CN102993440B - Photocuring nano hybrid material, and synthesis method and application thereof - Google Patents
Photocuring nano hybrid material, and synthesis method and application thereof Download PDFInfo
- Publication number
- CN102993440B CN102993440B CN201110276267.XA CN201110276267A CN102993440B CN 102993440 B CN102993440 B CN 102993440B CN 201110276267 A CN201110276267 A CN 201110276267A CN 102993440 B CN102993440 B CN 102993440B
- Authority
- CN
- China
- Prior art keywords
- photocuring
- reaction group
- hybrid material
- photocuring reaction
- nano hybrid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a photocuring nano hybrid material with photocuring reactive groups, and preparation and application thereof. Siloxane with photocuring reactive groups (also called photosensitive groups) is subjected to hydrolytic polycondensation under proper conditions to obtain the photocuring nano hybrid material with photocuring reactive groups. The photocuring nano hybrid material contains abundant photocuring reactive groups, has favorable solubility and dispersity, can effectively improve the curability of the photocuring paint, and can also effectively improve the mechanical properties of the photocuring paint.
Description
Technical field
The present invention relates to environmentally friendly photocuring macromolecular material, be specifically related to have light curing nano hybrid material and the preparation method and use thereof of photocuring active group.
Background technology
Photocuring high-molecular coating is to utilize UV-light as the curing energy, causes at normal temperatures the intermolecular generation chemical reaction of the different components of coating, at a kind of novel high polymer environmental protection coating material of moment Quick cross-linking film forming.Compare with traditional coating curing technology, its radiation curing have energy-saving and environmental protection, efficient, be applicable to the advantages such as heat-sensitive substrate material, excellent performance, facility investment are few.Along with the enhancing of mankind's environmental consciousness, radiation curing replaces traditional thermofixation will become a kind of trend.
Photocuring high-molecular coating feature comprises:
(1) curing speed is fast: photo-cured coating the most outstanding feature is exactly that curing speed is fast, can within the time of 0.05～0.1s, solidify the soonest, the fastest coating of dry solidification in current all kinds of coating, conventionally under the uv light irradiation of some kw of power, only need within several seconds or tens seconds, just curablely reach service requirements completely, this has improved production efficiency undoubtedly greatly, save the space that work in-process are stacked, and can meet the demand of mass automatic production.Meanwhile, the quality of photocuring product is also more easily guaranteed.
(2) environmental friendliness: another advantage of photo-cured coating is that it,, substantially not containing volatile solvent, has eco-friendly feature.Photo-cured coating is when illumination, and nearly all composition participates in crosslinking polymerization, enters in the middle of coating, becomes a part for cross-linked structure, can be considered the coating of 100% solid content.Therefore, reduced the pollution of environment and the harm to human body.
(3) save energy: compare with solvent based coating, ultraviolet light polymerization energy used is only equivalent to 1/5th left and right of solvent based coating thermofixation.The photo-cured coating at normal temperatures feature of quick cold-curing is also that other coating are too far behind to catch up.Photo-cured coating can effectively utilize ultraviolet source, and curing speed is fast, has in fact greatly strengthened effective utilization and saving to energy.
(4) expense is low: photocuring only needs the radiating capacity for exciting light initiator, therefore can save a large amount of energy consumptions; Meanwhile, because the active constituent content in photo-cured coating is high, material actual consumption amount is significantly reduced; In addition, uv equipment investment is relatively low, easily is automated, and can save a large amount of investments, and reduces factory building occupation of land.
Sum up, photo-cured coating has quick-drying, environmental protection, the advantage such as energy-conservation.Along with the pay attention to day by day of countries in the world to ecological environmental protection, to the strict legislation restriction of atmospheric emission, the importance of photo-cured coating is also more and more outstanding.The U.S., European Union, Japan etc. are one of major reason using the minimizing of VOC as preferential employing photocuring technology all.In China, along with rapid expansion and the pay attention to day by day to environment protection of economic scale, also will be day by day deeply universal as research, exploitation and the application of the photo-cured coating of environment-friendly technique.
Further improving one of effective measure of photo-cured coating over-all properties, is to carry out organosilicon/inorganic nano-hybrid.Carry out organosilicon/inorganic nano-hybrid, current common way is: adopt physical doping method, nano-powder (or surface treated nano-powder) is directly joined in photocuring system, but existing nanoparticle to be difficult to reach nano level disperses, and cause that photocuring system viscosity sharply rises, and affects the problems such as processing performance; Therefore, people have carried out the research at modified Nano particle surface condensation grafting ultraviolet curing group, still, there is no organic nanoparticle in grafting, still exist and disperse and agglomeration traits.
