 1: as embodiment 1 step 1, stir down and be heated to 80 ℃, adding 1.0g contains the acrylic ester monomer (R=-C wherein of polyhedral oligomeric silsesquioxane
6H
5, n=6, Y=-H) and 0.5g initiator dicumyl peroxide reaction 1h.
Step 2: as embodiment 1 step 2, add the 40.0g methyl methacrylate, the 5.0g butyl acrylate, the 1.0g methyl acrylate, the mix monomer of glycidyl acrylate 10.0g continues reaction 16h.
Step 3, be cooled to room temperature after, add Resorcinol 0.8g, DMF30ml and with the vinylformic acid of glycidyl methacrylate equivalent, be warming up to 120 ℃, reaction 4h.
Step 4: with embodiment 1;
Step 5: with epoxy acrylate oligomer 50g, (methyl) acrylic acid esters co-polymer active modifier 15g that contains polyhedral oligomeric silsesquioxane, hexanediyl ester 20g and pentaerythritol diacrylate 15g, light trigger 2-hydroxy-2-methyl-1-Propiophenone (HMPP) 3g, Dow Corning 163 silicone antifoam agent 5g, under 50 ℃, stir, promptly obtain based on organic-inorganic hybrid nanometer bunch acrylate paint.
Step 6: with embodiment 1 step 6, irradiation time is 120s, detects the hardness of this coating up to 4H with pencil hardness method.Shrinking percentage is 2.5%.
Embodiment 3～12:
Step 1～4: concrete operations just change the amount of each component with step 1～4 described in the embodiment 1, R=-n-C in the monomeric structural formula of POSS
4H
9, n=2, Y=-CH
3The concrete prescription of properties-correcting agent sees Table 1 among each embodiment.
Table 1
| Embodiment | POSS monomer (g) | Methyl methacrylate (g) | Butyl acrylate (g) | Methyl acrylate (g) | Glycidyl methacrylate (g) | Chain-transfer agent (g) | Dicumyl peroxide (g) |
| 3 | 1.0 | 30.0 | 10.0 | 1.0 | 5.0 | 0.0 | 0.5 |
| 4 | 2.0 | 40.0 | 5.0 | 10.0 | 8.0 | 0.5 | 0.7 |
| Embodiment | POSS monomer (g) | Methyl methacrylate (g) | Butyl acrylate (g) | Methyl acrylate (g) | Glycidyl methacrylate (g) | Chain-transfer agent (g) | Dicumyl peroxide (g) |
| 5 | 3.0 | 45.0 | 1.0 | 5.0 | 10.0 | 0.7 | 1.0 |
| 6 | 4.0 | 30.0 | 10.0 | 1.0 | 8.0 | 1.0 | 0.5 |
| 7 | 5.0 | 40.0 | 5.0 | 10.0 | 5.0 | 0.0 | 0.7 |
| 8 | 1.0 | 45.0 | 1.0 | 5.0 | 2.0 | 0.5 | 1.0 |
| 9 | 2.0 | 30.0 | 10.0 | 1.0 | 10.0 | 0.7 | 0.5 |
| 10 | 3.0 | 40.0 | 5.0 | 10.0 | 8.0 | 1.0 | 0.7 |
| 11 | 4.0 | 45.0 | 1.0 | 5.0 | 5.0 | 0.0 | 1.0 |
| 12 | 5.0 | 30.0 | 10.0 | 1.0 | 2.0 | 0.5 | 0.5 |
Step 5～6: concrete operations are added top resulting properties-correcting agent in the coating to the step 5 among the embodiment 1～6, and the hardness and the shrinking percentage of its each component concentration and the coating that obtains see Table 2.
Table 2
| Embodiment | Epoxy acrylic ester prepolymer (%) | Modifier content (%) | Hexanediyl ester (%) | Pentaerythritol diacrylate (%) | Light trigger HMPP (%) | Defoamer (%) | Time (S) | Pencil hardness | Shrinking percentage (%) |
| 3 | 50 | 20 | 25.7 | 19.3 | 1 | 3 | 60 | 6H | 5.8 |
| 4 | 55 | 5 | 11.4 | 8.6 | 3 | 5 | 90 | 4H | 7.8 |
| 5 | 40 | 10 | 14.3 | 10.7 | 5 | 8 | 120 | 4H | 3.4 |
| 6 | 45 | 15 | 20 | 15 | 7 | 10 | 40 | 5H | 3.6 |
| 7 | 50 | 20 | 23 | 17.3 | 10 | 2 | 50 | 6H | 3.1 |
| 8 | 55 | 5 | 25.7 | 19.3 | 1 | 3 | 60 | 4H | 7.2 |
| 9 | 40 | 10 | 11.4 | 8.6 | 3 | 5 | 90 | 3H | 3.2 |
| 10 | 45 | 15 | 14.3 | 10.7 | 5 | 8 | 120 | 4H | 2.9 |
| Embodiment | Epoxy acrylic ester prepolymer (%) | Modifier content (%) | Hexanediyl ester (%) | Pentaerythritol diacrylate (%) | Light trigger HMPP (%) | Defoamer (%) | Time (S) | Pencil hardness | Shrinking percentage (%) |
| 11 | 50 | 20 | 20 | 15 | 7 | 10 | 40 | 6H | 3.1 |
| 12 | 55 | 5 | 23 | 17 | 10 | 2 | 50 | 6H | 6.2 |
Claims (6)
1. a coated material that contains the POSS acrylate copolymer is characterized in that 40%～55% light-cured resin that consists of by massfraction, 5%～20% active modifier, 20%～45% thinner, 1%～10% light trigger, 2%～10% defoamer; Described active modifier is that polyhedral oligomeric silsesquioxane (methyl) acrylic ester monomer and other (methyl) acrylic ester monomer carry out the polymkeric substance after free-radical polymerized, and (methyl) acrylic ester monomer POSS of described polyhedral oligomeric silsesquioxane is as follows:
Wherein: R=-CH
3,-n-C
6H
11,-n-C
4H
9,-n-C
8H
17,-C
6H
5N=1～6; Y=-H ,-CH
3
Described a kind of preparation method who contains the coated material of POSS acrylate copolymer may further comprise the steps:
1) active modifier is synthetic
In reaction vessel, with dimethylbenzene as solvent, under the nitrogen protection, 80～130 ℃ of control reaction temperature, add (methyl) acrylic ester monomer that 20～100g/L contains polyhedral oligomeric silsesquioxane successively according to the xylene solvent amount then, 10～20g/L dicumyl peroxide, reaction 1h earlier; Drip 600～800g/L methyl methacrylate then, 20～200g/L butyl acrylate, 20～200g/L methyl acrylate, 40～200g/L glycidyl methacrylate mix monomer and the different monooctyl ester of 0～2g/L chain-transfer agent 3-thiohydracrylic acid, reaction 8～16h; After being cooled to room temperature, add 5～20g/L Resorcinol and with the volume ratio of dimethylbenzene be 0.4～0.8: 1 N, dinethylformamide and with the vinylformic acid of glycidyl methacrylate equivalent, be warming up to 60～120 ℃, react 4～12h again; Add ethanol multipolymer is precipitated, filter, use hot wash, and with standby after the methyl alcohol drip washing;
2) be 5%～20% active modifier and 40%～55% light-cured resin by the composition component of coated material with step 1 synthetic massfraction, 20%～45% thinner, 2%～10% defoamer, allotment is even down at 30～50 ℃, promptly obtains based on organic-inorganic hybrid nanometer bunch acrylate paint.
2. a kind of coated material that contains the POSS acrylate copolymer as claimed in claim 1 is characterized in that described light-cured resin is the epoxy acrylic oligopolymer.
3. a kind of coated material that contains the POSS acrylate copolymer as claimed in claim 1, it is characterized in that described thinner is hexanediyl ester and pentaerythritol triacrylate, the mass ratio of hexanediyl ester and pentaerythritol triacrylate two components is 4: 3.
4. a kind of coated material that contains the POSS acrylate copolymer as claimed in claim 1 is characterized in that described light trigger is 2-hydroxy-2-methyl-1-Propiophenone.
5. a kind of coated material that contains the POSS acrylate copolymer as claimed in claim 1 is characterized in that described defoamer is Dow Corning 163 siloxanes.
6. a kind of coated material that contains the POSS acrylate copolymer as claimed in claim 1 is characterized in that described other (methyl) acrylic ester monomer is methyl methacrylate, butyl acrylate, methyl acrylate and glycidyl methacrylate mix monomer.
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| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
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2007
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI586763B (en) * | 2016-01-30 | 2017-06-11 | Fu-Lun Xu | Quantum Resonance Coating and Its Construction Method |
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| CN101024751A (en) | 2007-08-29 |
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