CN101503378B - Ultra-low viscosity simple function group carbamate monomer, and preparation and use thereof - Google Patents
Ultra-low viscosity simple function group carbamate monomer, and preparation and use thereof Download PDFInfo
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- CN101503378B CN101503378B CN2009100807147A CN200910080714A CN101503378B CN 101503378 B CN101503378 B CN 101503378B CN 2009100807147 A CN2009100807147 A CN 2009100807147A CN 200910080714 A CN200910080714 A CN 200910080714A CN 101503378 B CN101503378 B CN 101503378B
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Abstract
The invention relates to an ultralow-viscosity single-functional-group carbamate monomer, preparation thereof, and application thereof in the photoreception polymer material field. When Isocyanate and a hydroxyl compound undergo addition reaction to prepare urethane acrylate, toxic and side effects exist and the product has high viscocity. The low-viscosity single-functional-group carbamate monomer provided by the invention has a structure indicated by a general formula I. In the formula, R1 is methyl, ethyl, isopropyl, phenyl or cyclohexyl; R2 is ethyl, isopropyl, phenyl or cyclohexyl; R3 is hydrogen atom or methyl; and R4 is hydrogen atom, methyl or ethyl. The invention obtains an amide-type intermediate product with hydroxyl by carrying out ring cleavage reaction onto cyclic carbonate and secondary amine; and the amide-type intermediate product with hydroxyl reacts with acyl chloride, thereby obtaining the ultralow-viscosity single-functional-group carbamate monomer. The monomer can be used as a reactive diluent to be used for preparing photo-curing coating materials. The method does not use isocyanate compound and has the advantages of low product viscosity and good photo-curing activity.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, be specifically related to a kind of employing non-isocyanate method synthetic ultra-low viscosity simple function group carbamate monomer and preparation thereof and application.
Background technology
Ammonia ester propenoate has a wide range of applications in fields such as photo-cured coating, printing ink, sizing agents.At present, adopt isocyanic ester and the compound that has hydroxyl to carry out addition usually, make ammonia ester propenoate.There are two defectives in this method: the one, and isocyanic ester has irritating smell, and skin, eyes and respiratory tract are had the strong impulse effect, and toxic side effect is bigger; The 2nd, contain the N-H key in the product that is generated, exist very strong hydrogen bond action, thereby the viscosity of product is generally bigger, has influenced its application.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and a kind of nonirritant and toxic side effect are provided, and low simple function group carbamate propenoate and preparation and the application of viscosity.
The structure of ultra-low viscosity simple function group carbamate monomer provided by the present invention is shown in general formula I:
In the formula, R
1A kind of in methyl, ethyl, sec.-propyl, phenyl or the cyclohexyl; R
2A kind of in ethyl, sec.-propyl, phenyl or the cyclohexyl; R
3Be Wasserstoffatoms or methyl; R
4A kind of in Wasserstoffatoms, methyl or the ethyl.
The preparation method of ultra-low viscosity simple function group carbamate monomer provided by the present invention may further comprise the steps:
1) with cyclic carbonate and secondary amine, in molar ratio 1: 1-2 is dissolved in the organic solvent, and in 30-120 ℃ of reaction 1-10h, makes the complete open loop of cyclic carbonate, then removes organic solvent, obtains the amides intermediate product of hydroxyl;
2) the amides intermediate product with the hydroxyl that obtains in the step 1) is dissolved in the organic solvent with acyl chlorides and tertiary amine adding; Wherein, The amides intermediate product of hydroxyl and the mol ratio of acyl chlorides are 1: 1-2, and the mol ratio of tertiary amine and acyl chlorides is 1: 1-3, behind-10-20 ℃ of reaction 3-5h; Unreacting substance and by product are removed in washing, obtain ultra-low viscosity simple function group carbamate monomer.
Wherein, the cyclic carbonate described in the step 1) is a kind of in NSC 11801, propylene carbonate or the butylene.
Secondary amine described in the step 1) is a kind of in dicyclohexyl amine, pentanoic, methylphenylamine, diethylamine or the Diisopropylamine.
Step 2) acyl chlorides described in is acrylate chloride or methacrylic chloride.
Step 2) tertiary amine described in is triethylamine, tripropyl amine, tri-isopropyl amine, tri-n-butylamine, N, a kind of in accelerine or the triphenylamine.But add the HCl that produces in the tertiary amine absorption reaction in the reaction system.
Step 1) and 2) organic solvent described in is a kind of in benzene,toluene,xylene, methylene dichloride, trichloromethane, ETHYLE ACETATE, normal hexane, hexanaphthene, octane or the pimelinketone.
Step 2) in except utilizing acyl chloride reaction to introduce two keys; Also can adopt the esterification of the amides intermediate product of a kind of and hydroxyl in the acrylic or methacrylic acid to introduce two keys; Acrylic or methacrylic acid is 1 with the mol ratio of the amides intermediate product of hydroxyl: 1-3 does not add tertiary amine.
Ultra-low viscosity simple function group carbamate monomer provided by the present invention can be used as reactive thinner, is used to prepare the light solidifying coating material, and concrete steps are following:
After ultra-low viscosity simple function group carbamate monomer and light trigger stirring and dissolving; Add the light reactive resin stirring and dissolving again; Obtain the light solidifying coating material; In the reaction system, the quality percentage composition of ultra-low viscosity simple function group carbamate monomer, light trigger and light reactive resin is respectively 20-60%, 1-10% and 30-70%;
Wherein, described light trigger is one or more in bitter almond oil camphor and verivate, benzil verivate, dialkyl group oxygen benzoylformaldoxime, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, UVNUL MS-40/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine or the camphorquinone/tertiary amine; Described light reactive resin is that epoxy (methyl) vinyl resin, urethane (methyl) vinyl resin, polyester (methyl) vinyl resin, polyethers (methyl) vinyl resin or acroleic acid esterification gather one or more in (methyl) vinyl resin.
Compared with prior art, the present invention has following beneficial effect:
1) ultra-low viscosity simple function group carbamate monomer provided by the present invention does not contain the N-H key, eliminated the influence of hydrogen bond, so viscosity is low.
2) method transformation efficiency provided by the present invention is high, reaction conditions is gentle, need not to add catalyzer, side reaction is few, separation and purification of products is easy, and does not contain deleterious isocyanate compound.
3) ultra-low viscosity simple function group carbamate monomer provided by the present invention is as reactive thinner, and when being used to prepare the light solidifying coating material, photopolymerization reaction is active high, and is also very good to the dilution capacity of oligopolymer.
Description of drawings
The infrared spectrum of the ultra-low viscosity simple function group carbamate monomer of Fig. 1, embodiment 1 preparation.
The double bond conversion rate of Fig. 2, light solidifying coating material and time relation figure; Wherein, curve 1 representative is with the ultra-low viscosity simple function group carbamate monomer that obtains among the embodiment 1 double bond conversion rate and the time relation as the light solidifying coating material of reactive thinner preparation; Curve 2 representatives are with double bond conversion rate and the time relation of iso-bornyl acrylate (IBOA) as the light solidifying coating material of reactive thinner preparation.
Below in conjunction with accompanying drawing and embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment
The preparation and the application of 2-(acryloxy) ethyl-dicyclohexyl carbamate
1) takes by weighing 8.81g (0.1mol) NSC 11801 and be dissolved in the 50ml toluene, add 18.13g (0.1mol) dicyclohexyl amine then, be heated to 90 ℃ of constant temperature and stir, react after 5 hours 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
2) after together adding 27.12g water white transparency dope, 20g triethylamine and 100ml methylene dichloride in the there-necked flask that has mechanical stirring device, temperature of reaction is-10 ℃, and measures the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night; Suction filtration obtains dark red liquid, uses dilute hydrochloric acid solution (1M), NaHCO successively
3Behind saturated solution and the distilled water wash dark red liquid (retaining liquid is subnatant), use anhydrous Na
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) ethyl-dicyclohexyl carbamate liquid, identifies that through ir spectra and nuclear-magnetism structure is suc as formula shown in the II
2-(acryloxy) ethyl-dicyclohexyl carbamate as reactive thinner, is used to prepare the light solidifying coating material:
After 4g 2-(acryloxy) ethyl-dicyclohexyl carbamate and 0.2g 1173 (2-hydroxy-2-methyl-1-phenyl-acetone-1) stirring and dissolving; Add 16g urethane acrylate CN964 (Sartomer company); Stir, obtain the light solidifying coating material.
Viscosity with the above-mentioned light solidifying coating material for preparing of rotational viscosimeter test.The UV-light light intensity is 30mW/cm
2The time, measure the double bond conversion rate and the time relation curve of above-mentioned light solidifying coating material with REAL TIME INFRARED THERMAL IMAGE.The viscosity of above-mentioned light solidifying coating material and photocuring activity all are superior to the light solidifying coating material of common simple function group reactive thinner preparation.Concrete outcome is seen table 1, Fig. 2.
The preparation and the application of 2-(acryloxy) ethyl-diisopropylaminoethyl manthanoate
1) takes by weighing 8.81g (0.1mol) NSC 11801 and be dissolved in the 50ml toluene, add 10.12g (0.1mol) Diisopropylamine then, be heated to 30 ℃ of constant temperature and stir, react after 10 hours 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
2) after together adding 18.93g water white transparency dope, 22g tripropyl amine and 100ml ETHYLE ACETATE in the there-necked flask that has mechanical stirring device, temperature of reaction is 0 ℃, and measures the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night, suction filtration obtains dark red liquid; After using dilute hydrochloric acid solution (1M), NaOH solution and distilled water wash dark red liquid successively, use anhydrous Na
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) ethyl-diisopropylaminoethyl manthanoate liquid, identifies that through ir spectra and nuclear-magnetism structure is shown in formula III
2-(acryloxy) ethyl-diisopropylaminoethyl manthanoate as reactive thinner, is used to prepare the light solidifying coating material:
After 5g 2-(acryloxy) ethyl-diisopropylaminoethyl manthanoate and 0.6g DMPA (α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone) stirring and dissolving, add 25g polyester acrylate EB811 (Cytec company), stir, obtain the light solidifying coating material.
Viscosity with the above-mentioned light solidifying coating material for preparing of rotational viscosimeter test.The UV-light light intensity is 10mW/cm
2The time, measure the double bond conversion rate and the time relation curve of above-mentioned light solidifying coating material with REAL TIME INFRARED THERMAL IMAGE.The viscosity of above-mentioned light solidifying coating material and photocuring activity all are superior to the light solidifying coating material of common simple function group reactive thinner preparation.
Embodiment 3
2-(acryloxy) ethyl-N, the preparation and the application of N-(methyl, phenyl) carbamate
1) takes by weighing 8.81g (0.1mol) NSC 11801 and be dissolved in the 50ml toluene, add 10.72g (0.1mol) methylphenylamine then, be heated to 120 ℃ of constant temperature and stir, react after 1 hour 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
2) after together adding 19.53g water white transparency dope, 25g tri-n-butylamine and 100ml normal hexane in the there-necked flask that has mechanical stirring device, temperature of reaction is 10 ℃, and measures the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night; Suction filtration obtains dark red liquid, uses dilute hydrochloric acid solution (1M), Na successively
2CO
3Behind solution and the distilled water wash dark red liquid, use anhydrous Na
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) ethyl-N, and N-(methyl, phenyl) carbamate liquid identifies that through ir spectra and nuclear-magnetism structure is suc as formula shown in the IV
With 2-(acryloxy) ethyl-N, N-(methyl, phenyl) carbamate is used to prepare the light solidifying coating material as reactive thinner:
With 10g 2-(acryloxy) ethyl-N, after N-(methyl, phenyl) carbamate and 0.8gDEAP (α, the α-diethoxy acetophenone) stirring and dissolving, add 30g amido propenoate 6106 (three wooden companies), stir, obtain the light solidifying coating material.
Viscosity with the above-mentioned light solidifying coating material for preparing of rotational viscosimeter test.The UV-light light intensity is 50mW/cm
2The time, measure the double bond conversion rate and the time relation curve of above-mentioned light solidifying coating material with REAL TIME INFRARED THERMAL IMAGE.The viscosity of above-mentioned light solidifying coating material and photocuring activity all are superior to the light solidifying coating material of common simple function group reactive thinner preparation.
Embodiment 4
The preparation of 2-(acryloxy) sec.-propyl-diethylamino manthanoate
1) takes by weighing 10.2g (0.1mol) propylene carbonate and be dissolved in the 50ml toluene, add 7.32g (0.1mol) diethylamine then, be heated to 70 ℃ of constant temperature and stir, react after 2 hours 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
2) after together adding 17.52g water white transparency dope, 20g triethylamine and 100ml methylene dichloride in the there-necked flask that has mechanical stirring device, temperature of reaction is in 20 ℃, and measures the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night; Suction filtration obtains dark red liquid, uses dilute hydrochloric acid solution (1M), NaHCO successively
3Behind saturated solution and the distilled water wash dark red liquid, use anhydrous Na
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) sec.-propyl-diethylamino manthanoate liquid, identifies that through ir spectra and nuclear-magnetism structure is suc as formula shown in the V
Embodiment 5
The preparation of 2-(acryloxy) sec.-propyl-diphenyl amino manthanoate
1) takes by weighing 11.6g (0.1mol) butylene and be dissolved in the 50ml toluene, add 16.93g (0.1mol) pentanoic then, be heated to 100 ℃ of constant temperature and stir, react after 7 hours 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
2) after together adding 28.53g water white transparency dope, 20g triethylamine and 100ml methylene dichloride in the there-necked flask that has mechanical stirring device, place ice bath (0-5 ℃), and measure the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night; Suction filtration obtains dark red liquid, uses dilute hydrochloric acid solution (1M), NaHCO successively
3Behind saturated solution and the distilled water wash dark red liquid (retaining liquid is subnatant), use anhydrous Na
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) sec.-propyl-diphenyl amino manthanoate liquid, identifies that through ir spectra and nuclear-magnetism structure is suc as formula shown in the VI
| Iso-bornyl acrylate | The ultra-low viscosity simple function group carbamate monomer that obtains among the |
With the light solidifying coating material of iso-bornyl acrylate as the reactive thinner preparation | With the ultra-low viscosity simple function group carbamate monomer that obtains among the |
|
| Viscosity (25 ℃, cps) | 9 | 5.5 | 34×10 4 | ?21.5×10 4 |
Table 1 is the viscosity number of the prepared light solidifying coating material of reactive thinner for the ultra-low viscosity simple function group carbamate monomer of embodiment 1 preparation and with the ultra-low viscosity simple function group carbamate monomer.
Claims (2)
1. a ultra-low viscosity simple function group carbamate monomer is characterized in that, this monomer is 2-(acryloxy) ethyl-dicyclohexyl carbamate, and its structure is as follows:
2. preparation method of ultra-low viscosity simple function group carbamate monomer according to claim 1 is characterized in that concrete steps are following:
(1) takes by weighing the 0.1mol NSC 11801 and be dissolved in the 50ml toluene, add the 0.1mol dicyclohexyl amine then, be heated to 90 ℃ of constant temperature and stir, react after 5 hours 1803cm in the ir spectra
-1About the absorption peak located disappear, stopped reaction is removed solvent toluene, the water white transparency dope;
(2) after together adding 27.12g water white transparency dope, 20g triethylamine and 100ml methylene dichloride in the there-necked flask that has mechanical stirring device, temperature of reaction is-10 ℃, measures the 8.5ml acrylate chloride; In 1 hour, splash in the there-necked flask, after dropwising, continue to stir 2 hours; Hold over night; Suction filtration obtains dark red liquid, uses 1M dilute hydrochloric acid solution, NaHCO successively
3Saturated solution and distilled water wash dark red liquid, retaining liquid is subnatant in the washing process, uses anhydrous Na subsequently
2SO
4Drying is filtered, and removes methylene dichloride, obtains light yellow 2-(acryloxy) ethyl-dicyclohexyl carbamate liquid.
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| CN101983959B (en) * | 2010-07-30 | 2014-11-05 | 北京化工大学 | Multifunctional acrylic ester monomer for photopolymerization and preparing method thereof |
| US9212132B2 (en) | 2011-12-05 | 2015-12-15 | Ricoh Company Ltd. | (Meth)acrylic acid ester, activation energy ray curing composition, and inkjet recording ink |
| CN104558600B (en) * | 2013-10-21 | 2016-08-17 | 乐凯华光印刷科技有限公司 | A kind of nitrogenous poly-functionality methyl acrylate, preparation method and applications |
| CN111056976A (en) * | 2019-12-31 | 2020-04-24 | 海聚高分子材料科技（广州）有限公司 | Urethane multi (methyl) acrylate and preparation method and application thereof |
| CN113321762B (en) * | 2021-06-25 | 2022-02-22 | 西北大学 | Preparation and application of polyacrylate dispersant and super-hydrophobic coating |
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| DE2422170A1 (en) * | 1974-05-08 | 1975-11-20 | Bayer Ag | Polymerisable disubstd. carbamoyloxyalkyl carboxylic acid esters - prepd. from disubstd. carbamic acid beta-hydroxy-alkyl esters and mono-olefinically unsatd. carboxylic acids |
| WO2004077511A2 (en) * | 2003-02-24 | 2004-09-10 | The Regents Of The University Of Colorado | (meth)acrylic and (meth)acrylamide monomers, polymerizable compositions, and polymers obtained |
| KR20070015665A (en) * | 2005-08-01 | 2007-02-06 | 주식회사 동진쎄미켐 | Photosensitive Polymer and photoresist composition including the same |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2422170A1 (en) * | 1974-05-08 | 1975-11-20 | Bayer Ag | Polymerisable disubstd. carbamoyloxyalkyl carboxylic acid esters - prepd. from disubstd. carbamic acid beta-hydroxy-alkyl esters and mono-olefinically unsatd. carboxylic acids |
| WO2004077511A2 (en) * | 2003-02-24 | 2004-09-10 | The Regents Of The University Of Colorado | (meth)acrylic and (meth)acrylamide monomers, polymerizable compositions, and polymers obtained |
| KR20070015665A (en) * | 2005-08-01 | 2007-02-06 | 주식회사 동진쎄미켐 | Photosensitive Polymer and photoresist composition including the same |
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| 吴刚强等.超低粘度氨基甲酸酯丙烯酸酯的合成及应用.《第八届中国辐射固化年会论文集》.2007,第138-141页. * |
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