CN102344539A - 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 UV-light simultaneously 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 photoinitiator curing-Re, tackiness agent, printing ink outward.
Background technology
UV-light (UV) curing technology has characteristics such as quick, solvent-free, suitable streamline production because of it, and obtains fast development.It can be used as the coating for surface protection of plastics, metal, timber, paper, optical fiber etc., widespread use in industry.The UV curing system is generally by photolytic activity oligopolymer (resin), simple function group and polyfunctional group thinner, compositions such as light trigger and auxiliary agent.The photolytic activity oligopolymer forms the three-dimensional net structure of polymkeric substance after curing, the physicochemical property of cured film is played conclusive effect.
Ultraviolet light polymerization divides by mechanism has radically curing and cationic curing.Advantages such as the radical photoinitiator 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 big, poor adhesive force, problem such as solidification without male offspring, at present, the ultraviolet light polymerization product is main with the radically curing system mainly.Cation photocuring system has that volumetric shrinkage is little, strong adhesion, can after fixing etc. advantage, but shortcoming such as it also has that curing speed is slow, oligopolymer and reactive thinner kind are few, it is mainly used in the 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 ultraviolet light polymerization system has now obtained attention more and more widely; Develop and the various forms of ultraviolet light polymerization systems that mix; Mainly containing UV-light free radical-cationic hybrid solidifies; UV-light free radical-Re mixes curing; UV-light-air mixes curing; UV-light-moisture mixes curing etc.; These mix curing system, and mainly to contain different curing groups mixed with resin with two or more be main, then relatively more rare about the report that has two kinds of curing groups resin study on the synthesis simultaneously.
In each specific admixture ultraviolet light polymerization system, most of investigator all adopts the mixing of several resins with different curing groups, uses problems such as existing between the uneven or resin of local solidification the consistency difference like this.
Resin commonly used in UV-light (UV) solidifying product has epoxy acrylate, urethane acrylate, polyester acrylate etc.; These resins can satisfy the needs that great majority are used; But in order to make cured film have some special performances; To satisfy special needs; Can in oligopolymer, simple function group or polyfunctional group thinner, introduce the group that contains elements such as fluorine, phosphorus, silicon; The introducing of fluorochemical monomer mainly is the surface property that improves cured film; But it is on the high side, has influenced its use; Synthetic and the use of phosphorous-containing monomers is primarily aimed at fire-retardant requirement and designs, and the unit that is engaged in this respect research at present is not a lot; Silicon-containing compound obtains extensive concern and research owing to have very low temperature coefficient of viscosity, lower price, excellent interface performance, flexibility, good lubricity, chemical stability and outstanding performances such as weathering resistance preferably.
Can be used in containing silicone resin and can be divided three classes in the UV curing system: a kind of is can be through polysiloxane, acrylate containing silicone thinner, carbamate polysiloxane or the mercaptan-alkene system etc. of free radical mechanism reaction solidified acroleic acid esterification; Two kinds is by cationic mechanism solidified epoxy grafted silicone resin; Three types is to cause the special SiH-Si vinyl organosilicon of solidified by precious metal.
Summary of the invention
The present invention provides a kind of and contains the organosilicon segment, and has 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 simultaneously.On the one hand be implemented in the group that has two kinds of different curing methods in the same molecular resin, solved that different resins is composite to mix resin compatible problem in the curing system; On the other hand, through urethane acrylate flexible chain and the modification of organosilicon segmental, 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 following:
(1) acrylic acid epoxy monoesters segmental is synthetic
In the 1000mL there-necked flask, add a certain amount of Resins, epoxy; Stir; Oil bath is to 90-110 ℃; The catalyzer that adds 0.1-1.0% then; The stopper of 0.1-0.8%; The vinylformic acid of metering; Every at a distance from the 30min sampling; Sodium hydroxide titration with 0.1mol/L; The transformation efficiency of carboxylic acid in the acid number of counting system and the reaction process; When the acid number in the reaction system during less than 3mgKOH/g, think that promptly esterification accomplishes, be the acrylic acid epoxy monoesters after the cooling; One end of molecular resin is acrylic double bond (radically curing); The other end is epoxide group (cationic curing or thermofixation), through reacting or self having hydroxyl, reflecting point is provided for follow-up modification is synthetic in the molecular resin segment.Its structural characteristics are as follows:? ?