At present, the report relevant for graft polymerization photosensitivity group on silicon dioxide nano powder, not yet has the report of preparing light curing nano hybrid material by having the siloxanes of photosensitivity group.
Summary of the invention
In order to overcome above-mentioned technical problem, the inventor finds through research with keen determination: the siloxanes that makes to have photocuring reaction group (also referred to as photosensitive group) is hydrolytie polycondensation under proper condition, obtain having the light curing nano hybrid material of photocuring reaction group, it has good solubility and dispersiveness in light-cured resin, thereby completes the present invention.
The object of the present invention is to provide a kind of light curing nano hybrid material with photocuring reaction group, its structure comprises with the structure division shown in following formula (1):
Formula (1)
Wherein, R is photocuring reaction group, is specially CH
2=CH-or CH
2=C (CH
3) COO-R
1-, R wherein
1for alkylidene group;
Wavy line represents repetitive extension or the hydrogen with structure division shown in above formula (1).
Another object of the present invention is to provide the above-mentioned preparation method with the light curing nano hybrid material of photocuring reaction group, the method comprises: under nitrogen atmosphere, under catalyzer exists, in organic solvent, at the temperature of 20-80 ℃, make to have siloxanes and the deionized water reaction of photocuring reaction group, the polycondensation of gained hydrolysate, solvent and other small molecules in reaction system removed in decompression, obtain having the light curing nano hybrid material of photocuring reaction group, wherein, the siloxanes with photocuring reaction group is selected from vinylsiloxane, (methyl) acryloyl-oxy radical siloxane.
A further object of the present invention is to provide the purposes of the above-mentioned light curing nano material with photocuring reaction group in preparing photo-cured coating.
A further object of the present invention is to provide a kind of photo-cured coating, it prepares two by the following method at the temperature of 20-50 ℃, make 10-30 weight part above-mentioned there is the light curing nano hybrid material of photocuring reaction group, the monomer reactivity thinner of the light-cured resin of 40-60 weight part, 10-40 weight part, the auxiliary agent of the free radical photo-initiation of 3-5 weight part and 1-5 weight part mix.
Light curing nano hybrid material provided by the invention has a large amount of photocuring reaction groups, often corresponding to a Siliciumatom, there is a photocuring reaction group, be that Siliciumatom is identical with the molar weight of photocuring reaction group, its light solidified is excellent, it has good solubility and dispersiveness, there is good intermiscibility with conventional light-cured resin, there is good intermiscibility with reactive monomer thinner, the curing performance of photo-cured coating can not only be effectively improved, and the mechanical property of photo-cured coating can be effectively improved.
Accompanying drawing explanation
Fig. 1 is the light curing nano hybrid material with photocuring reaction group of gained in the embodiment of the present invention 1
1h NMR spectrogram and vinylsiloxane monomer
1the contrast of H NMR spectrogram;
Wherein, 1 represents vinylsiloxane monomer, and 2 represent the light curing nano hybrid material with photocuring reaction group of gained in embodiment 1, a, and b, c represents the hydrogen atom of three different positionss.
Fig. 2 is the light curing nano hybrid material that in the embodiment of the present invention 1, gained has photocuring reaction group
29si NMR spectrogram.
Fig. 3 is the FT-IR spectrogram that in the embodiment of the present invention 1, gained has the light curing nano hybrid material of photocuring reaction group.
Fig. 4 is the MALDI TOF mass spectra of the light curing nano hybrid material that in the embodiment of the present invention 1, gained has photocuring reaction group.
Fig. 5 A represents gamma-methyl allyl acyloxypropyl trimethoxysilane monomer
1h NMR spectrogram, Fig. 5 B represents the light curing nano hybrid material with photocuring reaction group of gained in embodiment 10
1h NMR spectrogram.
Fig. 6 represents the infrared spectra (FTIR) of the light curing nano hybrid material with photocuring reaction group of gained in embodiment 10.
Fig. 7 A represents gamma-methyl allyl acyloxypropyl trimethoxysilane monomer
29si NMR spectrogram, Fig. 7 B represents the light curing nano hybrid material with photocuring reaction group of gained in embodiment 10
29si NMR spectrogram.
Fig. 8 represents transmission electron microscope (SEM) photo of the light curing nano hybrid material with photocuring reaction group of gained in embodiment 10.
Embodiment
Below by embodiment, the present invention is described in detail, and the features and advantages of the invention will become more clear, clear and definite along with these explanations.
