CN102344539B - Silicon-containing double-curing group resin and preparation method thereof - Google Patents
Silicon-containing double-curing group resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses silicon-containing double-curing group resin and a preparation method thereof. Two preparation methods can be applied in the invention. The first preparation method comprises the following steps of: synthesizing acrylic epoxy monoester firstly; reacting hydroxyl silicone oil, diisocyanate and hydroxyl acrylic resin to obtain urethane acrylate with an NCO functional group at one end; and reacting two kinds of resin together to obtain silicon-containing urethane acrylate-modified epoxy monoester; and the second preparation method comprises the following steps of: synthesizing the acrylic epoxy monoester firstly; reacting dihydric alcohol, the diisocyanate and the hydroxyl acrylic resin to obtain the urethane acrylate with the NCO functional group at one end; reacting two kinds of resin together and then reacting the mixture with amino silicone oil to obtain the silicon-containing double-curing group resin. According to the invention, groups with two different curing modes are contained in the same resin molecule and the problem of compatibility of resin in different resin compounding, mixing and curing systems is solved; and on the other hand, a urethane acrylate-modified flexible chain and an organic silicon chain segment are modified so as to improve the performance of the resin.
Description
Technical field
The present invention relates to the organic polymer synthesis technical field; Especially relate to a kind of organosilicon segment that contains, and have simultaneously UV-light and cause the preparation method that radically curing group (acrylic double bond) and UV-light cause cationic curing group or thermofixation group (epoxide group) resin, this resin can be applicable to free radical-cationic violet fields such as light mixing cured type or the mixing cured type coating of radical UV curing-Re, tackiness agent, printing ink outward.
Background technology
UV-light (UV) curing technology has the characteristics such as quick, solvent-free, applicable streamline production because of it, and is rapidly developed.It can be used as the coating for surface protection of plastics, metal, timber, paper, optical fiber etc., in industrial widespread use.The UV curing system is generally by photolytic activity oligopolymer (resin), simple function group and polyfunctional group thinner, the compositions such as light trigger and auxiliary agent.The photolytic activity oligopolymer forms the three-dimensional net structure of polymkeric substance after solidifying, the physicochemical property of cured film is played to conclusive effect.
Ultraviolet light polymerization divides radically curing and cationic curing is arranged by mechanism.The advantages such as the radical UV curing system has that curing speed is fast, initiator type is many, but also exist be difficult for that surface drying, polymerization volumetric shrinkage are large, poor adhesive force, the problem such as solidification without male offspring, at present, the ultraviolet light polymerization product mainly be take the radically curing system as main.Cation photocuring system has that volumetric shrinkage is little, strong adhesion, can after fixing etc. advantage, but it also has that curing speed is slow, oligopolymer and the shortcoming such as the reactive thinner kind is few, it is mainly used in dark coating or ink system.In order to bring into play the advantage of various curing modes, avoid its shortcoming, the research of each specific admixture UV curing system has now obtained paying attention to more and more widely, the various forms of UV curing systems that mix have been developed, mainly containing UV-light free radical-cationic hybrid solidifies, UV-light free radical-Re mixes curing, UV-light-air mixes curing, it is curing etc. that UV-light-moisture mixes, these mix curing system and take mainly that two or more contains different curing groups mixed with resin as main, more rare about the report that has simultaneously two kinds of curing groups resin study on the synthesis.
In each specific admixture UV curing system, most of investigator all adopts the mixing of several resins with different curing groups, uses like this problems such as consistency is poor that exist between local solidification inequality or resin.
Resin commonly used in UV-light (UV) solidifying product has epoxy acrylate, urethane acrylate, polyester acrylate etc., these resins can meet the needs of great majority application, but in order to make cured film have some special performances, to meet special needs, can in oligopolymer, simple function group or polyfunctional group thinner, introduce the group that contains the elements such as fluorine, phosphorus, silicon, the introducing of fluorochemical monomer is mainly the surface property that improves cured film, but it is on the high side, affected its use; Synthetic and the use of phosphorous-containing monomers designs mainly for fire-retardant requirement, and the unit that is engaged at present this respect research is not a lot; Silicon-containing compound, owing to having very low temperature coefficient of viscosity, lower price, excellent interface performance, flexibility, good oilness, chemical stability and the outstanding performances such as weathering resistance preferably, obtains extensive concern and research.