Described Resins, epoxy 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 the 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) the network zinc (II).
Described stopper is: a kind of in MEHQ, the Resorcinol.
(2) siliceous urethane acrylate segmental is synthetic
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, hydroxy silicon oil is dripped in the isocyanic ester of into stirring; 2h drips, and continues reaction 2h; In the hydroxy acrylate of 0.25mol, add the MEHQ of 0.1-0.8%, add above-mentioned reaction system, be warming up to 80-115 ℃ of reaction 3h, promptly obtain an end to also have-the siliceous urethane acrylate segment of NCO group.Its structure is as follows:
Described vulcabond is: a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), the PPDI (PPDI).
Described hydroxy silicon oil is a kind of among the hydroxy radical content 0.5-10%.
Described hydroxy acrylate is: a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, Rocryl 410, the vinylformic acid hydroxy butyl ester.
(3) siliceous urethane acrylate modified epoxy acrylic monoester is synthetic
500mL three-necked flask in a certain amount of epoxy acrylate monoester (1), adding measurement (2) a silicon-containing urethane acrylate segment (by epoxy group-NCO groups and the molar ratio of 1:0.8-1 added), the reaction at 70-100 ℃ for 4h, the structural characteristics of the obtained resin is as follows:
The synthetic route that wherein has the B structural resin is following:
(1) acrylic acid epoxy monoesters segmental is synthetic
In the 1000mL there-necked flask, add a certain amount of Resins, epoxy; Stir; Oil bath is to 90-110 ℃; The catalyzer that adds 0.1-1.0% then; The stopper of 0.1-0.8%; The vinylformic acid of metering; Every at a distance from the 30min sampling; Sodium hydroxide titration with 0.1mol/L; The transformation efficiency of carboxylic acid in the acid number of counting system and the reaction process; When the acid number in the reaction system during less than 3mgKOH/g, think that promptly esterification accomplishes, be the acrylic acid epoxy monoesters after the cooling; One end of molecular resin is acrylic double bond (radically curing); The other end is epoxide group (cationic curing or thermofixation), through reacting or self having hydroxyl, reflecting point is provided for follow-up modification is synthetic in the molecular resin segment.Its structure is as follows:
Described Resins, epoxy 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 the 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) the network zinc (II).
Described stopper is: a kind of in MEHQ, the Resorcinol.
(2) the urethane acrylate segmental is synthetic
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, dibasic alcohol is dripped in the isocyanic ester of into stirring; 2h drips, and continues reaction 2h; In the hydroxy acrylate of 1-1.1mol, add the MEHQ of 0.1-0.8%, add above-mentioned reaction system, be warming up to 80-115 ℃ of reaction 3h, promptly obtain an end to also have-the urethane acrylate segment of NCO group.Its structure is as follows:
Described vulcabond is: a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), the PPDI (PPDI).
Described dibasic alcohol is: polyether Glycols, polyester diol, Ucar 35, neopentyl glycol, 1,4-butyleneglycol, 1, a kind of in 6-hexylene glycol, the 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, Rocryl 400, Rocryl 410, the vinylformic acid hydroxy butyl ester.
(3) urethane acrylate modified epoxy acrylic monoester is synthetic
500mL three-necked flask in a certain amount of epoxy acrylate monoester (1), adding measurement (2) urethane acrylate segment (by epoxy group-NCO groups and the molar ratio of 1:0.8-1 added) at 70-100 ℃ for 4h reaction, the resulting resin structural features are as follows:
(4) aminosilane or amino-modified silicone resin is synthetic
In the 1000mL flask, add urethane acrylate modified epoxy acrylic monoester resin (3), add the aminosilane or the amido silicon oil (is that 1:0.5-1 adds by epoxide group and amino mol ratio) of metering, between 50-100 ℃, the reaction times is 16h.Acrylic acid esters with amino silane or silicone oil can be obtained by Michael addition reaction of silicon having the following structure group dual cure resin:
By the synthetic resin of said method with double curing groups; Relatively hard epoxy segment is arranged in the resinous molecular structure; Pliable and tough relatively polyurethane segment is arranged; And siliceous segment arranged; Have acrylic double bond (ultraviolet light radically curing) and two kinds of functional groups of epoxy (ultraviolet light cationic curing or heat cure) simultaneously; Can be mixed with free radical-cationic hybrid photocuring system on this basis; Perhaps be mixed with the mixing cured system of ultraviolet light free radical-Re; Can effectively bring into play the advantage of each segment, the cured film overall performance is improved and improve.
