CN101462973B - Nitrogen-containing polyfunctionality metacrylic acid ester monomer, preparation and use thereof - Google Patents
Nitrogen-containing polyfunctionality metacrylic acid ester monomer, preparation and use thereof Download PDFInfo
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- CN101462973B CN101462973B CN2009100769855A CN200910076985A CN101462973B CN 101462973 B CN101462973 B CN 101462973B CN 2009100769855 A CN2009100769855 A CN 2009100769855A CN 200910076985 A CN200910076985 A CN 200910076985A CN 101462973 B CN101462973 B CN 101462973B
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Abstract
The invention relates to a nitrogenous poly-functionality methyl acrylate monomer and a preparation method and application thereof. The structure of the monomer is shown in general formula (I): R1, R2 are hydrogen or methyl, m is an integer ranging from 0 to 4, and n is an integer ranging from 0 to 5. The preparation method of the monomer includes that (methyl) acrylate compound with hydroxy and (methyl) acryloyl chloride react with each other to obtain an intermediate product with acrylate double-bond and methyl acrylate double-bond; the intermediate product is led to carry out Michael addition reaction with polyamine compound, so as to obtain the product. The method has the advantages of high conversion rate, mild reaction condition and easy separation and purification of the product, and provides a novel photopolymerization active compound system with excellent application prospect.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, be specifically related to a series of nitrogenous poly-functionality methyl methyl acrylic ester monomers and preparation method thereof application in Photocurable composition with it.
Background technology
Any one Photocurable composition all comprises three kinds of main ingredients: light trigger, monomer and oligopolymer (resin).Because the viscosity of resin is usually higher, thereby need to add thinner (monomer) with adjusting viscosity.Containing acrylate more than 3 or 3 or the monomer of methacrylic ester optical active group is polyfunctional monomer.Because functional group content increases, these monomers have following characteristics: (1) laser curing velocity is fast; (2) cured product hardness is large; (3) because the general molecular weight of polyfunctional monomer is larger, so volatility is low; (4) can regulate some performance for service requirements,, as accelerating curing speed, increase the hardness of dry film and improve its scratch resistance etc.
Nitrogenous (methyl) acrylic ester compound,, as ammonia ester acrylate etc., be the important light-cured components of a class, in fields such as photo-cured coating, printing ink, sizing agent, gear division repair materials, has a wide range of applications.Add nitrogenous (methyl) acrylic ester compound can increase the kindliness of solidified coating in Photocurable composition, reducing stress shrinks, improve sticking power, particularly at the aspects such as photocuring application, stickup and printing of the soft grounds such as paper, nonrigid plastic, leather, fabric, pop can.Traditional nitrogenous (methyl) acrylic ester compound is all generally with carry out addition reaction with the compound of hydroxyl synthetic by isocyanic ester.There are two defects in the method: the one, and isocyanic ester is irritant smell all, and skin, eyes and respiratory tract are had the strong impulse effect, and toxic side effect is larger.The 2nd, this synthetic method side reaction is more, and hydrolysis reaction may occur for dibasic alcohol and isocyanic ester.The minor amount of water branch of containing in raw material and the reaction of isocyanide ester root form the contracting urea structure.In polymkeric substance, too much urea groups structure can cause the material hydrogen bond too much, and rete fragility increases, and water-repellancy descends.In addition, contain the N-H key in the product that generates, exist very strong hydrogen bond action, thereby the viscosity of product is common larger, has affected its application.
Summary of the invention
The objective of the invention is synthetic a series of nitrogenous poly-functionality methyl methyl acrylic ester monomers, and use it in the various photocurings fields such as photo-cured coating, printing ink, tackiness agent and gear division repair materials.
Nitrogenous poly-functionality methyl methacrylate monomer provided by the present invention, its structure is as shown in general formula (I):
In formula, R is
N is the integer of 0-5, and m is the integer of 0-4, R
1, R
2For hydrogen or methyl.
