CN103113534A - Preparation method of photo-curing organic-inorganic hybrid prepolymer and application thereof - Google Patents
Preparation method of photo-curing organic-inorganic hybrid prepolymer and application thereof Download PDFInfo
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- CN103113534A CN103113534A CN2013100226963A CN201310022696A CN103113534A CN 103113534 A CN103113534 A CN 103113534A CN 2013100226963 A CN2013100226963 A CN 2013100226963A CN 201310022696 A CN201310022696 A CN 201310022696A CN 103113534 A CN103113534 A CN 103113534A
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Abstract
The invention relates to a preparation method of photo-curing organic-inorganic hybrid prepolymer. The preparation method comprises the following steps: preparation of an organic modifier, wherein the organic modifier is obtained through the addition reaction of organosiloxane including active hydrogen atoms and multifunctional acrylate compound in the presence of catalysts; and (2) preparation of the prepolymer, wherein the orthosilicate and the modifier are cohydrolysis condensed in the presence of acid or base catalysts in the mixed solvent of water and alcohol, and then the modified nano silicon dioxide particle sol is obtained after purification. A photo-curing organic-inorganic hybrid prepolymer is prepared by the preparation method of the photo-curing organic-inorganic hybrid prepolymer. Paint added with the photo-curing organic-inorganic hybrid prepolymer is provided, the mechanical capacity of a film formed by the paint is significantly improved, and meanwhile, the water resistance and the ageing resistance of the film are also significantly improved.
Description
Technical field
The present invention relates to a kind of preparation method and application of organic-inorganic hybrid nanometer material, relate in particular to a kind of preparation method and application of photocuring organic inorganic hybridization prepolymer.
Background technology
It is a green science and technology that radiation curing technology is described as by the whole world,, what its widespread use brought is a revolution in surface working field.Since nineteen sixty-eight Bayer A.G's release UV-light (UV) is coating material solidified, come, because its curing speed is fast, production efficiency is high and, because irradiation time is short, dust pollution is few; Save space and space; Solidification value is low, saves the energy, and running cost is low; Numerous outstanding advantages such as VOC discharge is low and obtain broad research and promote rapidly; in the seventies and eighties in 20th century developed country and after area experienced a fast development stage; active demand due to the strong support that has obtained protection of the environment and eubiosis rules and fast-developing industry member; still be growing on and at present and, its Application Areas is still in continuous expansion.
Hybrid inorganic-organic materials (OIHMS) combines the good characteristic of organic polymer and inorganic materials, has good mechanical property, resistance to elevated temperatures and good snappiness.In addition, hybrid material can be controlled the structure of material with molecular level, makes the performance of material produce abundant variation.Different from general composite organic-inorganic material, on this compound nanometer level often in coating, the yardstick of disperse phase has at least one dimension to reach nano level.Like this, the mutual dispersiveness of organic phase and inorganic phase is higher, even disperses yardstick to reach the level of molecule, atom, and two alternate interactions are stronger.For so nano combined, custom is referred to as hydridization (Hybrid).Make organic resin and the compound coating obtained of inorganic materials by hybridization technique, be called organic-inorganic hybridization coating.The hybrid inorganic-organic photo-cured coating has snappiness and rigidity concurrently, between inorganic phase and organic phase with covalent bonds, the two-phase interface of organic and inorganic light solidifying coating surface is tightr, thereby make coating finer and close, hardness and the wear resistance of film all are greatly improved, paint film corrodibility makes moderate progress, and obviously to be better than organic polymer higher due to the thermotolerance of inorganic nano-particle and ageing-resistant performance, therefore also can significantly promote the heat-resisting and ageing-resistant performance of whole paint film.
Summary of the invention
The objective of the invention is, a kind of organic inorganic hybridization prepolymer of uV curable is provided, add it to mechanical property, water tolerance and ageing resistance that in coating, improvement is filmed.
For reaching above technical purpose, the technical solution used in the present invention is as follows,
A kind of preparation method of photocuring organic inorganic hybridization prepolymer, it comprises the following steps:
(1) preparation of organic modifiers: the addition under the existence of catalyzer of the organo-siloxane that contains active hydrogen atom and the acrylic compound of polyfunctionality obtains organic modifiers;
(2) preparation of photocuring organic inorganic hybridization prepolymer: ortho-silicate and aforesaid organic modifiers be cohydrolysis condensation in water and pure mixed solvent under the existence of acid or alkaline catalysts, obtains the modified manometer silicon dioxide colloidal sol after purifying.
