CN101462973A - 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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- CN101462973A CN101462973A CN 200910076985 CN200910076985A CN101462973A CN 101462973 A CN101462973 A CN 101462973A CN 200910076985 CN200910076985 CN 200910076985 CN 200910076985 A CN200910076985 A CN 200910076985A CN 101462973 A CN101462973 A CN 101462973A
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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) formula (II): 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 and its application in Photocurable composition.
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 higher usually, thereby need to add thinner (monomer) to regulate viscosity.Containing the 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 big; (3) because the general molecular weight of polyfunctional monomer is bigger, so volatility is low; (4) can regulate some performance at service requirements,, increase the hardness of dry film and improve its scratch resistance etc. as accelerating curing speed.
Nitrogenous (methyl) acrylic ester compound as ammonia ester acrylate etc., is the more important light-cured components of a class, has a wide range of applications in fields such as photo-cured coating, printing ink, sizing agent, tooth dental repair materials.Add the kindliness that nitrogenous (methyl) acrylic ester compound can increase solidified coating in the Photocurable composition, reducing stress shrinks, improve sticking power, particularly at the aspects such as photocuring application, stickup and printing of soft grounds such as paper, nonrigid plastic, leather, fabric, pop can.Traditional nitrogenous (methyl) acrylic ester compound generally all is to carry out the addition reaction synthetic by isocyanic ester and the compound that has hydroxyl.There are two defectives in this method: the one, and isocyanic ester all has irritating smell, and skin, eyes and respiratory tract are had the strong impulse effect, and toxic side effect is bigger.The 2nd, this synthetic method side reaction is more, and hydrolysis reaction may take place for dibasic alcohol and isocyanic ester.Minor amount of water branch of containing in the raw material and the reaction of isocyanide ester root form the urea structure that contracts.Too much urea groups structure can cause the material hydrogen bond too much in the polymkeric substance, and rete fragility increases, and water-repellancy descends.In addition, contain the N-H key in the product that is generated, exist very strong hydrogen bond action, thereby the viscosity of product is common bigger, has influenced 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 tooth dental repair material.
Nitrogenous poly-functionality methyl methacrylate monomer provided by the present invention, its structure is shown in general formula (I):
In the formula, R is
Or
N is the integer of 0-5, and m is the integer of 0-4, R
1, R
2Be hydrogen or methyl.
The preparation method of a kind of nitrogenous poly-functionality methyl methacrylate monomer provided by the present invention may further comprise the steps:
(1) with following formula (II) or (III) expression hydroxyl acrylic ester compound and methacrylic chloride, tertiary amine and organic solvent hybrid reaction, the hydroxyl in the wherein hydroxyl acrylic ester compound and the mol ratio of methacrylic chloride are 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 be dissolved in organic solvent with what obtain in the step (1) with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester, the polyamine compounds that adds following formula (VI) expression, wherein the hydrogen atom mol ratio on intermediate product and the polyamine compounds nitrogen-atoms is 1:1～2, temperature of reaction is-10～10 ℃, temperature is risen to 20～50 ℃ then, make the hydrogen complete reaction on the polyamine compounds nitrogen-atoms, remove the nitrogenous poly-functionality methyl methacrylate monomer that finally obtains formula (I) expression after desolvating.
Wherein, R
1, R
2Be hydrogen or methyl, m is the integer of 0-4, and n is the integer of 0-5.
Tertiary amine in the above-mentioned steps (1) is triethylamine, tripropyl amine, tri-isopropyl amine, tri-n-butylamine, N, accelerine, triphenylamine, pyridine or benzo pyridine.Preferred triethylamine, tripropyl amine, tri-isopropyl amine or tri-n-butylamine.
Organic solvent in the 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, cyclohexane, octane, cyclohexanone, N, dinethylformamide, dimethyl sulfoxide (DMSO) etc.
Organic solvent in the 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, cyclohexane, octane, cyclohexanone, N, dinethylformamide, dimethyl sulfoxide (DMSO) etc.
The methyl acrylic ester compound that above-mentioned steps (1) Chinese style (II) or the hydroxyl acrylic ester compound of (III) representing are represented with following formula (VII) or following formula (VIII) replaces, 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
2Be hydrogen or methyl.
The nitrogenous poly-functionality methyl methacrylate monomer one of is formed 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 multiple 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 the camphorquinone/tertiary amine.
In the container of agitator is housed, the reactive thinner and the 1-5% light trigger that add 5-60% nitrogenous poly-functionality methyl acrylate monomer, 0-60%, after the stirring and dissolving, add the light reactive resin of 10-60% again, stirring makes it to mix and promptly gets 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, photopolymerization reaction is active high, except reducing the viscosity of resin, can also increase the kindliness of solidified coating behind the adding Photocurable composition, reduces stress and shrinks, and improves sticking power.Advantages such as the preparation method has transformation efficiency height, reaction conditions gentleness simultaneously, side reaction is few, separation and purification of products is easy.
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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 65g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 65g is dissolved in the 50ml methyl alcohol, at-10 ℃ of following Dropwise 5 .29g quadrols.Dropwise the back and continue to stir 2 hours, be warming up to 20 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 65g N, N, N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2Be hydrogen, m is 0, and 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, and 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 the stirring and dissolving, add 45g urethane acrylate CN964 (Sartomer company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 30mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 81.25g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 81.25g is dissolved in the 50ml methyl alcohol, drips diethylenetriamine 9.10g down at 0 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 25 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 85g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen ethyl propyloic-diethylenetriamine, its structural formula (R
1, R
2Be hydrogen, m is 0, and 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, and 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 the stirring and dissolving; add 40g polyester acrylate EB811 (Cytec company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 10mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 113g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 113g is dissolved in the 50ml methyl alcohol, drips the 16.60g tetraethylene pentamine down at-10 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 50 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed 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
2Be hydrogen, m is 0, and 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, and 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 the stirring and dissolving, add 30g amido acrylate 6106 (three wooden companies) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 40mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 130g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 130g is dissolved in the 50ml methyl alcohol, drips 21.65g (0.1mol) six ethene seven amine down at 0 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 25 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed 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
2Be hydrogen, m is 0, and 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, and 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 the stirring and dissolving; add 30g polyester acrylate EB811 (Cytec company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 15mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 65g acryl oxygen ethyl-methyl acrylate;
(2) acryl oxygen ethyl-methyl acrylate 65g is dissolved in the 50ml methyl alcohol, at-10 ℃ of following Dropwise 5 .29g (0.1mol) quadrol.Dropwise the back and continue to stir 2 hours, be warming up to 20 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 65g N, N, N ', N '-tetramethyl-acryl oxygen ethyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2Be hydrogen, m is 0, and 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, and 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; (0.2g1173 2-hydroxy-2-methyl-1-phenyl-acetone-1); after the stirring and dissolving, add 16g urethane acrylate CN964 (Sartomer company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 30mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 105g acryl oxygen propyl methyl acid esters;
(2) acryl oxygen propyl methyl acid esters 105g is dissolved in the 50ml methyl alcohol, drips triethylene tetramine 12.50g down at 5 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 35 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed 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
2Be hydrogen, m is 1, and 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, and 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 the stirring and dissolving, add 50g amido acrylate 6106 (three wooden companies) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 50mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath (0-5 ℃), reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 120g acryl oxygen propyl methyl acid esters;
(2) acryl oxygen propyl methyl acid esters 120g is dissolved in the 100ml methyl alcohol, drips 19g five ethene hexamines down at 5 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 45 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 130g 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, its structural formula (R
1, R
2Be hydrogen, m is 1, and 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, and 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 the stirring and dissolving, add 20g amido acrylate 6106 (three wooden companies) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 50mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 95g acryl oxygen isobutyl-methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 95g is dissolved in the 50ml methyl alcohol, drips the 9.23g diethylenetriamine down at 0 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 25 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 99g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen isobutyl-propyloic-diethylenetriamine, its structural formula (R
1Be hydrogen, R
2Be methyl, m is 1, and 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, and 4.24-4.16,2.85-2.75,2.46-2.35,1.93,1.06.
In the container of agitator is housed, add 30g N
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) is after the stirring and dissolving; add 30g bisphenol A epoxy acrylate 6210 (Changxing company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 30mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 76g acryl oxygen-butyl methacrylic ester;
(2) acryl oxygen-butyl methacrylic ester 76g is dissolved in the 50ml methyl alcohol, at-10 ℃ of following Dropwise 5 .38g quadrols.Dropwise the back and continue to stir 2 hours, be warming up to 20 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 75g N, N, N ', N '-tetramethyl-acryl oxygen-butyl propyloic-ethane-1,2 diamines, its structural formula (R
1, R
2Be hydrogen, m is 2, and 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, and 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, 3g1173 (2-hydroxy-2-methyl-1-phenyl-acetone-1) is after the stirring and dissolving; add 20g polyester acrylate EB811 (Cytec company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 40mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 100g acryl oxygen tertiary butyl methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 100g is dissolved in the 50ml methyl alcohol, drips the 9.23g diethylenetriamine down at 0 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 25 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed 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
1Be methyl, R
2Be methyl, m is 1, and 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, and 4.07-4.00,2.85-2.75,2.46-2.35,1.11.
In the container of agitator is housed, add 30g N
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) is after the stirring and dissolving; add 30g bisphenol A epoxy acrylate 6210 (Changxing company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 30mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, 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, in ice bath 0-5 ℃, reacts, react after 4 hours, stop to stir standing over night.Finish reaction after the standing over night, successively water, 1M hydrochloric acid, 1MNaOH solution washing are removed unreacted reactant and by product, except that after desolvating, obtain 200g acryl oxygen polyoxyethylene glycol (6) methacrylic ester;
(2) acryl oxygen isopropyl methyl acrylate 200g is dissolved in the 100ml methyl alcohol, drips the 9.23g diethylenetriamine down at 0 ℃.Dropwise the back and continue to stir 2 hours, be warming up to 25 ℃ then and continue the constant temperature stirring, until infrared detection 1640 and 810cm
-1Left and right sides double bond absorption peak disappears, and stopped reaction is removed solvent methanol, obtains 195g N
1, N
1, N
2, N
3, N
3-pentamethyl-acryl oxygen polyoxyethylene glycol (6) propyloic-diethylenetriamine, (m is 1 to its structural formula, and n is 1.) 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, and 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) is after the stirring and dissolving; add 30g bisphenol A epoxy acrylate 6210 (Changxing company) again, stir to make it to mix and obtain Photocurable composition.Placing light intensity is 30mW/cm
2UV-light under shine, measure the photocuring activity with REAL TIME INFRARED THERMAL IMAGE, its polymerization velocity and double bond conversion rate are suitable with commercial monomer effect.
Claims (10)
1. nitrogenous poly-functionality methyl methacrylate monomer, its structure is shown in general formula (I):
Wherein, R is
Or
R
1, R
2Be hydrogen or methyl, m is 0～4 integer, and n is 0～5 integer.
2. monomer according to claim 1 is characterized in that R is
R
1, R
2Be hydrogen or methyl, m is 0～2 integer, and n is 1～3 integer.
3. the preparation method of nitrogenous poly-functionality methyl methacrylate monomer according to claim 1 is characterized in that may further comprise the steps:
(1) with following formula (II) or (III) expression hydroxyl acrylic ester compound and methacrylic chloride, tertiary amine and organic solvent hybrid reaction, the hydroxyl in the wherein hydroxyl acrylic ester compound and the mol ratio of methacrylic chloride are 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 be dissolved in organic solvent with what obtain in the step (1) with acrylic double bond but also with the intermediate product of the two keys of methacrylic ester, the polyamine compounds that adds following formula (VI) expression, wherein the hydrogen atom mol ratio on intermediate product and the polyamine compounds nitrogen-atoms is 1:1～2, temperature of reaction is-10～10 ℃, temperature is risen to 20～50 ℃ then, make the hydrogen complete reaction on the polyamine compounds nitrogen-atoms, remove the nitrogenous poly-functionality methyl methacrylate monomer that finally obtains formula (I) expression after desolvating.
Wherein, R
1, R
2Be hydrogen or methyl, m is the integer of 0-4, and n is the integer of 0-5.
4. according to the method described in the claim 3, it is characterized in that the tertiary amine described in the step (1) is triethylamine, tripropyl amine, tri-isopropyl amine, tri-n-butylamine, N, accelerine, triphenylamine, pyridine or benzo pyridine.
5. method according to claim 3 is characterized in that the tertiary amine described in the step (1) is triethylamine, tripropyl amine, tri-isopropyl amine or tri-n-butylamine.
6. method according to claim 3, it is characterized in that the methyl acrylic ester compound replacement of the hydroxyl acrylic ester compound of step (1) Chinese style (II) or formula (III) expression with following formula (VII) or following formula (VIII) expression, methacrylic chloride replaces with acrylate chloride.
Wherein, R
1, R
2Be hydrogen or methyl, m is 0～4 integer.
7. the purposes of nitrogenous poly-functionality methyl methacrylate monomer according to claim 1 is characterized in that described monomer as one of Photocurable composition 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%.
8. purposes according to claim 7 is characterized in that described 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.
9. purposes according to claim 7 is characterized in that described reactive thinner is any or multiple monomer in simple function group, bifunctional and polyfunctional group (methyl) acrylate monomer.
10. purposes according to claim 7 is characterized in that described 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 the camphorquinone/tertiary amine.
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