On the one hand, the invention provides a kind of light curing nano hybrid material with photocuring reaction group, its structure comprises with the structure division shown in following formula (1):
Formula (1)
Wherein, R is photocuring reaction group CH
2=C (CH
3) COO-CH
2cH
2cH
2-or CH
2=C (CH
3) COO-R
1-, R wherein
1for alkylidene group;
Wavy line represents repetitive extension or the hydrogen with structure division shown in above formula (1).
More preferably, the invention provides a kind of light curing nano hybrid material with photocuring reaction group, its structure comprises with the structure division shown in following formula (1):
Formula (1)
Wherein, R is photocuring reaction group CH
2=C (CH
3) COO-R
1-, R wherein
1for alkylidene group, R
1be preferably propylidene-CH
2cH
2cH
2-, R is preferably CH
2=C (CH
3) COO-CH
2cH
2cH
2-;
Wavy line represents repetitive extension or the hydrogen with structure division shown in above formula (1).
The described light curing nano hybrid material with photocuring reaction group is prepared by the following method: under nitrogen atmosphere, under catalyzer exists, in organic solvent, at the temperature of 20-80 ℃, make to have siloxanes and the deionized water reaction of photocuring reaction group, the polycondensation of gained hydrolysate, solvent and other small molecules in reaction system removed in decompression, obtain having the light curing nano hybrid material of photocuring reaction group, wherein, the siloxanes with photocuring reaction group is selected from vinylsiloxane, (methyl) acryloyl-oxy radical siloxane, preferred γ-methacryloxypropyl trimethoxy silane.
The light curing nano hybrid material that has photocuring reaction group provided by the invention, it has space crosslinking structure, the space crosslinking structure of Siliciumatom and Sauerstoffatom mode bonding as shown in above formula (1) specifically, wherein, photocuring reaction radicals R of bonding on each Siliciumatom, and on each Siliciumatom, go back three Sauerstoffatoms of bonding, two Siliciumatoms of bonding on each Sauerstoffatom, in this way in spatial spread.Because this hybrid material has the photocuring reaction group of high-content like this, so the photocuring activity of this light curing nano hybrid material is very high.
In the light curing nano hybrid material with photocuring reaction group provided by the invention, the number of the structure division shown in above formula (1) can, from several to tens hundreds ofs even, as required, can be controlled the repetition number of this structure division.Particularly, after siloxanes reacts with deionization hydrolysis, the polycondensation time of controlled hydrolysis product just can be controlled the repetition number of this structure division, and the polycondensation time of hydrolysate is longer, and the repetition number of this structure division is higher.
The light curing nano hybrid material with photocuring reaction group provided by the invention consists of the structure division shown in above formula (1) substantially.The meaning of term used herein " substantially " refers to that the structure division shown in above formula (1) accounts for the more than 95% of light curing nano hybrid material, even more than 99%.
On the other hand, the invention provides the above-mentioned preparation method with the light curing nano hybrid material of photocuring reaction group, the method comprises: under nitrogen atmosphere, under catalyzer exists, in organic solvent, at the temperature of 20-80 ℃, make to have siloxanes and the deionized water reaction of photocuring reaction group, the polycondensation of gained hydrolysate, solvent and other small molecules in reaction system removed in decompression, obtain having the light curing nano hybrid material of photocuring reaction group, wherein, the siloxanes with photocuring reaction group is selected from vinylsiloxane, (methyl) acryloyl-oxy base silane, preferred γ-methacryloxypropyl trimethoxy silane.
According in the preparation method's of the light curing nano hybrid material with photocuring reaction group of the present invention preferred embodiment, the siloxanes with photocuring reaction group is γ-methacryloxypropyl trimethoxy silane.
According in the preparation method's of the light curing nano hybrid material with photocuring reaction group of the present invention preferred embodiment, the mol ratio with siloxanes, organic solvent, deionized water and the catalyzer of photocuring reaction group is 40: 30: 1: 0.1-10: 100: 0.2: 0.01, and more preferably 30: 30: 0.3: 0.1-30: 90: 0.3: 0.05.
According in the preparation method's of the light curing nano hybrid material with photocuring reaction group of the present invention preferred embodiment, catalyzer is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Phenylsulfonic acid and methylsulphonic acid.These catalyzer may be used alone, can also be used in combination.These catalyzer can the above-mentioned hydrolysis condensation reaction with the siloxanes of photocuring reaction group of catalysis.