The preparation method of a kind of nitrogenous poly-functionality methyl methacrylate monomer provided by the present invention comprises the following steps:
(1) with following formula (II) or (III) expression hydroxyl acrylic ester compound and methacrylic chloride, tertiary amine and organic solvent hybrid reaction, wherein the mol ratio of the hydroxyl in hydroxyl acrylic ester compound and methacrylic chloride is 1: 1～2, temperature of reaction is-10～20 ℃, after reaction finishes, unreacting substance and by product are removed in washing, finally obtain formula (IV) or (V) expression not only with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester.
(2) not only with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester, be dissolved in organic solvent with what obtain in step (1), the polyamine compounds that adds following formula (VI) expression, wherein the hydrogen atom mol ratio on intermediate product and polyamine compounds nitrogen-atoms is 1: 1～2, temperature of reaction is-10～10 ℃, then temperature is risen to 20～50 ℃, make the hydrogen complete reaction on the polyamine compounds nitrogen-atoms, except the nitrogenous poly-functionality methyl methacrylate monomer that finally obtains formula (I) expression after desolventizing.
Wherein, R
1, R
2For hydrogen or methyl, m is the integer of 0-4, and n is the integer of 0-5.
Tertiary amine in above-mentioned steps (1) is triethylamine, tripropyl amine, tri-isopropyl amine, tri-n-butylamine, DMA, triphenylamine, pyridine or benzo pyridine.Preferred triethylamine, tripropyl amine, tri-isopropyl amine or tri-n-butylamine.
Organic solvent in above-mentioned steps (1) is organic solvent commonly used, as acetone, butanone, benzene,toluene,xylene, methylene dichloride, trichloromethane, ethyl acetate, propyl acetate, butylacetate, normal hexane, hexanaphthene, octane, pimelinketone, DMF, dimethyl sulfoxide (DMSO) etc.
Organic solvent in above-mentioned steps (2) is organic solvent commonly used, as acetone, butanone, benzene,toluene,xylene, methylene dichloride, trichloromethane, ethyl acetate, propyl acetate, butylacetate, normal hexane, hexanaphthene, octane, pimelinketone, N, dinethylformamide, dimethyl sulfoxide (DMSO) etc.
Above-mentioned steps (1) Chinese style (II) or the hydroxyl acrylic ester compound that (III) represents replace with the methyl acrylic ester compound of following formula (VII) or following formula (VIII) expression, methacrylic acid chlorine replaces with the vinylformic acid chloro, finally obtain formula (IV) or (V) expression not only with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester.
Wherein, m is 0～4 integer, R
1, R
2For hydrogen or methyl.
The nitrogenous poly-functionality methyl methacrylate monomer one of forms as Photocurable composition, and the quality percentage composition of each component of Photocurable composition is:
Light reactive resin 10～60%
Reactive thinner 0～60%
Nitrogenous poly-functionality methyl methacrylate monomer 5～60%
Light trigger 1～5%
Above-mentioned light reactive resin is any or various kinds of resin in poly-(methyl) acrylic resin of epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin and acroleic acid esterification.
Above-mentioned reactive thinner is any or various of monomer in simple function group, bifunctional and polyfunctional group (methyl) acrylate monomer.
Above-mentioned light trigger is any or multiple in bitter almond oil camphor and derivative, benzil derivative, dialkyl group oxygen benzoylformaldoxime, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine.
In the container of agitator is housed, the reactive thinner and the 1-5% light trigger that add 5-60% nitrogenous polyfunctional acrylic ester monomer, 0-60%, after stirring and dissolving, then add the light reactive resin of 10-60%, stir to make it to mix and namely obtain Photocurable composition.
Compared with prior art, the present invention has following beneficial effect:
This class novel nitrogen-containing polyfunctionality methacrylate monomer that the present invention is prepared, the photopolymerization reaction activity is high, adds after Photocurable composition except reducing the viscosity of resin, can also increase the kindliness of solidified coating, reduces stress and shrinks, and improves sticking power.The preparation method has the advantages such as transformation efficiency is high, reaction conditions is gentle, side reaction is few, separation and purification of products is easy simultaneously.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
(1) methacrylic chloride 34ml is added drop-wise in the methylene dichloride 200ml solution that contains Hydroxyethyl acrylate 46.45g and triethylamine 80g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 65g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 65g is dissolved in 50ml methyl alcohol, drips the 5.29g quadrol under-10 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 20 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 65g N, N, N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2For hydrogen, m is that 0, n is 0.) as follows:
Wherein, R
3For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.43-4.36,2.75,2.46-2.35,1.93
In the container of agitator is housed; add 35g N; N; N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines; 2g 1173 (2-hydroxy-2-methyl-1-phenyl-acetone-1); after stirring and dissolving, then add 45g urethane acrylate CN964 (Sartomer company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 30mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 2
(1) methacrylic chloride 43ml is added drop-wise in the ethyl acetate 300ml solution that contains Hydroxyethyl acrylate 58.06g and tripropyl amine 110g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 81.25g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 81.25g is dissolved in 50ml methyl alcohol, drips diethylenetriamine 9.10g under 0 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 25 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 85gN
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen ethyl propyloic-diethylenetriamine, its structural formula (R
1, R
2For hydrogen, m is that 0, n is 1.) as follows:
Wherein, R
3For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.43-4.36,2.75,2.46-2.35,1.93
In the container of agitator is housed, add 20g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen ethyl propyloic-diethylenetriamine; 10g tripropylene glycol double methacrylate; 1g DMPA (α; alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone); after stirring and dissolving; add again 40g polyester acrylate EB811 (Cytec company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 10mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 3
(1) methacrylic chloride 61ml is added drop-wise in the normal hexane 500ml solution that contains Hydroxyethyl acrylate 81.28g and tri-n-butylamine 175g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 113g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 113g is dissolved in 50ml methyl alcohol, drips the 16.60g tetraethylene pentamine under-10 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 50 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 120g N
1, N
1, N
2, N
3, N
4, N
5, N
5-seven methacryloyl oxygen ethyl propyloic-tetraethylene pentamine, its structural formula (R
1, R
2For hydrogen, m is that 0, n is 3.) as follows:
Wherein, R
3For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.43-4.36,2.75,2.46-2.35,1.93.
In the container of agitator is housed, add 20g N
1, N
1, N
2, N
3, N
4, N
5, N
5-seven methacryloyl oxygen ethyl propyloic-tetraethylene pentamine; 5g tetramethylolmethane triolefin acid esters; 0.8g DEAP (α; α-diethoxy acetophenone); after stirring and dissolving; add again 30g amido acrylate 6106 (three wooden companies), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 40mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 4
(1) methacrylic chloride 77ml is added drop-wise in the ethyl acetate 300ml solution that contains Hydroxyethyl acrylate 104.51g (0.9mol) and tripropyl amine 110g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 130g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 130g is dissolved in 50ml methyl alcohol, drips 21.65g (0.1mol) six ethene seven amine under 0 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 25 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 140g N
1, N
1, N
2, N
3, N
4, N
5, N
6, N
7, N
7-nine methacryloyl oxygen ethyl propyloic-six ethene seven amine, its structural formula (R
1, R
2For hydrogen, m is that 0, n is 5.) as follows:
Wherein, R
3For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.43-4.36,2.75,2.46-2.35,1.93.
In the container of agitator is housed, add 10g N
1, N
1, N
2, N
3, N
4, N
5, N
6, N
7, N
7-nine methacryloyl oxygen ethyl propyloic-six ethene seven amine; 10g tripropylene glycol double methacrylate; 0.6g DMPA (α; alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone); after stirring and dissolving; add again 30g polyester acrylate EB811 (Cytec company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 15mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 5
(1) acrylate chloride 34ml is added drop-wise in the methylene dichloride 200ml solution that contains hydroxyethyl methylacrylate 52.06g and triethylamine 80g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 65g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 65g is dissolved in 50ml methyl alcohol, drips 5.29g (0.1mol) quadrol under-10 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 20 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 65g N, N, N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2For hydrogen, m is that 0, n is 0.) as follows:
Wherein, R
3For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.43-4.36,2.75,2.46-2.35,1.93
In the container of agitator is housed; add 4g N; N; N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines; 0.2g 1173 (2-hydroxy-2-methyl-1-phenyl-acetone-1); after stirring and dissolving, then add 16g urethane acrylate CN964 (Sartomer company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 30mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 6
(1) methacrylic chloride 52ml is added drop-wise in the normal hexane 400ml solution that contains Propylene glycol monoacrylate 78.00g and tri-n-butylamine 150g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 105g acryl oxygen propyl methyl acid esters;
(2) acryl oxygen propyl methyl acid esters 105g is dissolved in 50ml methyl alcohol, drips triethylene tetramine 12.50g under 5 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 35 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 110g N
1, N
1, N
2, N
3, N
4, N
4-hexamethyl acryl oxygen propyl group propyloic-triethylene tetramine, its structural formula (R
1, R
2For hydrogen, m is that 1, n is 2.) as follows:
Wherein, R
4For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.15-4.08,2.75,2.46-2.35,1.93,1.85.
In the container of agitator is housed, add 30g N
1, N
1, N
2, N
3, N
4, N
4-hexamethyl acryl oxygen propyl group propyloic-triethylene tetramine, 5g tetramethylolmethane triolefin acid esters, 2g DEAP (α; α-diethoxy acetophenone); after stirring and dissolving, then add 50g amido acrylate 6106 (three wooden companies), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 50mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 7
(1) methacrylic chloride 68ml is added drop-wise in the normal hexane 400ml solution that contains Propylene glycol monoacrylate 78.00g and tri-n-butylamine 150g, reacts in ice bath (0-5 ℃), react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 120g acryl oxygen propyl methyl acid esters;
(2) acryl oxygen propyl methyl acid esters 120g is dissolved in 100ml methyl alcohol, drips 19g five ethene hexamines under 5 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 45 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 130gN
1, N
1, N
2, N
3, N
4, N
5, N
6, N
6-prestox acryl oxygen propyl group propyloic-five ethene hexamine, its structural formula (R
1, R
2For hydrogen, m is that 1, n is 4.) as follows:
Wherein, R
4For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.15-4.08,2.75,2.46-2.35,1.93,1.85.
In the container of agitator is housed, add 10g N
1, N
1, N
2, N
3, N
4, N
5, N
6, N
6-prestox acryl oxygen propyl group propyloic-five ethene hexamine; 10g tetramethylolmethane triolefin acid esters; 3g DEAP (α; α-diethoxy acetophenone); after stirring and dissolving; add again 20g amido acrylate 6106 (three wooden companies), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 50mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 8
(1) methacrylic chloride 43ml is added drop-wise in the ethyl acetate 300ml solution that contains vinylformic acid hydroxyl isobutyl ester 72.09g and tripropyl amine 110g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 95g acryl oxygen isobutyl-methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 95g is dissolved in 50ml methyl alcohol, drips the 9.23g diethylenetriamine under 0 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 25 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 99g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen isobutyl-propyloic-diethylenetriamine, its structural formula (R
1For hydrogen, R
2For methyl, m is that 1, n is 1.) as follows:
Wherein, R
5For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.24-4.16,2.85-2.75,2.46-2.35,1.93,1.06.
In the container of agitator is housed, add 30gN
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen isobutyl-propyloic-diethylenetriamine; 1g DMPA (α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone), after stirring and dissolving; add again 30g bisphenol A epoxy acrylate 6210 (Changxing company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 30mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 9
(1) methacrylic chloride 34ml is added drop-wise in the methylene dichloride 200ml solution that contains vinylformic acid hydroxy butyl ester 57.67g and triethylamine 80g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 76g acryl oxygen-butyl methacrylic ester;
(2) acryl oxygen-butyl methacrylic ester 76g is dissolved in 50ml methyl alcohol, drips the 5.38g quadrol under-10 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 20 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 75g N, N, N ', N '-tetramethyl-acryl oxygen-butyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2For hydrogen, m is that 2, n is 0.) as follows:
Wherein, R
6For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.15,4.08,2.75,2.46-2.35,1.93,1.57.
In the container of agitator is housed; add 10g N; N, N ', N '-tetramethyl-acryl oxygen-butyl propyloic-ethane-1; 2 diamines; 10g neopentyl glycol double methacrylate, 3g 1173 (2-hydroxy-2-methyl-1-phenyl-acetone-1), after stirring and dissolving; add again 20g polyester acrylate EB811 (Cytec company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 40mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 10
(1) methacrylic chloride 43ml is added drop-wise in the ethyl acetate 300ml solution that contains vinylformic acid hydroxyl tert-butyl ester 79.09g and tripropyl amine 110g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 100g acryl oxygen tertiary butyl methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 100g is dissolved in 50ml methyl alcohol, drips the 9.23g diethylenetriamine under 0 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 25 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 105g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen tertiary butyl propyloic-diethylenetriamine, its structural formula (R
1For methyl, R
2For methyl, m is that 1, n is 1.) as follows:
Wherein, R
7For
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.07-4.00,2.85-2.75,2.46-2.35,1.11.
In the container of agitator is housed, add 30gN
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen tertiary butyl propyloic-diethylenetriamine; 1g DMPA (α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone), after stirring and dissolving; add again 30g bisphenol A epoxy acrylate 6210 (Changxing company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 30mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Embodiment 11
(1) methacrylic chloride 43ml is added drop-wise in the ethyl acetate 500ml solution that contains 210.27g polypropylene-base ethylene glycol (6) acrylate and tripropyl amine 110g, reacts in ice bath 0-5 ℃, react after 4 hours, stop stirring standing over night.Finish reaction after standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product,, except after desolventizing, obtain 200g acryl oxygen polyoxyethylene glycol (6) methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 200g is dissolved in 100ml methyl alcohol, drips the 9.23g diethylenetriamine under 0 ℃.Dropwise rear continuation and stirred 2 hours, then be warming up to 25 ℃ and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1The left and right double bond absorption peak disappears, and stopped reaction, remove solvent methanol, obtains 195g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen polyoxyethylene glycol (6) propyloic-diethylenetriamine, (m is that 1, n is 1 to its structural formula.) as follows:
Wherein, R is
Ir data is (cm
-1): 2977,2931,1712,1641,810
Proton magnetic spectrum data are (ppm): 6.15,5.58,4.73,4.45-4.16,2.75,2.35,1.40.
In the container of agitator is housed, add 30g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen polyoxyethylene glycol (6) propyloic-diethylenetriamine; 1g DMPA (α; alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone); after stirring and dissolving; add again 30g bisphenol A epoxy acrylate 6210 (Changxing company), stir to make it to mix and obtain Photocurable composition.Being placed in light intensity is 30mW/cm
2UV-light under shine, measure photocuring with REAL TIME INFRARED THERMAL IMAGE active, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Claims (4)
1. method for preparing nitrogenous poly-functionality methyl methacrylate monomer as shown in general formula (I),
Wherein,
R is
R
1, R
2For hydrogen or methyl, m is 0～4 integer, and n is 0,
The method comprises the following steps:
(1) with hydroxyl acrylic ester compound and methacrylic chloride, tertiary amine and the organic solvent hybrid reaction of following formula (II) expression, wherein the mol ratio of the hydroxyl in hydroxyl acrylic ester compound and methacrylic chloride is 1: 1～2, temperature of reaction is-10～20 ℃, after reaction finishes, unreacting substance and by product are removed in washing, finally obtain formula (IV) expression not only with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester;
(2) not only with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester, be dissolved in organic solvent with what obtain in step (1), the polyamine compounds that adds following formula (VI) expression, wherein the hydrogen atom mol ratio on intermediate product and polyamine compounds nitrogen-atoms is 1: 1～2, temperature of reaction is-10～10 ℃, then temperature is risen to 20～50 ℃, make the hydrogen complete reaction on the polyamine compounds nitrogen-atoms, except the nitrogenous poly-functionality methyl methacrylate monomer that finally obtains formula (I) expression after desolventizing;
2. method according to claim 1, is characterized in that, m is 0～2 integer.
3. method according to claim 1, is characterized in that, the tertiary amine described in step (1) is triethylamine, tripropyl amine, tri-isopropyl amine, tri-n-butylamine, DMA, triphenylamine, pyridine or benzo pyridine.
4. method according to claim 3, is characterized in that, the tertiary amine described in step (1) is triethylamine, tripropyl amine, tri-isopropyl amine or tri-n-butylamine.
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| CN106279241A (en) * | 2016-07-16 | 2017-01-04 | 北京化工大学 | A kind of single functionality acrylate monomer of silicone-containing structure and preparation method thereof |
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