Particularly, the temperature of reaction of step (1) is 23-50 ℃.The NH group that is masked as its product organic modifiers that step (1) reacts completely or the infrared signature absorption peak of SH group disappear.
With stoichiometric ratio, calculate, described in step (1), the acrylic compound of polyfunctionality is 55-75%, and the described organo-siloxane containing active hydrogen atom is 12-22%, and catalyzer is 0.7-1.0 ‰.The acrylic compound of described polyfunctionality is the hexa-methylene diacrylate, the tetramethylene diacrylate, the cyclohexyl diacrylate, bisphenol a diacrylate, bisphenol-a epoxy acrylate, the tirethylene glycol diacrylate, the triethylene Glycol diacrylate, the tripropylene glycol diacrylate, Viscoat 295, two contracting trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythrityl ether six acrylate, the Viscoat 295 of ethoxylation, the pentaerythritol triacrylate of ethoxylation, the ethoxylation tetramethylol methane tetraacrylate, aliphatic urethane acrylate, aromatic urethane acrylate, the trimeric cyanamide triacrylate, any one of trimeric cyanamide six acrylate and polyester triacrylate.
The described organo-siloxane containing active hydrogen atom is the gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-(β-aminoethyl)-γ aminopropyltriethoxy silane, any one of γ mercaptopropyitrimethoxy silane and γ-sulfydryl propyl-triethoxysilicane.
Described catalyzer is triethylamine, dimethylaminoethanol, trolamine, 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene, benzyltriethylammoinium chloride, triethylamine, hexahydropyridine, sodium hydroxide, sodium ethylate, 1,1,3,3-tetramethyl guanidine and 1, any one of 5-diazacyclo [4,3,0]-nine carbon-5-alkene.
Further, the temperature of reaction of step (2) is room temperature, the reaction times be 24 hours or more than.
The modified manometer silicon dioxide colloidal sol median size of step (2) gained is 1-500nm, and dispersity is 0.18, and moisture is less than or equal to 0.5%, and solids content is 50wt%.
With stoichiometric ratio, calculate, described in step (2), ortho-silicate is 15-35%, and the described organic modifiers obtained by step (1) of use is 12-22%, and described acid or alkaline catalysts are 1-2.5 ‰.Described ortho-silicate comprises the combination of any one or any two or more (containing two kinds) of original quanmethyl silicate, tetraethyl orthosilicate and orthosilicic acid four butyl esters.
Described acid catalyst is any one of formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and oxalic acid.
Described alkaline catalysts is any one of ammoniacal liquor, potassium hydroxide and sodium hydroxide.
A kind of photocuring organic inorganic hybridization prepolymer, it adopts preparation method's preparation of photocuring organic inorganic hybridization prepolymer as the aforementioned.
A kind of coating that adds aforesaid photocuring organic inorganic hybridization prepolymer, wherein, in parts by weight, described coating comprises 1 part of light trigger, matrix resin 20-34 part, reactive thinner 9-15 part, 1 part of auxiliary agent, 49 parts of solvents and aforementioned photocuring organic inorganic hybridization prepolymer 10-40 part.
Particularly, described matrix resin comprise high functionality polyurethane acrylate resin and in the epoxy acrylic resin of low functionality.
Compared with prior art, the present invention has following advantage: but organic inorganic hybridization prepolymer provided by the invention rolls into one the unit structure of inorganic silicon dioxide nano particle and UV-light photocuring, specifically, the organic group of grafting uV curable on the inorganic silicon dioxide particle surface, form the organic inorganic hybridization compound of covalent linkage coupling, and, this organic inorganic hybridization prepolymer is to be prepared from by the organic modifiers with uV curable group and siloxane groups and the condensation of ortho-silicate cohydrolysis, the coating that has added this prepolymer can significantly improve the mechanical property that it is filmed, water tolerance and the ageing resistance of filming also had to obvious improvement simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The preparation of organic modifiers A1:
Prolong is being housed, agitator, add 592 weight part Viscoat 295s (TMPTA) in the four-hole round-bottomed flask of thermometer and constant pressure funnel, heated and stirred is warming up to 23 ℃, slowly drip 221 weight part γ aminopropyltriethoxy silanes (APTES) in the situation that stir by dropping funnel, 0.7 weight part 1, 8-diazabicylo [5, 4, 0] mixing solutions of the organic solvent of 11 carbon-7-alkene (DBU) and 187 weight parts, controlling a speed makes mixed solution dropwise in 3 hours, continue the constant temperature stirring reaction, the reaction process sampling, by NH group (the characteristic absorbance 3300-3500cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described NH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, naming this product is organic modifiers solution A 1.