According in the preparation method's of the light curing nano hybrid material with photocuring reaction group of the present invention preferred embodiment, organic solvent is selected from methyl alcohol, ethanol and Virahol.These organic solvents may be used alone, can also be used in combination.In these organic solvents, the above-mentioned siloxanes with photocuring reaction group can with the deionized water reaction that is hydrolyzed, there is subsequently polycondensation.
According in the preparation method of the light curing nano hybrid material with photocuring reaction group of the present invention, temperature of reaction is 20-80 ℃, in this range of reaction temperature, described in there is photocuring reaction group the siloxanes polycondensation that can be hydrolyzed.If temperature of reaction lower than 20 ℃, causes because temperature is too low being hydrolyzed, reaction or hydrolysis reaction speed are excessively slow, if temperature of reaction is higher than 80 ℃, between active reactive group, easily react, and produce micro-crosslinked.Therefore temperature of reaction is preferably 20-80 ℃, more preferably 40-80 ℃.
According in the preparation method of the light curing nano hybrid material with photocuring reaction group of the present invention, be not particularly limited for the reaction times, as long as can generate the light curing nano hybrid material with photocuring reaction group, but the reaction times is preferably 3-60 hour, more preferably 5-48 hour, also more preferably 5-24 hour.
By preparation method of the present invention, can provide the light curing nano hybrid material with photocuring reaction group, it has good performance, is specially adapted to photo-cured coating.
Again on the one hand, the invention provides the purposes of the above-mentioned light curing nano hybrid material with photocuring reaction group in preparing photo-cured coating.
Again on the one hand, the invention provides photo-cured coating, it is prepared by the following method: at the temperature of 20-50 ℃, make the above-mentioned of 10-30 weight part there is the light curing nano hybrid material of photocuring reaction group, the monomer reactivity thinner of the light-cured resin of 40-60 weight part, 10-40 weight part,, the auxiliary agent of the free radical photo-initiation of 3-5 weight part and 1-5 weight part mixes, obtains photo-cured coating.
According in the preferred embodiment of photo-cured coating of the present invention, it is prepared by the following method: at the temperature of 20～50 ℃, above-mentioned light curing nano hybrid material, 40-50 weight part light-cured resin, 20-30 weight parts monomers reactive thinner, 4-5 weight part free radical photo-initiation and the 1-3 weight part auxiliary agent with photocuring reaction group of 10-20 weight part mixed, obtain photo-cured coating.
According in photo-cured coating of the present invention, at the temperature of 20-50 ℃, each composition can fully mix.If temperature, lower than 20 ℃, because temperature is too low, mixes and needs the long period between each composition, otherwise, if mixing temperature higher than 50 ℃, on the one hand energy expenditure is large, and easily produce micro-crosslinked, thereby affect the coating use of coating.Further, temperature is preferably 25-40 ℃, also 30-40 ℃ more preferably.
According in the preferred embodiment of photo-cured coating of the present invention, light-cured resin is selected from epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyethers (methyl) acrylic resin, polyester (methyl) acrylic resin and acroleic acid esterification polyacrylic resin.Can use separately wherein any, also can be used in combination wherein two or more.Above-mentioned resin and the light curing nano hybrid material with photocuring reaction group of the present invention have good intermiscibility, thereby are particularly suitable for using.
According in the preferred embodiment of photo-cured coating of the present invention, monomer reactivity thinner be selected from simple function-, difunctionality-and multifunctional-(methyl) acrylate monomer.Described simple function-, difunctionality-and multifunctional-(methyl) acrylate monomer can be for example Viscoat 295,1,6-hexylene glycol double methacrylate, tripropylene glycol double methacrylate, dipropylene glycol diacrylate, neopentyl glycol double methacrylate, pentaerythritol triacrylate, phthalic acid Diethylene Glycol double methacrylate, benzene oxygen ethyl propylene acid esters and ethoxylated trimethylolpropane triacrylate, preferred Viscoat 295,1,6-hexylene glycol double methacrylate, tripropylene glycol double methacrylate.Can use separately wherein any, also can arbitrary combination use wherein two or more.
In photo-cured coating according to the present invention, free radical photo-initiation can, for conventional free radical photo-initiation, be not particularly limited.As free radical photo-initiation, for example enumerate 2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone, 1-hydroxyl-ring ethyl benzophenone, 2-hydroxy-2-methyl-1-to hydroxyethyl ether phenyl-acetone, can use separately wherein any, also can arbitrary combination use wherein two or more.
In photo-cured coating according to the present invention, auxiliary agent is the usual auxiliaries of photo-cured coating, comprises such as defoamer, advection agent, oxidation inhibitor and uv-absorbing agent etc., can use the corresponding known substance of this area.As required, can use one or more in these auxiliary agents.