The containing silicone resin that can be used in the UV curing system can be divided three classes: a kind of is to react by free radical mechanism polysiloxane, acrylate containing silicone thinner, carbamate polysiloxane or the mercaptan-alkene system etc. of the acroleic acid esterification solidified; Two kinds is the silicone resin by the curing epoxy grafting of cationic mechanism; Three classes are to cause by precious metal the special SiH-Si vinyl organosilicon solidified.
Summary of the invention
The invention provides and a kind ofly contain the organosilicon segment, and have simultaneously the preparation method that UV-light causes radically curing group (acrylic double bond) and UV-light initiation cationic curing group or thermofixation group (epoxide group) resin.Realize on the one hand in same molecular resin, having the group of two kinds of different curing methods, solved that different resins is composite mixes resin compatible problem in curing system; On the other hand, by the modification of urethane acrylate flexible chain and organosilicon segment, improved the performance of resin.
The invention provides two synthetic technology routes of resin:
The synthetic route that wherein has the A structural resin is as follows:
(1) acrylic acid epoxy monoesters segment is synthetic
In the 1000mL there-necked flask, add a certain amount of epoxy resin, stir, oil bath is to 90-110 ℃, then the catalyzer that adds 0.1-1.0%, the stopper of 0.1-0.8%, the vinylformic acid of metering, every 30min, take a sample, sodium hydroxide titration with 0.1mol/L, the transformation efficiency of carboxylic acid in the acid number of counting system and reaction process, when the acid number in reaction system is less than 3mgKOH/g, think that namely esterification completes, after cooling, be the acrylic acid epoxy monoesters, one end of molecular resin is acrylic double bond (radically curing), the other end is epoxide group (cationic curing or thermofixation), in the molecular resin segment by the reaction or self have hydroxyl, reflecting point is provided for follow-up modification is synthetic.Its following structural features:
Described epoxy resin is: bisphenol A epoxide resin and homologue thereof, novolac epoxy, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxy polyoxytrimethylene, naphthalene are a kind of in epoxy, aliphatic epoxy and alicyclic epoxy.
Described catalyzer is: N, N-dimethyl benzylamine (BDMA), N, the N-diethyl benzylamine, triethylamine, trolamine, four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, tri acetylacetonato network aluminium (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (methyl ethyl diketone) network zirconium, tri acetylacetonato network iron (III), two (methyl ethyl diketone) network copper (II), two (methyl ethyl diketone) network cobalt (II), dichloride two (methyl ethyl diketone) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (methyl ethyl diketone) network nickel (II), tri acetylacetonato network vanadium (III), two (methyl ethyl diketone) network vanadyl (IV), two (methyl ethyl diketone) network beryllium (II), a kind of in two (methyl ethyl diketone) network zinc (II).
Described stopper is: a kind of in MEHQ, Resorcinol.
(2) the silicon-based polyurethane acrylate segment is synthetic
Toward the vulcabond that adds 0.5mol in the 1000mL there-necked flask, be heated to 50-80 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil that contains the 0.5mol hydroxyl by the 0.1-0.6% of total mass, and hydroxy silicon oil is dripped in the isocyanic ester of stirring, 2h drips, and continues reaction 2h; The MEHQ that adds 0.1-0.8% in the hydroxy acrylate of 0.25mol, add above-mentioned reaction system, is warming up to 80-115 ℃ of reaction 3h, namely obtains an end to also have-the silicon-based polyurethane acrylate segment of NCO group.Its following structural features:
Described vulcabond is: a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI).
Described hydroxy silicon oil is a kind of in hydroxy radical content 0.5-10%.
Described hydroxy acrylate is: a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester.