Embodiment 2
The preparation of organic modifiers A2:
Prolong is being housed, agitator, add 1156 weight part dipentaerythrityl ether six acrylate (DPHA) in the four-hole round-bottomed flask of thermometer and constant pressure funnel, heated and stirred is warming up to 40 ℃, slowly drip 221 weight part γ aminopropyltriethoxy silanes (APTES) in the situation that stir by dropping funnel, 1.38 the mixing solutions of the organic solvent of weight part triethylamine (TEA) and 223 weight parts, controlling a speed makes mixed solution dropwise in 6 hours, continuing constant temperature stirs, the reaction process sampling, by NH group (the characteristic absorbance 3300-3500cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described NH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, reaction terminating when the infrared signature absorption peak of described two groups disappears, naming this product is organic modifiers solution A 2.
Embodiment 3
The preparation of organic modifiers A3:
Prolong is being housed, agitator, add 578 weight part dipentaerythrityl ether six acrylate (DPHA) in the four-hole round-bottomed flask of thermometer and constant pressure funnel, heated and stirred is warming up to 50 ℃, slowly drip 196 weight part γ mercaptopropyitrimethoxy silanes (SPTMS) in the situation that stir by dropping funnel, 0.8 weight part 1, 5-diazacyclo [4, 3, the mixing solutions of the organic solvent of 0]-nine carbon-5-alkene (DBN) and 226 weight parts, controlling a speed makes mixed solution dropwise in 4 hours, continuing constant temperature stirs, the reaction process sampling, by SH group (the characteristic absorbance 2500-2600cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described SH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, naming this product is organic modifiers solution A 3.
Embodiment 4
The preparation of organic modifiers A4:
Prolong is being housed, agitator, add 1200 weight part trimeric cyanamide triacrylate (BMA-200 in the four-hole round-bottomed flask of thermometer and constant pressure funnel, Bomar company product), heated and stirred is warming up to 50 ℃, slowly drip 221 weight part γ aminopropyltriethoxy silanes (APTES) in the situation that stir by dropping funnel, 1.5 weight part 1, 1, 3, the mixing solutions of the organic solvent of 3-tetramethyl guanidine (TMG) and 179 weight parts, controlling a speed makes mixed solution dropwise in 5 hours, continuing constant temperature stirs, the reaction process sampling, by NH group (the characteristic absorbance 3300-3500cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described NH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, naming this product is organic modifiers solution A 4.
Embodiment 5
The preparation of organic modifiers A5:
Prolong is being housed, agitator, add 1000 wt fat family urethane six acrylate (EBECRYL1290N in the four-hole round-bottomed flask of thermometer and constant pressure funnel, Cytec company product), heated and stirred is warming up to 50 ℃, slowly drip 196 weight part γ mercaptopropyitrimethoxy silanes (SPTMS) in the situation that stir by dropping funnel, 1.2 the mixing solutions of the organic solvent of weight part hexahydropyridine and 304 weight parts, controlling a speed makes mixed solution dropwise in 5 hours, continuing constant temperature stirs, the reaction process sampling, by SH group (the characteristic absorbance 2500-2600cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described SH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, naming this product is organic modifiers solution A 5.
Embodiment 6
The preparation of organic modifiers A6:
Prolong is being housed, agitator, add 1500 weight part bisphenol-a epoxy acrylate (EBECRYL600 in the four-hole round-bottomed flask of thermometer and constant pressure funnel, Cytec company product) heated and stirred is warming up to 30 ℃, slowly drip 264 weight part N-(β-aminoethyl)-γ aminopropyltriethoxy silane (DEAPTES) in the situation that stir by dropping funnel, 1.8 the mixing solutions of the organic solvent of parts by weight of ethanol sodium and 236 weight parts, controlling a speed makes mixed solution dropwise in 8 hours, continuing constant temperature stirs, the reaction process sampling, by NH group (the characteristic absorbance 3300-3500cm in this sample of examination of infrared spectrum
-1), when the infrared signature absorption peak of described NH group disappears, show that reaction finishes, obtain faint yellow transparent thickness product, naming this product is organic modifiers solution A 6.