Come by the following examples further to explain the present invention, but embodiments of the present invention are also only not limited to these embodiment.
Embodiment 1 has light curing nano hybrid material synthetic of photocuring reaction group
To adding the ethanolic soln of 1.4 moles, 0.05 mole of deionized water, 0.01 mole hydrochloride in 0.2 molar ethylene radical siloxane, at 65 ℃, to react, reaction was carried out after 48 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 2 has light curing nano hybrid material synthetic of photocuring reaction group
To adding the ethanolic soln of 10 moles, 0.5 mole of deionized water, 0.01 mol sulfuric acid in 1 molar ethylene radical siloxane, at 40 ℃, to react, reaction was carried out after 10 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 3 has light curing nano hybrid material synthetic of photocuring reaction group
To adding the methanol solution of 3.0 moles, 0.2 mole of deionized water, 0.03 mole of phosphoric acid in 1 mole of γ-methacryloxypropyl trimethoxy silane, at 20 ℃, react, reaction was carried out after 60 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 4 has light curing nano hybrid material synthetic of photocuring reaction group
In 1 mole of γ-methacryloxypropyl trimethoxy silane, add the b propanol solution of 10 moles, 0.3 mole of deionized water, 0.01 mole of methylsulphonic acid, at 50 ℃, react, reaction was carried out after 35 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 5 has light curing nano hybrid material synthetic of photocuring reaction group
In 1 molar ethylene radical siloxane, add the ethanolic soln of 8.5 moles, 0.18 mole of deionized water, the 0.07 mole of Phenylsulfonic acid of take is catalyzer, at 80 ℃, reacts, and reaction was carried out after 9 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 6 has light curing nano hybrid material synthetic of photocuring reaction group
In 1 mole of γ-methacryloxypropyl trimethoxy silane, add the b propanol solution of 7.0 moles, 0.03 mole of deionized water, take 0.002 mol sulfuric acid as catalyzer, at 80 ℃, react, reaction was carried out after 12 hours, removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 7 has light curing nano hybrid material synthetic of photocuring reaction group
In 1 molar ethylene radical siloxane, add the ethanolic soln of 6.0 moles, 0.4 mole of deionized water, take 0.004 molar nitric acid as catalyzer, at 70 ℃, react, reaction was carried out after 17 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 8 has light curing nano hybrid material synthetic of photocuring reaction group
The ethanolic soln of 2.5 moles, 0.1 mole of deionized water will be added in 1 mole of γ-methacryloxypropyl trimethoxy silane, take 0.06 molar nitric acid as catalyzer, at 20 ℃, react, reaction was carried out after 56 hours, removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 9 has light curing nano hybrid material synthetic of photocuring reaction group
In 1 molar ethylene radical siloxane, add the ethanolic soln of 2.5 moles, 0.2 mole of deionized water, the 0.007 mole of Phenylsulfonic acid of take is catalyzer, at 65 ℃, reacts, and reaction was carried out after 30 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Embodiment 10 has light curing nano hybrid material synthetic of photocuring reaction group
To adding the ethanolic soln of 1.4 moles, 0.05 mole of deionized water, 0.01 mole hydrochloride in 0.2 mole of γ-methacryloxypropyl trimethoxy silane, at 65 ℃, react, reaction was carried out after 48 hours, and removal of solvent under reduced pressure and other small molecules, obtain product.
Its
1h NMR spectrogram as shown in Figure 5 B.Known by Fig. 5 A and Fig. 5 B, gamma-methyl allyl acyloxypropyl trimethoxysilane monomer is after hydrolytic condensation, methoxy group reduces greatly at δ=3.2ppm place resonance peak, shows through after abundant hydrolysis-condensation reaction, and the methoxyl group of the overwhelming majority has all reacted.
Shown in its infrared spectra Fig. 6, as we can see from the figure, 1715cm
-1near peak be-C=O shrinks vibration absorption peak, 1637cm
-1be-C=C-stretching vibration absorption peak.Show to have photosensitive group in system, can carry out photocuring reaction.At 1100cm
-1～1000cm
-1what occur is-the stretching vibration absorption peak of Si-O-Si-key; At 815cm
-1near be-the flexural vibration absorption peak of Si-O-Si-key; At 500cm
-1near place, be-the rocking vibration absorption peak of Si-O-Si-key; 1169cm
-1near be the absorption peak of Si-O-C key, show the formation of Si-O-C hybridization network structure in system; These all illustrate that hydrolysis-condensation reaction has occurred gamma-methyl allyl acyloxypropyl trimethoxysilane.