Embodiment
Below in conjunction with specific embodiment the present invention is explained further details.
Embodiment 1:
First step in the three-necked flask was added 1000mL 520g of bisphenol A epoxy (epoxy E51), the oil bath to 100 ℃, stirring, and the other to measure the acid (epoxy group and acrylic acid molar ratio of 2:1) 0.2% of the total mass of the catalyst added N, N-dimethylbenzylamine (BDMA) and 0.3% of inhibitor-hydroxyanisole, epoxy resin was added dropwise, the reaction system after the acid value is less than 5h 3mgKOH / g, namely epoxy acrylic monoesters?
; the second step, three-necked flask were added 1000mL 0.5mol toluene diisocyanate (TDI), heated to 60 ℃, dibutyl tin dilaurate, 0.2% of the total mass added to the hydroxyl group-containing hydroxyl 0.5mol oil (hydroxyl content of 6%), was added dropwise to toluene diisocyanate (TDI) solution was added dropwise the reaction was continued 2.5h, hydroxyethyl acrylate in 0.25mol added parahydroxybenzoate 0.2% ether was added the reaction system, the reaction temperature was raised to 100 ℃ 2h, i.e. to obtain an end-NCO groups and urethane acrylate
; third step, three-necked flask certain amount of epoxy acrylic monoesters
, adding polyurethane metering acrylate segment
(by epoxy group-NCO groups and the molar ratio of 1:0.8 to join), reacted at 90 ℃ for 4h i.e. radical initiator having UV-curable group (the acrylate double bond) have UV cationic photoinitiator or thermal curable group curable group (epoxy group) of silicon dual cure resin (structure A).
Embodiment 2:
First step in the three-necked flask was added 500mL 250g of bisphenol A epoxy (epoxy E44), the oil bath to 110 ℃, stirring, and the other to measure the acid (epoxy group and acrylic acid molar ratio of 2:1) 0.4% of the total mass of the catalyst added triethyl benzyl ammonium chloride and 0.3% of hydroquinone inhibitor, epoxy resin was added dropwise, the reaction system after the acid value is less than 4.5h 3mgKOH / g, i.e. epoxy acrylic acid monoester
; the second step, three-necked flask were added 1000mL 1mol diphenylmethane diisocyanate (MDI), heated to 60 ℃, dibutyl tin dilaurate, 0.3% of the total mass added to the hydroxyl group-containing 1mol hydroxy silicone oil (hydroxyl content 9%), was added dropwise diphenyl methane diisocyanate (MDI) solution was added dropwise the reaction was continued 2.5h, in 0.5mol of hydroxyethyl methacrylate was added p-hydroxybenzoate 0.3% Ether was added the reaction system, the reaction temperature was raised to 100 ℃ 2.5h, i.e. to obtain an end-NCO groups and urethane acrylate
; third step, three-necked flask certain amount of epoxy acrylic monoesters
, adding metering The urethane acrylate chains
(by epoxy group-NCO groups and the molar ratio of 1:0.95 to join), and reacted at 95 ℃ 4h i.e. radical initiator having UV-curable group (the acrylate double bond) and a cationic UV irradiation or heat-curable group curable group (epoxy group) of the resin (structure A).
Embodiment 3:
First step in the three-necked flask was added 600g 1000mL of tetrabromobisphenol A epoxy resin, an oil bath to 90 ℃, stirring, and the other to measure the acid (epoxy groups with acrylic acid molar ratio of 2:1) was added 0.5% of the total mass of the catalyst tris (acetylacetonate) Contact Iron (Ⅲ) and 0.5% of inhibitor-hydroxyanisole, epoxy resin was added dropwise, the reaction system after the acid value is less than 6h 3mgKOH / g, i.e. epoxy acrylic acid monoester
; the second step, three-necked flask 1000mL 1mol of hexamethylene diisocyanate (HDI), heated to 80 ℃, dibutyl tin dilaurate, 0.2% of the total mass added to the hydroxyl group-containing 1mol hydroxy silicone oil (hydroxyl content 3.5%) was added dropwise hexamethylene diisocyanate (HDI) solution was added dropwise the reaction was continued 2.5h, hydroxypropyl acrylate in 0.5mol of adding 0.5% of the p-hydroxyanisole , added to the above reaction system, the reaction temperature was raised to 90 ℃ 3h, i.e. to obtain an end-NCO groups and urethane acrylate
; third step, three-necked flask certain amount of epoxy acrylic monoesters
, adding measurement urethane acrylate ester chains
(by epoxy group-NCO groups and the molar ratio of 1:1 to join), the reaction at 100 ℃ for 3.5h the radical initiator having the UV-curable group (the acrylate double bond) have UV cationic photoinitiator or thermal curable group curable group (epoxy group) of the resin (structure A).
Embodiment 4:
First step in the three-necked flask was added 500g 1000mL phenol resin, an oil bath to 105 ℃, stirring, and the other to measure the acid (epoxy groups with acrylic acid molar ratio of 2:1) was added 0.8% of total mass catalyst, and 0.8% of triethanolamine inhibitor hydroxyanisole, epoxy resin was added dropwise, the reaction system after the acid value is less than 4h 3mgKOH / g, i.e. epoxy acrylate monoesters
; second step, the three 1000mL flask 1mol of isophorone diisocyanate (IPDI), heated to 80 ℃, dibutyltin dilaurate 0.6% of the total mass added to the hydroxyl group-containing hydroxyl 1mol oil (hydroxyl content 5%) was added dropwise isophorone diisocyanate (IPDI) solution was added dropwise the reaction was continued 2.5h, in 0.5mol of hydroxypropyl methacrylate, 0.8% of the p-hydroxyanisole, added to the above reaction system was heated to 115 ℃ reaction 3h, that there be an end-NCO groups urethane acrylate
; third step, three-necked flask was added a certain amount of epoxy acrylate monoesters
, adding measurement urethane acrylate chains
(by epoxy groups and -NCO group molar ratio of 1:0.80 to join), reacted at 70 ℃ 4h i.e. radical initiator having UV-curable group (the acrylate double bond) have cationic UV initiator or heat-curable group curable group (epoxy group) resin (structure A).
Embodiment 5:
First step in the three-necked flask was added 500g 1000mL aliphatic epoxy resin, an oil bath to 110 ℃, stirring, and the other to measure the acid (epoxy groups with acrylic acid molar ratio of 2:1) was added 0.5 Total mass % catalyst, tris (acetylacetonate) Network Chromium (Ⅲ) and 0.1% of hydroquinone inhibitor, epoxy resin was added dropwise, the reaction system after the acid value is less than 4h 3mgKOH / g, i.e. epoxy acrylate monoesters
; The second step in the three-necked flask 1000mL 2mol dicyclohexyl methane diisocyanate (HMDI), heated to 50 ℃, dibutyltin dilaurate 0.2% of the total mass added to 1mol of 1,6 - diol was added dropwise dicyclohexylmethane diisocyanate (HMDI) solution was added dropwise the reaction was continued 3h, in 1mol of hydroxypropyl acrylate was added 0.5% p-hydroxyanisole, added to the above reaction system was heated to 115 ℃ for 2h, ie, get well-NCO end groups urethane acrylate
; third step, three-necked flask was added a certain amount of epoxy acrylate monoesters
, adding measurement urethane acrylate chains
(by epoxy groups the-NCO group molar ratio of 1:0.85 to join), the reaction at 100 ℃ for 3.5h to give a resin that
; fourth step, the flask by adding a certain amount of resin
, adding measurable N-cyclohexyl-3 - aminopropyl methyl dimethoxy silane (epoxy group with an amino group at a molar ratio of 1:0.7 to join), the reaction at 80 ℃ 20h derived silicon dual cure resin (structure B).