(3) silicon-based polyurethane Acrylate Modified Epoxy acrylic monoester is synthetic
In the 500mL there-necked flask, add a certain amount of epoxy monoacrylate (1), add metering (2) silicon-based polyurethane acrylate segment (by epoxide group with-the NCO group molar ratio is that 1:0.8-1 adds), reaction 4h gets final product under 70-100 ℃, the following structural features of gained resin:
The synthetic route that wherein has the B structural resin is as follows:
(1) acrylic acid epoxy monoesters segment is synthetic
In the 1000mL there-necked flask, add a certain amount of epoxy resin, stir, oil bath is to 90-110 ℃, then the catalyzer that adds 0.1-1.0%, the stopper of 0.1-0.8%, the vinylformic acid of metering, every 30min, take a sample, sodium hydroxide titration with 0.1mol/L, the transformation efficiency of carboxylic acid in the acid number of counting system and reaction process, when the acid number in reaction system is less than 3mgKOH/g, think that namely esterification completes, after cooling, be the acrylic acid epoxy monoesters, one end of molecular resin is acrylic double bond (radically curing), the other end is epoxide group (cationic curing or thermofixation), in the molecular resin segment by the reaction or self have hydroxyl, reflecting point is provided for follow-up modification is synthetic.Its following structural features:
Described epoxy resin is: bisphenol A epoxide resin and homologue thereof, novolac epoxy, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxy polyoxytrimethylene, naphthalene are a kind of in epoxy, aliphatic epoxy and alicyclic epoxy.
Described catalyzer is: N, N-dimethyl benzylamine (BDMA), N, the N-diethyl benzylamine, triethylamine, trolamine, four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, tri acetylacetonato network aluminium (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (methyl ethyl diketone) network zirconium, tri acetylacetonato network iron (III), two (methyl ethyl diketone) network copper (II), two (methyl ethyl diketone) network cobalt (II), dichloride two (methyl ethyl diketone) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (methyl ethyl diketone) network nickel (II), tri acetylacetonato network vanadium (III), two (methyl ethyl diketone) network vanadyl (IV), two (methyl ethyl diketone) network beryllium (II), a kind of in two (methyl ethyl diketone) network zinc (II).
Described stopper is: a kind of in MEHQ, Resorcinol.
(2) the urethane acrylate segment is synthetic
Toward the vulcabond that adds 2mol in the 1000mL there-necked flask, be heated to 50-80 ℃, dibutyl tin dilaurate joins in the dibasic alcohol of 1mol by the 0.1-0.6% of total mass, and dibasic alcohol is dripped in the isocyanic ester of stirring, 2h drips, and continues reaction 2h; The MEHQ that adds 0.1-0.8% in the hydroxy acrylate of 1-1.1mol, add above-mentioned reaction system, is warming up to 80-115 ℃ of reaction 3h, namely obtains an end to also have-the urethane acrylate segment of NCO group.Its following structural features:
Described vulcabond is: a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI).
Described dibasic alcohol is: polyether Glycols, polyester diol, propylene glycol, neopentyl glycol, BDO, 1, a kind of in 6-hexylene glycol, polyoxyethylene glycol (molecular weight 200,400,600,800,1000,2000,4000 etc.).
Described hydroxy acrylate is: a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester.
(3) urethane acrylate modified epoxy acrylic monoester is synthetic
In the 500mL there-necked flask, add a certain amount of epoxy monoacrylate (1), add metering (2) urethane acrylate segment (by epoxide group with-the NCO group molar ratio is that 1:0.8-1 adds), reaction 4h gets final product under 70-100 ℃, the following structural features of gained resin:
(4) aminosilane or amino-modified silicone resin is synthetic
In the 1000mL flask, add urethane acrylate modified epoxy acrylic monoester resin (3), the aminosilane or the amido silicon oil (being that 1:0.5-1 adds by epoxide group and amino mol ratio) that add metering, between 50-100 ℃, the reaction times is 16h.Acrylate and aminosilane or amido silicon oil can obtain the silicon-containing double-curing group resin with following structure by Michael reaction:
The resin with double curing groups synthesized by aforesaid method, relatively hard epoxy segment is arranged in resinous molecular structure, relatively pliable and tough urethane segment is arranged, and siliceous segment arranged, have simultaneously acrylic double bond (UV-light radically curing) and two kinds of functional groups of epoxy (UV-light cationic curing or thermofixation), can be mixed with on this basis free radical-cationic hybrid photocuring system, perhaps be mixed with the mixing cured system of UV-light free radical-Re, can effectively bring into play the advantage of each segment, make the cured film overall performance improve and improve.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment 1:
The first step, in the 1000mL there-necked flask, add 520g bisphenol-A epoxy (epoxy E51), oil bath to 100 ℃, stir, in another vinylformic acid (epoxide group and acrylic acid mol ratio are 2:1) toward measuring, add total mass 0.2% catalyst n, N-dimethyl benzylamine (BDMA) and 0.3% stopper MEHQ, be added dropwise in epoxy resin, after reaction 5h, the system acid number is less than 3mgKOH/g, epoxy monoacrylate namely
Second step, the tolylene diisocyanate (TDI) that adds 0.5mol in the there-necked flask of 1000mL, be heated to 60 ℃, dibutyl tin dilaurate joins the hydroxy silicon oil (hydroxy radical content 6%) that contains the 0.5mol hydroxyl by 0.2% of total mass, be added dropwise in tolylene diisocyanate (TDI) solution, drip off rear continuation reaction 2.5h, in the Hydroxyethyl acrylate of 0.25mol, add 0.2% MEHQ, add above-mentioned reaction system, be warming up to 100 ℃ of reaction 2h, namely obtain an end to also have-urethane acrylate of NCO group
The 3rd step, add a certain amount of epoxy monoacrylate in there-necked flask
, add the urethane acrylate segment of metering
(by epoxide group with-the NCO group molar ratio is that 1:0.8 adds), reaction 4h namely obtains having UV-light and causes radically curing group (acrylic double bond) and have again UV-light to cause the siliceous double cured resin (structure A) of cationic curing group or thermofixation group (epoxide group) under 90 ℃.
Embodiment 2:
The first step, in the 500mL there-necked flask, add 250g bisphenol-A epoxy (epoxy E44), oil bath to 110 ℃, stir, the hydroquinone of polymerization retarder that adds total mass 0.4% catalyzer triethyl benzyl ammonia chloride and 0.3% in another vinylformic acid (epoxide group and acrylic acid mol ratio are 2:1) toward measuring, be added dropwise in epoxy resin, after reaction 4.5h, the system acid number is less than 3mgKOH/g, epoxy monoacrylate namely
Second step, the diphenylmethanediisocyanate (MDI) that adds 1mol in the there-necked flask of 1000mL, be heated to 60 ℃, dibutyl tin dilaurate joins the hydroxy silicon oil (hydroxy radical content 9%) that contains the 1mol hydroxyl by 0.3% of total mass, be added dropwise in diphenylmethanediisocyanate (MDI) solution, drip off rear continuation reaction 2.5h, in the hydroxyethyl methylacrylate of 0.5mol, add 0.3% MEHQ, add above-mentioned reaction system, be warming up to 100 ℃ of reaction 2.5h, namely obtain an end to also have-urethane acrylate of NCO group
The 3rd step, add a certain amount of epoxy monoacrylate in there-necked flask
, add the urethane acrylate segment of metering
(by epoxide group with-the NCO group molar ratio is that 1:0.95 adds), reaction 4h namely obtains having UV-light and causes radically curing group (acrylic double bond) and have again UV-light to cause the resin (structure A) of cationic curing group or thermofixation group (epoxide group) under 95 ℃.
Embodiment 3:
The first step, in the 1000mL there-necked flask, add the 600g tetrabromo bisphenol-a epoxy resin, oil bath to 90 ℃, stir, the stopper MEHQ that adds total mass 0.5% catalyzer tri acetylacetonato network iron (III) and 0.5% in another vinylformic acid (epoxide group and acrylic acid mol ratio are 2:1) toward measuring, be added dropwise in epoxy resin, after reaction 6h, the system acid number is less than 3mgKOH/g, epoxy monoacrylate namely
Second step, the hexamethylene diisocyanate (HDI) that adds 1mol in the there-necked flask of 1000mL, be heated to 80 ℃, dibutyl tin dilaurate joins the hydroxy silicon oil (hydroxy radical content 3.5%) that contains the 1mol hydroxyl by 0.2% of total mass, be added dropwise in hexamethylene diisocyanate (HDI) solution, drip off rear continuation reaction 2.5h, in the Propylene glycol monoacrylate of 0.5mol, add 0.5% MEHQ, add above-mentioned reaction system, be warming up to 90 ℃ of reaction 3h, namely obtain an end to also have-urethane acrylate of NCO group
The 3rd step, add a certain amount of epoxy monoacrylate in there-necked flask
, add the urethane acrylate segment of metering
(by epoxide group with-the NCO group molar ratio is that 1:1 adds), reaction 3.5h namely obtains having UV-light and causes radically curing group (acrylic double bond) and have again UV-light to cause the resin (structure A) of cationic curing group or thermofixation group (epoxide group) under 100 ℃.
Embodiment 4:
The first step, in the 1000mL there-necked flask, add the 500g novolac epoxy, oil bath to 105 ℃, stir, the stopper MEHQ that adds total mass 0.8% catalyzer trolamine and 0.8% in another vinylformic acid (epoxide group and acrylic acid mol ratio are 2:1) toward measuring, be added dropwise in epoxy resin, after reaction 4h, the system acid number is less than 3mgKOH/g, epoxy monoacrylate namely
Second step, the isophorone diisocyanate (IPDI) that adds 1mol in the there-necked flask of 1000mL, be heated to 80 ℃, dibutyl tin dilaurate joins the hydroxy silicon oil (hydroxy radical content 5%) that contains the 1mol hydroxyl by 0.6% of total mass, be added dropwise in isophorone diisocyanate (IPDI) solution, drip off rear continuation reaction 2.5h, in the Rocryl 410 of 0.5mol, add 0.8% MEHQ, add above-mentioned reaction system, be warming up to 115 ℃ of reaction 3h, namely obtain an end to also have-urethane acrylate of NCO group
The 3rd step, add a certain amount of epoxy monoacrylate in there-necked flask
, add the urethane acrylate segment of metering
(by epoxide group with-the NCO group molar ratio is that 1:0.80 adds), reaction 4h namely obtains having UV-light and causes radically curing group (acrylic double bond) and have again UV-light to cause the resin (structure A) of cationic curing group or thermofixation group (epoxide group) under 70 ℃.
Embodiment 5:
The first step, in the 1000mL there-necked flask, add the 500g aliphatic epoxy resin, oil bath to 110 ℃, stir, the hydroquinone of polymerization retarder that adds total mass 0.5% catalyzer tri acetylacetonato network chromium (III) and 0.1% in another vinylformic acid (epoxide group and acrylic acid mol ratio are 2:1) toward measuring, be added dropwise in epoxy resin, after reaction 4h, the system acid number is less than 3mgKOH/g, epoxy monoacrylate namely
Second step, the dicyclohexyl methane diisocyanate (HMDI) that adds 2mol in the there-necked flask of 1000mL, be heated to 50 ℃, dibutyl tin dilaurate joins 1 of 1mol by 0.2% of total mass, the 6-hexylene glycol, be added dropwise in dicyclohexyl methane diisocyanate (HMDI) solution, drip off rear continuation reaction 3h, in the Propylene glycol monoacrylate of 1mol, add 0.5% MEHQ, add above-mentioned reaction system, be warming up to 115 ℃ of reaction 2h, namely obtain an end to also have-urethane acrylate of NCO group
The 3rd step, add a certain amount of epoxy monoacrylate in there-necked flask
, add the urethane acrylate segment of metering
(by epoxide group with-the NCO group molar ratio is that 1:0.85 adds), under 100 ℃ the reaction 3.5h namely obtain resin
The 4th step, add a certain amount of resin in flask
, adding the N-cyclohexyl of metering-3-aminopropyl methyl dimethoxysilane (being that 1:0.7 adds by epoxide group and amino mol ratio), reaction 20h namely obtains siliceous double cured resin (structure B) under 80 ℃.
Foregoing description and explanation can not limit the scope of the invention with this.Allly according to the present invention, conceive the equivalence that essence does and change or modify, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. method for preparing the silicon-containing double-curing group resin with following structure,
Comprise the steps:
(1) acrylic acid epoxy monoesters segment is synthetic: in reaction vessel, add epoxy resin, 90～110 ℃ of oil baths; Then adding massfraction is 0.1～1.0% catalyzer and/or 0.1～0.8% stopper; Add vinylformic acid, described acrylic acid add-on meets epoxide group and acrylic acid mol ratio is 2:1 again; By the acid number≤3mgKOH/g of alkalimetric titration to system, obtain acrylic acid epoxy monoesters segment, described acrylic acid epoxy monoesters segment has following structure:
(2) the silicon-based polyurethane acrylate segment is synthetic: in reaction vessel, add vulcabond, be heated to 50～80 ℃; Hydroxy silicon oil is added in vulcabond, and the mol ratio that described hydroxy silicon oil add-on meets vulcabond and hydroxyl is 1:1; Described hydroxy silicon oil is added with the dibutyl tin dilaurate that accounts for total mass 0.1～0.6%; In reaction system, add hydroxy acrylate, the mol ratio that the add-on of described hydroxy acrylate meets hydroxy acrylate and vulcabond is 0.5～0.55:1, and described hydroxy acrylate is added with 0.1～0.8% MEHQ; Reaction system is warming up to 80～115 ℃, reaction 2～4h, obtaining an end has-the silicon-based polyurethane acrylate segment of NCO group, described urethane acrylate segment has following structure:
(3) silicon-based polyurethane Acrylate Modified Epoxy acrylic monoester resin is synthetic: in reaction vessel, add the synthetic acrylic acid epoxy monoesters segment of step (1) and the synthetic silicon-based polyurethane acrylate segment of step (2), the add-on of described acrylic acid epoxy monoesters segment and urethane acrylate segment meet epoxide group with-the NCO group molar ratio is 1:0.8～1; Under 70～100 ℃, react 3～5h, obtain silicon-based polyurethane Acrylate Modified Epoxy acrylic monoester resin, described silicon-based polyurethane Acrylate Modified Epoxy acrylic monoester resin has following structure:
2. prepare as claimed in claim 1 the method for silicon-containing double-curing group resin, it is characterized in that: the epoxy resin of mentioning in described step is that bisphenol A epoxide resin, novolac epoxy, tetrabromo bisphenol-a epoxy resin, bisphenol F epoxy resin, naphthalene are a kind of in epoxy, aliphatic epoxy and alicyclic epoxy.
3. prepare as claimed in claim 1 the method for silicon-containing double-curing group resin, it is characterized in that: described catalyzer is N, the N-dimethyl benzylamine, N, the N-diethyl benzylamine, triethylamine, trolamine, four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, praseodynium network aluminium (III), praseodynium network lanthanum (III), praseodynium network chromium (III), tetrem acyl acetone network zirconium, praseodynium network iron (III), diacetyl acetone network copper (II), diacetyl acetone network cobalt (II), dichloride diacetyl acetone network titanium (IV), praseodynium network cobalt (III), praseodynium network manganese (III), diacetyl acetone network nickel (II), praseodynium network vanadium (III), diacetyl acetone network vanadyl (IV), diacetyl acetone network beryllium (II), a kind of in diacetyl acetone network zinc (II).
4. prepare as claimed in claim 1 the method for silicon-containing double-curing group resin, it is characterized in that: described stopper is a kind of in MEHQ, Resorcinol.
5. prepare as claimed in claim 1 the method for silicon-containing double-curing group resin, it is characterized in that: described vulcabond is a kind of in tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, PPDI.
6. prepare as claimed in claim 1 the method for silicon-containing double-curing group resin, it is characterized in that: described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester.
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| CN101824152A (en) * | 2010-04-13 | 2010-09-08 | 深圳职业技术学院 | Preparation method and application of resin having double curing groups |
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