Its
29si NMR is as shown in figure B.Known by Fig. 7 A and Fig. 7 B, gamma-methyl allyl acyloxypropyl trimethoxysilane monomer is T at δ=the unimodal of-43ppm place
0[Si (OCH
3)
3] vibration peak, Siliciumatom connects three methoxy groups.After hydrolysis-condensation reaction, there is T
1[(CH
3o)
2siOSi, (HO)
2siOSi-, HO (CH
3o) SiOSi] singlet, also go out T simultaneously
2[(CH
3o) Si (OSi)
2, (HO) Si (OSi)
2] doublet and T
3[Si (OSi)
3] triplet, they have replaced T
0[Si (OCH
3)
3].Hydrolysis condensation product contains T3 structure, shows to contain in product high branched structure or ring texture.Just because of the polymolecularity of gamma-methyl allyl acyloxypropyl trimethoxysilane, make Siliciumatom in a lot of different chemical micro-environments, therefore, at δ=-60ppm place, there is broad peak.
Its transmission electron microscope photo as shown in Figure 8, has Fig. 8 known, and nano-particles size, in 70～80nm left and right, the phenomenon that nanoparticle is assembled does not occur
The preparation of embodiment 11 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 20g, HDDA (1, 6-hexylene glycol double methacrylate) 13g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.7g defoamer Dow Corning 163, 1g flow agent BYK-UV3500, 0.7g surface active agent BYK2700, at 30 ℃, stir, the product 20g and the bisphenol A epoxy acrylate 40g that add again embodiment 1, evenly mix, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on PVC buckle, under the 500W high voltage mercury lamp that to be placed in apart from PVC buckle surface vertical range be 25cm, irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 12 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 12g, DPGDA (two contracting propylene glycol double methacrylates) 20g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 1g, 0.5g flow agent BYK 361,0.5g defoamer Airex900, the product 13g and the bisphenol A epoxy acrylate 50g that add again embodiment 2, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 13 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent HDDA (1,6-hexylene glycol double methacrylate) 12g, DPGDA (two contracting propylene glycol double methacrylates) 12g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, 0.6g defoamer BYK 380,0.7g flow agent BYK3510, the product 10g and urethane (methyl) the acrylic resin 60g that add again embodiment 9, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 14 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent HDDA (1, 6-hexylene glycol double methacrylate) 17g, TMPTA (Viscoat 295) 23g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.7g defoamer Deuchem 2700, 0.7g flow agent Wacker Addid 130, the product 12g and polyester (methyl) the acrylic resin 40g that add again embodiment 1, at 30 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 15 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent DPGDA (two contracting propylene glycol double methacrylates) 8g, HDDA (1,6-hexylene glycol double methacrylate) 9g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 3g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 1g, 0.8g defoamer Dow Corning 163,0.7g flow agent TegoFlow 300,0.4g surface active agent BYK2700, the product 30g and polyester (methyl) the acrylic resin 46g that add again embodiment 8, at 40 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 16 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 10g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 1g, 0.6g defoamer Dow Corning 163,0.7g flow agent Tego 2250, the product 25g and polyester (methyl) the acrylic resin 60g that add again embodiment 7, at 25 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 17 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent thinner TPGDA (tri (propylene glycol) diacrylate) 10g, HDDA (1, 6-hexylene glycol double methacrylate) 10g, TMPTA (Viscoat 295) 20g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.7g defoamer Dow Corning163, 1g flow agent BYK361, the product 10g and polyester (methyl) the acrylic resin 47g that add again embodiment 6, at 25 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 18 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 12g, DPGDA (two contracting propylene glycol double methacrylates) 8g, HDDA (1, 6-hexylene glycol double methacrylate) 7g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, 0.7g defoamer Deuchem 3600, 0.8g flow agent Tego 2250, the product 20g and polyethers (methyl) the acrylic resin 45g that add again embodiment 8, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 19 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent DPGDA (two contracting propylene glycol double methacrylates) 10g, HDDA (1, 6-hexylene glycol double methacrylate) 7g, TMPTA (Viscoat 295) 15g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 1g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.8g defoamer Dow Corning 163, 1.2g flow agent Wacker Addid200, 1g surface active agent BYK2700, the product 25g and polyethers (methyl) the acrylic resin 40g that add again embodiment 9, at 40 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 20 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent HDDA (1, 6-hexylene glycol double methacrylate) 12g, TMPTA (Viscoat 295) 10g, DPGDA (two contracting propylene glycol double methacrylates) 5g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 1g, 0.7g defoamer Dow Corning 163, 0.9g flow agent Deuchem 3600, the product 30g and urethane (methyl) the