CN104530071A - Preparation method of trifunctional acrylate photopolymerizable monomer in dual-loop structure - Google Patents
Preparation method of trifunctional acrylate photopolymerizable monomer in dual-loop structure Download PDFInfo
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- CN104530071A CN104530071A CN201410836286.7A CN201410836286A CN104530071A CN 104530071 A CN104530071 A CN 104530071A CN 201410836286 A CN201410836286 A CN 201410836286A CN 104530071 A CN104530071 A CN 104530071A
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- QLEIDMAURCRVCX-UHFFFAOYSA-N CCCN1CCNCC1 Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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Abstract
The invention discloses a preparation method of a trifunctional acrylate photopolymerizable monomer in a dual-loop structure, belongs to preparation of a functional monomer, and can be applied to an active diluent of a photopolymerizable coating. The general formula of the structure is as shown in the specification, wherein R=R=H, -CH3. The preparation method comprises the following steps: constructing a dual-loop structure by carrying out reaction on furancarboxylic acid or derivatives thereof and D-A of maleic acid to obtain a tricarboxyl product; and carrying out ring-opening reaction with glycidyl acrylate to obtain the functional monomer with photopolymerizable activity. The monomer has the advantages of being quick in reaction rate, great in rigidity of cured coating and the like and is simple in preparation process and relatively high in reaction conversion rates.
Description
Technical field
The present invention relates to a kind of preparation with the acrylic ester monomer of twin nuclei that can be used as photo polymerization monomer.
Technical background
Photocuring a kind ofly utilizes UV-light to cause to produce spike to be active function groups cross-linking reaction in system and the external coating technology that forms solidified coating.Photopolymerization has the feature such as efficient energy-saving, environmental protection and economy.Not containing volatile solvent in photocuring product, adopt the small molecule monomer adjusting viscosity with active function groups, the injury that the volatilization avoiding solvent in coating process causes human body and environment and pollution.
Photo polymerization monomer is a kind of organic molecule containing active function groups, participates in crosslinking reaction, mainly plays the effect of dissolved dilution oligopolymer and regulation system viscosity in photopolymerization product compositions.Because it participates in the process of crosslinking curing, so its structure and functionality affect the overall performance of final coating, therefore select to design the important step that suitable photo polymerization monomer is also photocuring product development.
The monomer of esters of acrylic acid is the reactive monomer of a type free base initiated polymerization, can by radical photoinitiator initiated polymerization.Usually there is the advantages such as low viscosity, high reaction activity, quick solidifying.Along with the raising of functionality, viscosity increases relatively, and cross-linking density and speed of reaction increase fast, and simultaneously the volumetric shrinkage of coating obviously and easily causes degradation defect under loss of adhesion, water-fast weathering resistance gradually.The monomer of usual esters of acrylic acid by polyvalent alcohol and acrylic or methacrylic Esterification and prepare, also can be prepared by transesterify, acrylate chloride method and glycidyl ether ring-opening reaction.By design, there is the polyvalent alcohol of different structure or the molecular skeleton of carboxylic acid acquisition acrylate monomer, prepared the main thought and method that acrylic ester monomer is the exploitation of current acrylic ester monomer by the reaction such as esterification or transesterify.Can obtain the functionalization monomer with specific function by designing suitable molecular structure, the rigid backbone such as designing polynuclear plane can significantly improve the second-order transition temperature of the rear coating of solidification, and makes coating have good hardness and wear resistance.
Summary of the invention
The invention discloses a kind of three-functionality-degree acrylate photo polymerization monomer with twin nuclei, its structure is as follows:
Wherein R=H ,-CH
3,
The reaction equation of the three-functionality-degree acrylate containing twin nuclei that the present invention relates to is as follows:
The concrete preparation process of the three-functionality-degree acrylate monomer of a kind of twin nuclei of the present invention is as follows:
1) 0.05mol furancarboxylic acid or derivatives thereof being dissolved in 10ml DMF (DMF) with waiting mole toxilic acid, being heated to 80 ~ 120 DEG C of reaction 5 ~ 6h; Revolved by product and steam except being dissolved in 20ml acetone after desolventizing, join in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid;
2) by step 1) prepared by product 0.02mol join in there-necked flask, 5ml butanone wherein, add the glycidyl acrylate of 0.06mol, and add catalyzer and stopper, 8 ~ 10h is reacted, stopped reaction during test acid number <10mgKOH/g under 75 ~ 80 DEG C of conditions.