Embodiment 7
The organic inorganic hybridization prepolymer P1 preparation of uV curable:
The organic modifiers solution A 1 and the required total ethanol of part that add tetraethyl orthosilicate (TEOS), described embodiment 1 preparation in the four-hole round-bottomed flask of prolong, agitator, thermometer and constant pressure funnel is housed, be uniformly mixed, under room temperature, in the situation that stir the mixed solution that slowly drips deionized water, remainder ethanol and proper catalyst by dropping funnel, controlling a speed makes mixed solution at the uniform velocity dropwise in 24 hours, continue the constant temperature stirring reaction to having reacted, obtain being the translucent colloidal sol product of blue-opalescent.Described product is transferred in single necked round bottom flask after removing by filter a small amount of solid micelle, add appropriate organic solvent, the organic inorganic hybridization prepolymer colloidal sol that ethanol in this product and residual moisture content obtain the uV curable that organic solvent disperses is removed in underpressure distillation, be labeled as P1, the about 35nm of described colloidal sol median size, dispersity 0.18(dynamic light scattering method is measured), moisture content≤0.5%, the about 50wt% of solid content content.
Embodiment 8 ~ 12
The organic inorganic hybridization prepolymer P2 of uV curable ~ P6 preparation, remove the corresponding A2 ~ A6 that changes into of organic modifiers, and its preparation process is identical with embodiment 7, and its synthesizing formula and product essential information are in Table 1.
Embodiment 13
Coating containing described photocuring organic inorganic hybridization prepolymer P1 ~ P6:
According to the consumption of described each composition of coating shown in table 2, at first, light trigger (as the I-184 of Ciba company) and partial solvent are mixed to abundant dissolving and obtain the solution that contains light trigger; Second step, the solution that contains light trigger as described in epoxy acrylic resin (as the 621-100 in Changxing), reactive thinner DPHA and the TMPTA of the polyurethane acrylate resin of six functionality (as the 7605B of Japanese synthetic chemistry), two functionality are added successively, be uniformly mixed, obtain the second mixing solutions; The 3rd step, appropriate auxiliary agent (BYK333) and appropriate solvent is even, join under agitation condition in described the second mixing solutions and mix, obtain the 3rd mixing solutions; The 4th step, add the concentration that solvent is adjusted described the 3rd mixing solutions, and rear use 400 order silks filter, and obtain coating composition; The 5th step adds respectively the described organic inorganic hybridization prepolymer P1 ~ P6 of different umbers in coating composition, makes the coating C1～C9 containing described photocuring organic inorganic hybridization prepolymer.
The preparation formula of the organic inorganic hybridization prepolymer of table 1 uV curable and the basic proterties of product
Described coating C1～C6 is adjusted to viscosity to 9s(NK-2 with thinner, 25 ℃), then be sprayed on respectively on 600mm*100mm plastics PMMA plate, levelling three minutes, at the temperature of 60 ℃, baking is 5 minutes, then at 680mj/cm
2under ability condition, the process UV-irradiation is 10 seconds, at plastic casing, obtains the paint film that thickness is 18 ± 2 μ m.Resulting paint film is carried out to a series of performance test, and the preparation formula of described coating and the results of property of filming thereof are as shown in table 2.
Wherein, sticking power test reference GB GB/T9286-1998, test is rear by 5 times of lens examination peeling paint situations; Hardness test is with reference to GB GB/T6739-1996, and wherein the load of nib is 750g, and pencil and horizontal plane angle are 45 °; 60 ° of angle gloss data of the miniature glossometer test record of BYK for glossiness; Water boiling resistance test is soaked 1h by test sample plate in 80 ℃ of deionized waters, observe paint film have or not peel off, explosion or spot, the sticking power test has or not to fall lattice; The wear-resisting test of RCA adopts special-purpose RormanRCA tester and special-purpose paper tape, applies 175g load, drives paper tape in the model surface friction, calculates the number of times that paint is revealed the exact details; The ageing-resistant test of QUV: UVA-340nm light irradiation 4h, temperature 60 C; Then place 4h in steam ambient, 50 ° of C of temperature; Test altogether 12 circulations, each circulation 8 hours, observe paint film and change and test xanthochromia △ b value.
Table 2 is containing the preparation formula of the coating of photocuring organic inorganic hybridization prepolymer P1 ~ P6 and the performance of filming thereof
From the film performance test result of table 2, can find out, the coating that has added described photocuring organic inorganic hybridization prepolymer has obviously improved the hardness of filming that this coating is made, i.e. mechanical property.In addition, it is ageing-resistant that the interpolation of described prepolymer has also suitably improved this anti-QUV(filmed) character and the character of water boiling resistance (being water tolerance), according to the kind of added prepolymer and the difference of umber, the improvement degree of anti-QUV and water boiling resistance is different.
In sum, photocuring organic inorganic hybridization prepolymer provided by the present invention has improved the mechanical property of filming, water tolerance and the ageing resistance of coating.
Above-described embodiment is preferably embodiment of the present invention; but not merely be restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within all being included in protection scope of the present invention.
Claims (16)
1. the preparation method of a photocuring organic inorganic hybridization prepolymer is characterized in that comprising the following steps:
(1) preparation of organic modifiers: the addition under the existence of catalyzer of the organo-siloxane that contains active hydrogen atom and the acrylic compound of polyfunctionality obtains organic modifiers;
(2) preparation of photocuring organic inorganic hybridization prepolymer: ortho-silicate and aforesaid organic modifiers be cohydrolysis condensation in water and pure mixed solvent under the existence of acid or alkaline catalysts, obtains the modified manometer silicon dioxide colloidal sol after purifying.
2. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 1, it is characterized in that: the temperature of reaction of step (1) is 23-50 ℃.
3. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 2, is characterized in that: the NH group that is masked as its product organic modifiers that step (1) reacts completely or the disappearance of the infrared signature absorption peak of SH group.
4. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 3, it is characterized in that: with stoichiometric ratio, calculate, described in step (1), the acrylic compound of polyfunctionality is 55-75%, the described organo-siloxane containing active hydrogen atom is 12-22%, and catalyzer is 0.7-1.0 ‰.
5. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 4, it is characterized in that: the acrylic compound of described polyfunctionality is the hexa-methylene diacrylate, the tetramethylene diacrylate, the cyclohexyl diacrylate, bisphenol a diacrylate, bisphenol-a epoxy acrylate, the tirethylene glycol diacrylate, the triethylene Glycol diacrylate, the tripropylene glycol diacrylate, Viscoat 295, two contracting trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythrityl ether six acrylate, the Viscoat 295 of ethoxylation, the pentaerythritol triacrylate of ethoxylation, the ethoxylation tetramethylol methane tetraacrylate, aliphatic urethane acrylate, aromatic urethane acrylate, the trimeric cyanamide triacrylate, any one of trimeric cyanamide six acrylate and polyester triacrylate.
6. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 4, it is characterized in that: the described organo-siloxane containing active hydrogen atom is the gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-(β-aminoethyl)-γ aminopropyltriethoxy silane, any one of γ mercaptopropyitrimethoxy silane and γ-sulfydryl propyl-triethoxysilicane.
7. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 4, it is characterized in that: described catalyzer is triethylamine, dimethylaminoethanol, trolamine, 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene, benzyltriethylammoinium chloride, triethylamine, hexahydropyridine, sodium hydroxide, sodium ethylate, 1,1,3,3-tetramethyl guanidine and 1,5-diazacyclo [4,3,0] any one of-nine carbon-5-alkene.
8. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 7, it is characterized in that: the temperature of reaction of step (2) is room temperature, the reaction times be 24 hours or more than.
9. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 8, it is characterized in that: the modified manometer silicon dioxide colloidal sol median size of step (2) gained is 1-500nm, dispersity is 0.18, and moisture is less than or equal to 0.5%, and solids content is 50wt%.
10. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 9, it is characterized in that: with stoichiometric ratio, calculate, described in step (2), ortho-silicate is 15-35%, the described organic modifiers obtained by step (1) used is 12-22%, and described acid or alkaline catalysts are 1-2.5 ‰.
11. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 10 is characterized in that: described ortho-silicate comprises any one or any two or more combination of original quanmethyl silicate, tetraethyl orthosilicate and orthosilicic acid four butyl esters.
12. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 10 is characterized in that: described acid catalyst be formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid,
Any one of phosphoric acid and oxalic acid.
13. the preparation method of photocuring organic inorganic hybridization prepolymer as claimed in claim 10 is characterized in that: described alkaline catalysts is any one of ammoniacal liquor, potassium hydroxide and sodium hydroxide.
14. a photocuring organic inorganic hybridization prepolymer is characterized in that: it adopts the preparation method's preparation as the described photocuring organic inorganic hybridization of claim 1-13 any one prepolymer.
A 15. coating that adds photocuring organic inorganic hybridization prepolymer as claimed in claim 14, it is characterized in that: in parts by weight, described coating comprises 1 part of light trigger, matrix resin 20-34 part, reactive thinner 9-15 part, 1 part of auxiliary agent, 49 parts of organic solvents and photocuring organic inorganic hybridization prepolymer 10-40 part as claimed in claim 15.
16. the coating containing photocuring organic inorganic hybridization prepolymer as claimed in claim 15 is characterized in that: described matrix resin comprise high functionality polyurethane acrylate resin and in the epoxy acrylic resin of low functionality.
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