acrylic resin 38g that add again embodiment 2, at 20 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 21 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 11g, DPGDA (two contracting propylene glycol double methacrylates) 13g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, 0.9g defoamer Dow Corning 163,1.3g flow agent BYK-UV3500, the product 20g and urethane (methyl) the acrylic resin 50g that add again embodiment 5, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 22 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 16g, HDDA (1,6-hexylene glycol double methacrylate) 10g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 3g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.7g defoamer SolutiaPC-1344,1g flow agent BYK-UV3500, the product 15g and urethane (methyl) the acrylic resin 50g that add again embodiment 1, at 30 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 23 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent HDDA (1,6-hexylene glycol double methacrylate) 15g, TMPTA (Viscoat 295) 18g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 3g, 0.9g defoamer BYK 380,1g flow agent BYK330, the product 16g and the bisphenol A epoxy acrylate 45g that add again embodiment 3, at 40 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 24 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TPGDA (tri (propylene glycol) diacrylate) 5g, TMPTA (Viscoat 295) 5g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, 0.5g defoamer Deuchem 2700,1g flow agent Wacker Addid130,1.2g surface active agent BYK200, the product 22g and polyester (methyl) the acrylic resin 60g that add again embodiment 4, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 25 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TPGDA (tri (propylene glycol) diacrylate) 7g, TMPTA (Viscoat 295) 15g, HDDA (1, 6-hexylene glycol double methacrylate) 6g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 1g, 0.1g defoamer Solutia PC-1344, 0.7g flow agent BYK3510, 0.5g surface active agent BYK2700, evenly, the product 13g and polyester (methyl) the acrylic resin 50g that add again embodiment 5, at 20 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 26 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 20g, DPGDA (two contracting propylene glycol double methacrylates) 18g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 184 (1-hydroxyl-ring ethyl benzophenone) 2g, 0.4g defoamer BYK380,0.7g flow agent Tego Flow300, the product 17g and polyester (methyl) the acrylic resin 40g that add again embodiment 6, at 35 ℃, stir, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on base material, is placed under 500W high voltage mercury lamp and irradiates 30s, obtain ultraviolet light polymerization and film.
The preparation of embodiment 27 photo-cured coating
Under lucifuge condition, in being housed, the container of agitator adds monomer diluent TMPTA (Viscoat 295) 20g, HDDA (1, 6-hexylene glycol double methacrylate) 13g, light trigger 1173 (2-hydroxyl-2 methyl isophthalic acid-phenyl-acetone) 2g, light trigger 2959 (2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone) 2g, 0.7g defoamer DowCorning163, 1g flow agent BYK-UV3500, 0.7g surface active agent BYK2700, at 30 ℃, stir, add again products therefrom 20g and bisphenol A epoxy acrylate 40g in embodiment 10, evenly mix, obtain ultraviolet-curing paint.
The ultraviolet-curing paint preparing is evenly applied on PVC buckle, under the 500W high voltage mercury lamp that to be placed in apart from PVC buckle surface vertical range be 25cm, irradiates 26s, the ultraviolet light polymerization that obtains completion of cure is filmed.
By embodiment and preferred embodiment, describe the present invention above; but should understand; scope of the present invention is not limited to above-mentioned explanation; in the case of without departing from the spirit and scope of protection of the present invention; those skilled in the art can do various modifications, replacement or improvement to the present invention, and these equivalent form of values are equally in the application's appended claims limited range.
Claims (2)
1. a method of preparing the light curing nano hybrid material with photocuring reaction group, described in there is photocuring reaction group light curing nano hybrid material structure comprise with the structure division shown in following formula (1):
Wherein, R is photocuring reaction group CH
2=CH-or CH
2=C (CH
3) COO-CH
2cH
2cH
2-;
Wavy line represents repetitive extension or the hydrogen with structure division shown in above formula (1);
The method comprises: under nitrogen atmosphere, under catalyzer exists, in organic solvent, at the temperature of 20-80 ℃, make to have siloxanes and the deionized water reaction of photocuring reaction group, the polycondensation of gained hydrolysate, solvent and other small molecules in reaction system removed in decompression, obtain having the light curing nano hybrid material of photocuring reaction group, wherein, siloxanes with photocuring reaction group is selected from vinylsiloxane and γ-methacryloxypropyl trimethoxy silane
Wherein, described catalyzer is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Phenylsulfonic acid and methylsulphonic acid;
Wherein, the mol ratio with siloxanes, organic solvent, deionized water and the catalyzer of photocuring reaction group is 40:30:1:0.1-10:100:0.2:0.01;
Wherein, organic solvent is selected from methyl alcohol, ethanol and Virahol.