Foregoing description can not limit protection scope of the present invention with this with explanation.Allly conceive equivalence that essence does according to the present invention and change or modify, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a siliceous double curing groups resin comprises acrylic acid epoxy monoesters and acrylate containing silicone segment, and described siliceous double curing groups resin has following two kinds of structures:
A：
Or
B：
。
2. a method for preparing the siliceous double curing groups resin with A structure comprises the steps:
(1) acrylic acid monoester of ethylene segments: In a reaction vessel, the epoxy resin, 90 ~ 110 ℃ oil bath; then the mass fraction of 0.1 to 1.0% of the catalyst and / or 0.1 to 0.8% of the polymerization inhibitor ; then add acrylic acid, acrylic acid added in an amount to meet the epoxy groups with acrylic acid molar ratio of 2:1; system by the alkali titration to an acid value of ≤ 3mgKOH / g, to obtain an acrylic monoester of ethylene segments, said epoxy acrylic monoesters segment has the following structure:
;
(2) a silicon-containing urethane acrylate segments: In a reaction vessel, the diisocyanate heated to 50 ~ 80 ℃; the hydroxy silicone oil added to the diisocyanate, said hydroxy silicone oil added in an amount to meet the diisocyanate to hydroxyl molar ratio 1:1; said hydroxyl silicone oil is added 0.1 to 0.6 percent of the total mass of dibutyltin dilaurate; the reaction system by adding hydroxy acrylates, hydroxy acrylates of the added amount of hydroxy acrylates meet diisocyanate with a molar ratio of from 0.5 to 0.55:1, said hydroxy acrylate is added 0.1 to 0.8 percent hydroxy anisole; the reaction system was heated to 80 ~ 115 ℃, reaction 2 ~ 4h, to obtain one end -NCO group-containing silicon segment urethane acrylates, urethane acrylates described in the segment has the following structure:
;
(3) a silicon-containing modified epoxy acrylate urethane acrylate mono-ester resin: In a reaction vessel of step (1) Synthesis of epoxy acrylic monoesters segment and step (2) Synthesis of a silicon-containing urethane acrylate segment , monoesters of the acrylic epoxy and polyurethane acrylate segments segments added in an amount to meet the epoxy group-NCO groups and the molar ratio of 1:0.8 ~ 1; 70 ~ 100 ℃ reaction 3 ~ 5h, mixture containing silicone-modified epoxy acrylate urethane acrylate resin monoesters, the silicon containing urethane acrylate modified epoxy acrylate resin has the following structure monoesters:
.
3. a method for preparing the siliceous double curing groups resin with B structure is characterized in that comprising the steps:
(1) acrylic acid monoester of ethylene segments: In a reaction vessel, the epoxy resin, 90 ~ 110 ℃ oil bath; then the mass fraction of 0.1 to 1.0% of the catalyst and / or 0.1 to 0.8% of the polymerization inhibitor ; then add acrylic acid, acrylic acid added in an amount to meet the epoxy groups with acrylic acid molar ratio of 2:1; system by the alkali titration to an acid value of ≤ 3mgKOH / g, to obtain an acrylic monoester of ethylene segments, said epoxy acrylic monoesters segment has the following structure:
;
(2) Urethane acrylate segments: In a reaction vessel, the diisocyanate heated to 50 ~ 80 ℃; the diol added diisocyanate, said dihydric alcohol added in an amount to meet the diisocyanate and a diol molar ratio of 2:1; said diol is added 0.1 to 0.6 percent of the total mass of dibutyltin dilaurate; the reaction system by adding hydroxy acrylates, said hydroxyl acrylic ester added to meet hydroxy acrylate and a diisocyanate in a molar ratio of (0.5 to 0.55): 1, said hydroxy acrylate is added 0.1 to 0.8 percent hydroxy anisole; the reaction system was heated to 80 ~ 115 ℃, reaction of 2 - 4h, to obtain end-NCO groups with urethane acrylate segment, the segment of the urethane acrylate has the following structure:
;
(3) a polyurethane acrylate-modified epoxy ester resin acrylic monomers: In a reaction vessel, Step 1) Synthesis of epoxy acrylic monoesters segment and step 2) Synthesis of urethane acrylate segment, the acrylic epoxy monoesters segment and the segment polyurethane acrylate added in an amount to meet the epoxy group-NCO groups and the molar ratio of 1:0.8 ~ 1; 70 ~ 100 ℃ reaction 3 ~ 5h, to obtain a polyurethane modified epoxy acrylate monoesters of acrylic resin, a urethane acrylate-modified epoxy ester resin, acrylic monomers having the following structure:
;
(4): add urethane acrylate modified epoxy acrylic monoester resin in the reaction vessel, add aminosilane or amido silicon oil (is that 1:0.5-1 adds by epoxide group and amino mol ratio) again, between 50-100 ℃, the reaction times is 5-24h.
4 acrylic acid esters with amino silane or silicone oil can be obtained by Michael addition reaction of silicon having the following structure group dual cure resin:
.
5. like the methods of claim 2 or 3 described synthetic siliceous double curing groups resins, it is characterized in that: described Resins, epoxy is that bisphenol A epoxide resin and homologue thereof, novolac epoxy, tetrabromo bisphenol-a epoxy resin, bisphenol F epoxy resin, naphthalene are a kind of in epoxy, diepoxy polyoxytrimethylene, aliphatic epoxy and the alicyclic epoxy.
6. like claim 2 or 3 described methods of synthesizing siliceous double curing groups resins; It is characterized in that: 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) the network zinc (II).
7. like the methods of claim 2 or 3 described synthetic siliceous double curing groups resins, it is characterized in that: described stopper is a kind of in MEHQ, the Resorcinol.
8. like the methods of claim 2 or 3 described synthetic siliceous double curing groups resins, it is characterized in that: described vulcabond is a kind of in tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), the PPDI (PPDI).
9. like the methods of claim 2 or 3 described synthetic siliceous double curing groups resins, it is characterized in that: described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, Rocryl 410, the vinylformic acid hydroxy butyl ester.
10. the method for synthetic siliceous double curing groups resin as claimed in claim 2, it is characterized in that: described hydroxy silicon oil is any hydroxy silicon oil among the hydroxy radical content 0.5-10%.
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| CN103194104A (en) * | 2013-03-21 | 2013-07-10 | 中山金利宝胶粘制品有限公司 | Plastic film surface coating composition and labeled product thereof |
| CN103709365A (en) * | 2013-12-13 | 2014-04-09 | 深圳职业技术学院 | High refractive resin containing silicon and preparation method of resin |
| CN104788644A (en) * | 2015-04-29 | 2015-07-22 | 烟台德邦科技有限公司 | UV/moisture dual-curing resin and synthesis method thereof |
| CN105315901A (en) * | 2014-06-26 | 2016-02-10 | 戴马士股份公司 | Actinic radiation and moisture dual curable composition |
| CN105441012A (en) * | 2015-12-15 | 2016-03-30 | 东莞市派乐玛新材料技术开发有限公司 | UV adhesive for sealing quantum dot material, and preparation method thereof |
| CN105754108A (en) * | 2016-04-26 | 2016-07-13 | 深圳职业技术学院 | Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof |
| CN108299945A (en) * | 2018-04-09 | 2018-07-20 | 天津科技大学 | General plastic intaglio printing aqueous UV ink and preparation method |
| CN108587304A (en) * | 2018-04-09 | 2018-09-28 | 天津科技大学 | A kind of wood surface silk-screen printing aqueous UV ink and preparation method |
| CN108641472A (en) * | 2018-04-09 | 2018-10-12 | 天津科技大学 | General plastic intaglio printing water-based ink and preparation method |
| CN109337638A (en) * | 2018-09-05 | 2019-02-15 | 深圳职业技术学院 | A kind of ultraviolet light mixes cure package glue composition |
| CN109957086A (en) * | 2017-12-14 | 2019-07-02 | 惠州市长润发涂料有限公司 | A kind of synthetic method of the polyurethane acrylate resin of high-performance and low-cost |
| CN110078928A (en) * | 2019-04-26 | 2019-08-02 | 深圳职业技术学院 | A kind of low-surface-energy highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof |
| CN110105578A (en) * | 2019-04-26 | 2019-08-09 | 深圳职业技术学院 | A kind of highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof with siliceous segment |
| CN110452361A (en) * | 2019-07-09 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of synthetic method and waterproofing agent of the polyurethane acroleic acid modified organic silicon without fluoro water proofing agent |
| CN110467901A (en) * | 2018-05-10 | 2019-11-19 | 上海本诺电子材料有限公司 | OLED heats dual UV curable paint organic silicon modified epoxy acrylate glue and preparation method with UV |
| CN111194328A (en) * | 2017-10-13 | 2020-05-22 | 科思创德国股份有限公司 | Method for forming oxazolidinones to prepare crosslinkable polymers |
| CN111205815A (en) * | 2020-03-12 | 2020-05-29 | 东莞市联灏新材料技术开发有限公司 | OLED sealant composition capable of being cured in UV hybrid mode |
| CN112358841A (en) * | 2020-12-29 | 2021-02-12 | 烟台信友新材料有限公司 | Flexible UV-thermal dual-curing transparent conductive adhesive and preparation method thereof |
| CN112552870A (en) * | 2020-12-29 | 2021-03-26 | 烟台信友新材料有限公司 | High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof |
| CN113372816A (en) * | 2021-05-21 | 2021-09-10 | 无锡时生高分子科技有限公司 | Solvent-free UV (ultraviolet) curing type organic silicon three-proofing adhesive |
| CN113817121A (en) * | 2021-09-28 | 2021-12-21 | 泉州师范学院 | Acrylic acid group-terminated silicon chain polyurethane photosensitive prepolymer and preparation method thereof |
| CN113881013A (en) * | 2021-10-27 | 2022-01-04 | 上海古原草科技有限公司 | Acrylic acid modified polyurethane epoxy toughening agent and preparation method thereof |
| CN113999618A (en) * | 2021-11-22 | 2022-02-01 | 曹云来 | Low-odor and low-irritation dual-curing adhesive and preparation method thereof |
| CN114231162A (en) * | 2021-11-12 | 2022-03-25 | 广东腐蚀科学与技术创新研究院 | Organic silicon modified polyurethane acrylate ultraviolet light and moisture dual-curing three-proofing paint and preparation method thereof |
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| CN117089279A (en) * | 2023-10-19 | 2023-11-21 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
| CN117567752A (en) * | 2024-01-15 | 2024-02-20 | 广东腐蚀科学与技术创新研究院 | Modified UV/moisture dual-curing resin, three-proofing paint for protecting automobile electronic circuit board and preparation method of three-proofing paint |
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| CN103194104A (en) * | 2013-03-21 | 2013-07-10 | 中山金利宝胶粘制品有限公司 | Plastic film surface coating composition and labeled product thereof |
| CN103709365A (en) * | 2013-12-13 | 2014-04-09 | 深圳职业技术学院 | High refractive resin containing silicon and preparation method of resin |
| CN105315901A (en) * | 2014-06-26 | 2016-02-10 | 戴马士股份公司 | Actinic radiation and moisture dual curable composition |
| CN104788644A (en) * | 2015-04-29 | 2015-07-22 | 烟台德邦科技有限公司 | UV/moisture dual-curing resin and synthesis method thereof |
| CN105441012B (en) * | 2015-12-15 | 2019-02-15 | 东莞市派乐玛新材料技术开发有限公司 | A kind of UV glue and preparation method thereof for quanta point material sealing |
| CN105441012A (en) * | 2015-12-15 | 2016-03-30 | 东莞市派乐玛新材料技术开发有限公司 | UV adhesive for sealing quantum dot material, and preparation method thereof |
| CN105754108A (en) * | 2016-04-26 | 2016-07-13 | 深圳职业技术学院 | Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof |
| US11905360B2 (en) | 2017-10-13 | 2024-02-20 | Stratasys, Inc. | Method for producing a cross-linkable polymer with the formation of oxazolidinones |
| CN111194328A (en) * | 2017-10-13 | 2020-05-22 | 科思创德国股份有限公司 | Method for forming oxazolidinones to prepare crosslinkable polymers |
| CN109957086A (en) * | 2017-12-14 | 2019-07-02 | 惠州市长润发涂料有限公司 | A kind of synthetic method of the polyurethane acrylate resin of high-performance and low-cost |
| CN108299945A (en) * | 2018-04-09 | 2018-07-20 | 天津科技大学 | General plastic intaglio printing aqueous UV ink and preparation method |
| CN108641472A (en) * | 2018-04-09 | 2018-10-12 | 天津科技大学 | General plastic intaglio printing water-based ink and preparation method |
| CN108587304A (en) * | 2018-04-09 | 2018-09-28 | 天津科技大学 | A kind of wood surface silk-screen printing aqueous UV ink and preparation method |
| CN110467901A (en) * | 2018-05-10 | 2019-11-19 | 上海本诺电子材料有限公司 | OLED heats dual UV curable paint organic silicon modified epoxy acrylate glue and preparation method with UV |
| CN109337638B (en) * | 2018-09-05 | 2021-04-20 | 深圳职业技术学院 | Ultraviolet hybrid curing packaging adhesive composition |
| CN109337638A (en) * | 2018-09-05 | 2019-02-15 | 深圳职业技术学院 | A kind of ultraviolet light mixes cure package glue composition |
| CN110078928A (en) * | 2019-04-26 | 2019-08-02 | 深圳职业技术学院 | A kind of low-surface-energy highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof |
| CN110105578A (en) * | 2019-04-26 | 2019-08-09 | 深圳职业技术学院 | A kind of highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof with siliceous segment |
| CN110078928B (en) * | 2019-04-26 | 2021-10-01 | 深圳职业技术学院 | Low-surface-energy high-water-solubility ultraviolet-curing water-based resin and preparation method thereof |
| CN110105578B (en) * | 2019-04-26 | 2021-12-21 | 深圳职业技术学院 | High-water-solubility ultraviolet-curing water-based resin with silicon-containing chain segment and preparation method thereof |
| CN110452361A (en) * | 2019-07-09 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of synthetic method and waterproofing agent of the polyurethane acroleic acid modified organic silicon without fluoro water proofing agent |
| CN110452361B (en) * | 2019-07-09 | 2021-09-21 | 广东德美精细化工集团股份有限公司 | Synthetic method of polyurethane acrylic acid modified organic silicon fluoride-free waterproof agent and waterproof agent |
| CN111205815B (en) * | 2020-03-12 | 2022-02-01 | 东莞市联灏新材料技术开发有限公司 | OLED sealant composition capable of being cured in UV hybrid mode |
| CN111205815A (en) * | 2020-03-12 | 2020-05-29 | 东莞市联灏新材料技术开发有限公司 | OLED sealant composition capable of being cured in UV hybrid mode |
| CN112358841A (en) * | 2020-12-29 | 2021-02-12 | 烟台信友新材料有限公司 | Flexible UV-thermal dual-curing transparent conductive adhesive and preparation method thereof |
| CN112358841B (en) * | 2020-12-29 | 2022-02-08 | 烟台信友新材料有限公司 | Flexible UV-thermal dual-curing transparent conductive adhesive and preparation method thereof |
| CN112552870A (en) * | 2020-12-29 | 2021-03-26 | 烟台信友新材料有限公司 | High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof |
| CN113372816A (en) * | 2021-05-21 | 2021-09-10 | 无锡时生高分子科技有限公司 | Solvent-free UV (ultraviolet) curing type organic silicon three-proofing adhesive |
| CN113817121A (en) * | 2021-09-28 | 2021-12-21 | 泉州师范学院 | Acrylic acid group-terminated silicon chain polyurethane photosensitive prepolymer and preparation method thereof |
| CN113881013A (en) * | 2021-10-27 | 2022-01-04 | 上海古原草科技有限公司 | Acrylic acid modified polyurethane epoxy toughening agent and preparation method thereof |
| CN114231162A (en) * | 2021-11-12 | 2022-03-25 | 广东腐蚀科学与技术创新研究院 | Organic silicon modified polyurethane acrylate ultraviolet light and moisture dual-curing three-proofing paint and preparation method thereof |
| CN113999618A (en) * | 2021-11-22 | 2022-02-01 | 曹云来 | Low-odor and low-irritation dual-curing adhesive and preparation method thereof |
| CN115043986A (en) * | 2022-04-29 | 2022-09-13 | 广州大学 | High-strength photocuring 3D printing resin and preparation method thereof |
| CN117089279A (en) * | 2023-10-19 | 2023-11-21 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
| CN117089279B (en) * | 2023-10-19 | 2023-12-19 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
| CN117567752A (en) * | 2024-01-15 | 2024-02-20 | 广东腐蚀科学与技术创新研究院 | Modified UV/moisture dual-curing resin, three-proofing paint for protecting automobile electronic circuit board and preparation method of three-proofing paint |
| CN117567752B (en) * | 2024-01-15 | 2024-04-12 | 广东腐蚀科学与技术创新研究院 | Modified UV/moisture dual-curing resin, three-proofing paint for protecting automobile electronic circuit board and preparation method of three-proofing paint |
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