The step 1 of above-mentioned steps) described in furancarboxylic acid or derivatives thereof be 2-furancarboxylic acid, 3-furancarboxylic acid, 4-methyl-2-furancarboxylic acid, 5-methyl-2-furancarboxylic acid, 5-(morpholine-4-methyl)-2-furancarboxylic acid;
The step 2 of above-mentioned steps) described in catalyzer be tetramethyl ammonium chloride, Tetrabutyl amonium bromide, benzyltrimethylammonium bromide; Consumption is 0.5 ~ 1wt% of reactant total mass;
The step 2 of above-mentioned steps) described in stopper be MEHQ, hydroquinone; Consumption is 0.1 ~ 0.5wt% of glycidyl acrylate;
The invention has the advantages that reaction is simple, and productive rate is higher with D-A reaction structure bicyclic skeleton; Prepared product speed of reaction is fast, and photopolymerization transformation efficiency is higher;
Accompanying drawing explanation
Fig. 1 is monomer (S1) prepared by embodiment and Viscoat 295 (TMPTA) photopolymerization rate of polymerization and transformation efficiency comparison diagram, 30% monomer mixes than with commercially available photopolymerization resin SM6001,1wt% initiator 184, light intensity 115mw/cm
2, REAL TIME INFRARED THERMAL IMAGE detects photopolymerization rate of polymerization;
Embodiment
Following embodiment describes the present invention in detail, but does not limit the scope of the invention
Embodiment 1
5.6g (0.05mol) 2-furancarboxylic acid is joined in there-necked flask, adds toxilic acid 5.8g (0.05mol), add 10ml DMF (DMF) and be heated to 60 DEG C, dissolve post-heating to 100 DEG C reaction 5h completely; Product is steamed removing solvent DMF in 100 DEG C of backspins, is then dissolved in 20ml acetone by product, joins in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid; Take prepared white solid 4.56g (0.02mol) in there-necked flask, 5ml butanone wherein, 7.68g glycidyl acrylate is added after dissolving completely, 0.06 tetramethyl ammonium chloride, 0.007g MEHQ, be warming up to 75 DEG C, after reaction 8h, detect acid number, the stopped reaction as acid number <10mgKOH/g; 50 DEG C of backspins steam except desolventizing, obtain transparent liquid, 5%NaOH solution washing, Calcium Chloride Powder Anhydrous dried overnight; Product structure formula as shown in structural formula 1,
1h NMR (250MHz) in CDCl
3: δ 3.3 ~ 3.9ppm (2H, dicyclo C
h-C
h); δ 5.05ppm (1H, dicyclo end of the bridge is hydrocarbon); δ 5.7 ~ 6.4ppm (11H, double bond); δ 6.32ppm (3H ,-OC
h(OH) CH
2-) δ 4.6 ~ 4.9ppm (6H ,-CH
2o-); δ 2.5ppm (hydroxyl);
Structural formula 1
Embodiment 2
5.6g (0.05mol) 3-furancarboxylic acid is joined in there-necked flask, adds toxilic acid 5.8g (0.05mol), add 10ml DMF (DMF) and be heated to 60 DEG C, dissolve post-heating to 120 DEG C reaction 5h completely; Product is steamed removing solvent DMF in 100 DEG C of backspins, is then dissolved in 20ml acetone by product, joins in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid; Take prepared white solid 4.56g (0.02mol) in there-necked flask, 5ml butanone wherein, 7.68g glycidyl acrylate is added after dissolving completely, 0.06 tetramethyl ammonium chloride, 0.035g MEHQ, be warming up to 75 DEG C, after reaction 8h, detect acid number, the stopped reaction as acid number <10mgKOH/g; 50 DEG C of backspins steam except desolventizing, obtain transparent liquid, 5%NaOH solution washing, Calcium Chloride Powder Anhydrous dried overnight; Product structure formula as shown in structural formula 2,
1h NMR (250MHz) in CDCl
3: δ 3.30 ~ 3.90ppm (2H, dicyclo C
h-C
h); δ 5.25ppm (2H, dicyclo end of the bridge is hydrocarbon); δ 5.72 ~ 7.04ppm (10H, double bond); δ 6.32ppm (3H ,-OC
h(OH) CH
2-) δ 4.62 ~ 4.91ppm (6H ,-CH
2o-); δ 2.5ppm (hydroxyl);
Structural formula 2
Embodiment 3
6.3g (0.05mol) 4-methyl 2-furancarboxylic acid is joined in there-necked flask, add toxilic acid 5.8g (0.05mol), add 10ml DMF (DMF) and be heated to 60 DEG C, dissolve post-heating to 80 DEG C reaction 5h completely; Product is steamed removing solvent DMF in 100 DEG C of backspins, is then dissolved in 20ml acetone by product, joins in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid; Take prepared white solid 4.84g (0.02mol) in there-necked flask, 5ml butanone wherein, 7.68g glycidyl acrylate is added after dissolving completely, 0.12g Tetrabutyl amonium bromide, 0.025g MEHQ, be warming up to 75 DEG C, after reaction 8h, detect acid number, the stopped reaction as acid number <10mgKOH/g; 50 DEG C of backspins steam except desolventizing, obtain transparent liquid, 5%NaOH solution washing, Calcium Chloride Powder Anhydrous dried overnight; Product structure formula as shown in structural formula 3,
1h NMR (250MHz) in CDCl
3: δ 1.73ppm (3H ,-CH
3); δ 3.30 ~ 3.97ppm (2H, dicyclo C
h-C
h); δ 5.05ppm (1H, dicyclo end of the bridge is hydrocarbon); δ 5.72 ~ 6.44ppm (10H, double bond); δ 6.32ppm (3H ,-OC
h(OH) CH
2-) δ 4.62 ~ 4.91ppm (6H ,-CH
2o-); δ 2.5ppm (hydroxyl);
Structural formula 3
Embodiment 4
6.3g (0.05mol) 5-methyl 2-furancarboxylic acid is joined in there-necked flask, add toxilic acid 5.8g (0.05mol), add 10ml DMF (DMF) and be heated to 60 DEG C, dissolve post-heating to 100 DEG C reaction 5h completely; Product is steamed removing solvent DMF in 100 DEG C of backspins, is then dissolved in 20ml acetone by product, joins in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid; Take prepared white solid 4.84g (0.02mol) in there-necked flask, 5ml butanone wherein, 7.68g glycidyl acrylate is added after dissolving completely, 0.12g benzyltrimethylammonium bromide, 0.015g Resorcinol, be warming up to 85 DEG C, after reaction 8h, detect acid number, the stopped reaction as acid number <10mgKOH/g; 50 DEG C of backspins steam except desolventizing, obtain transparent liquid, 5%NaOH solution washing, Calcium Chloride Powder Anhydrous dried overnight; Product structure formula as shown in structural formula 4,
1h NMR (250MHz) in CDCl
3: δ 1.41ppm (3H ,-CH
3); δ 3.30 ~ 3.97ppm (2H, dicyclo C
h-C
h); δ 5.72 ~ 6.44ppm (11H, double bond); δ 6.32ppm (3H ,-OC
h(OH) CH
2-) δ 4.62 ~ 4.91ppm (6H ,-CH
2o-); δ 2.5ppm (hydroxyl);
Structural formula 4
Embodiment 5
10.05g (0.05mol) 5-(morpholine-4-methyl)-2-furancarboxylic acid is joined in there-necked flask, add toxilic acid 5.8g (0.05mol), add 10ml N, dinethylformamide (DMF) is heated to 60 DEG C, dissolves post-heating to 110 DEG C reaction 5h completely; Product is steamed removing solvent DMF in 100 DEG C of backspins, is then dissolved in 20ml acetone by product, joins in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid; Take prepared white solid 6.54g (0.02mol) in there-necked flask, 5ml butanone wherein, 7.68g glycidyl acrylate is added after dissolving completely, 0.12g Tetrabutyl amonium bromide, 0.020g MEHQ, be warming up to 85 DEG C, after reaction 8h, detect acid number, the stopped reaction as acid number <10mgKOH/g; 50 DEG C of backspins steam except desolventizing, obtain transparent liquid, 5%NaOH solution washing, Calcium Chloride Powder Anhydrous dried overnight; Product structure formula as shown in structural formula 5,
1h NMR (250MHz) in CDCl
3: δ 2.35 ~ 2.49ppm (6H ,-C
h 2 -N); δ 3.61 ~ 3.68 (4H, O-C
h 2 -N); δ 3.30 ~ 3.97ppm (2H, dicyclo C
h-C
h); δ 5.72 ~ 6.44ppm (11H, double bond); δ 6.32ppm (3H ,-OC
h(OH) CH
2-) δ 4.62 ~ 4.91ppm (6H ,-CH
2o-); δ 2.0ppm (hydroxyl)
Claims (6)
1. the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei, its structure is as follows:
。
2. the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei according to claim 1, is characterized in that wherein R=H ,-CH3,
.
3. the preparation method of the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei according to claim 1 and 2, is characterized in that carrying out in the steps below:
1) 0.05mol furancarboxylic acid or derivatives thereof being dissolved in 10ml DMF (DMF) with waiting mole toxilic acid, being heated to 80 ~ 120 DEG C of reaction 5 ~ 6h; Revolved by product and steam except being dissolved in 20ml acetone after desolventizing, join in ether, filter out precipitation, by 10ml methanol wash 2 times, dried overnight in vacuum drying oven, obtains white solid;
2) by step 1) prepared by product 0.02mol join in there-necked flask, 5ml butanone wherein, add the glycidyl acrylate of 0.06mol, and add catalyzer and stopper, 8 ~ 10h is reacted, stopped reaction during test acid number <10mgKOH/g under 75 ~ 80 DEG C of conditions.
4. the preparation method of the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei according to claim 3, is characterized in that wherein step 1) described in furancarboxylic acid or derivatives thereof be 2-furancarboxylic acid, 3-furancarboxylic acid, 4-methyl-2-furancarboxylic acid, 5-methyl-2-furancarboxylic acid, 5-(morpholine-4-methyl)-2-furancarboxylic acid.
5. the preparation method of the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei according to claim 3, is characterized in that wherein step 2) described in catalyzer be tetramethyl ammonium chloride, Tetrabutyl amonium bromide, benzyltrimethylammonium bromide; Consumption is 0.5 ~ 1wt% of reactant total mass.
6. the preparation method of the three-functionality-degree acrylate photo polymerization monomer containing twin nuclei according to claim 3, is characterized in that wherein step 2) described in stopper be MEHQ, hydroquinone; Consumption is 0.1 ~ 0.5wt% of glycidyl acrylate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019199436A (en) * | 2018-05-16 | 2019-11-21 | 東洋インキＳｃホールディングス株式会社 | Morpholine ring-containing (meth)acrylate compound and polymerizable composition using same |
| CN115960298A (en) * | 2021-10-12 | 2023-04-14 | 上海新阳半导体材料股份有限公司 | Resin and ArF dry-process photoresist composition containing same |
| CN115960299A (en) * | 2021-10-12 | 2023-04-14 | 上海新阳半导体材料股份有限公司 | Preparation method of resin for ArF dry photoetching |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019199436A (en) * | 2018-05-16 | 2019-11-21 | 東洋インキＳｃホールディングス株式会社 | Morpholine ring-containing (meth)acrylate compound and polymerizable composition using same |
| CN115960298A (en) * | 2021-10-12 | 2023-04-14 | 上海新阳半导体材料股份有限公司 | Resin and ArF dry-process photoresist composition containing same |
| CN115960299A (en) * | 2021-10-12 | 2023-04-14 | 上海新阳半导体材料股份有限公司 | Preparation method of resin for ArF dry photoetching |
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Application publication date: 20150422 |