2. method according to claim 1 wherein, is 30:30:0.3:0.1-30:90:0.3:0.05 with the mol ratio of siloxanes, organic solvent, deionized water and the catalyzer of photocuring reaction group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110276267.XA CN102993440B (en) | 2011-09-16 | 2011-09-16 | Photocuring nano hybrid material, and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110276267.XA CN102993440B (en) | 2011-09-16 | 2011-09-16 | Photocuring nano hybrid material, and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102993440A CN102993440A (en) | 2013-03-27 |
| CN102993440B true CN102993440B (en) | 2014-08-13 |
Family
ID=47922592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110276267.XA Active CN102993440B (en) | 2011-09-16 | 2011-09-16 | Photocuring nano hybrid material, and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993440B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865271B (en) * | 2014-03-20 | 2017-04-05 | 北京化工大学 | A kind of preparation method of the modified organosilicon heat conductive electronic pouring sealant of nano-hybrid material |
| CN104513607B (en) * | 2014-12-24 | 2016-09-28 | 浙江佑谦特种材料有限公司 | A kind of wear-resisting anti-fog coating of photocuring and construction method thereof |
| CN108586754A (en) * | 2018-05-14 | 2018-09-28 | 中科广化（重庆）新材料研究院有限公司 | A kind of hyperbranched silicone acrylic resin and the preparation method and application thereof |
| CN109776802B (en) * | 2019-01-11 | 2022-01-14 | 广州艾科普新材料有限公司 | Preparation method of methacryloxypropyl trialkoxy polysilsesquioxane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1968992A (en) * | 2004-07-16 | 2007-05-23 | 陶氏康宁公司 | Radiation sensitive silicone resin composition |
-
2011
- 2011-09-16 CN CN201110276267.XA patent/CN102993440B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1968992A (en) * | 2004-07-16 | 2007-05-23 | 陶氏康宁公司 | Radiation sensitive silicone resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993440A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100378174C (en) | Organosilicon resin composition and molded organosilicon resin body | |
| CN101974143B (en) | Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof | |
| CN101070329A (en) | Phosphates acrylate and its synthesizing method and use | |
| CN100503757C (en) | Ultraviolet light solidifying paint containing POSS and its preparation method | |
| CN101967342B (en) | Ultraviolet curing coating | |
| CN102993440B (en) | Photocuring nano hybrid material, and synthesis method and application thereof | |
| CN100339408C (en) | Silicone resin compositions and moldings thereof | |
| CN102925052B (en) | Double-curing vacuum plating UV (Ultraviolet) coating finish | |
| JP2006028514A (en) | New polymeric initiator | |
| CN1754915A (en) | Silicone resin composition and molded product thereof | |
| CN102232081A (en) | Silsesquioxane photoinitiators | |
| CN102030884A (en) | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof | |
| CN102775593B (en) | Catalyst composite and method for preparing polycarbonate | |
| Li et al. | One-step synthesis of novel multifunctional silicone acrylate prepolymers for use in UV-curable coatings | |
| CN104271623A (en) | Silicon-containing (meth)acrylate compounds | |
| CN101171280A (en) | Radiation curable methacrylate polyesters | |
| CN102046708B (en) | Modification of the surface chemistry of macromolecular species in the presence of a conjugated guanidine | |
| CN112940203A (en) | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof | |
| Liu et al. | Novel UV-curable epoxy resins modified with alkyne: Cured through thiol-yne click reaction | |
| CN101418148A (en) | Method for producing ultraviolet curing coating | |
| US20200299462A1 (en) | Method for preparing ultraviolet (uv) curing polymethyl siloxane containing acrylate structure | |
| EP1985646A2 (en) | Polysilane compound, synthesis method thereof, ultraviolet-ray curable ink composition using the polysilane compound, inkjet recording method using the ultraviolet ray-curable ink composition, and ink container and inkjet recording apparatus containing the ultraviolet ray-curable ink composition | |
| CN101418144A (en) | Make the method for ultraviolet-curing paint | |
| CN101085820A (en) | Acrylic acid esterified acrylic ester macromolecule and its synthetic method and application | |
| CN110183664A (en) | A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |