CN112457191A - (meth) acrylic acid ester compound - Google Patents
(meth) acrylic acid ester compound Download PDFInfo
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- CN112457191A CN112457191A CN202011337380.XA CN202011337380A CN112457191A CN 112457191 A CN112457191 A CN 112457191A CN 202011337380 A CN202011337380 A CN 202011337380A CN 112457191 A CN112457191 A CN 112457191A
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
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- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C09D11/00—Inks
- C09D11/02—Printing inks
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C07C2601/14—The ring being saturated
Abstract
The invention relates to a (methyl) acrylate compound, a preparation method and application thereof. The compound has the following structure:
Description
Technical Field
The invention relates to a (methyl) acrylic ester compound which can be used as a reactive diluent, can carry out free radical polymerization reaction and is used in photocuring printing ink, photocuring adhesive and photocuring paint. The invention also relates to a preparation method of the compound and application of the compound in photocuring printing ink, coating and adhesive.
Background
Reactive diluent (reactive diluent) is a small organic molecule containing a polymerizable functional group. The (methyl) acrylate reactive diluent can not only dissolve and dilute polymers and adjust the viscosity of a system in products such as coating, adhesives, printing ink and the like, but also participate in the polymerization process to influence the reaction rate and various performances of final products. Generally, the reactive diluents used in photocurable material systems which polymerize by free radical initiation are mainly acrylate compounds, such as compounds containing acryloxy and methacryloxy groups. Early acrylate reactive diluents were mainly alkyl acrylates and methacrylates, which have the advantages of low viscosity and strong dilutability, but their use was limited by the disadvantages of strong odor, volatility, flammability, etc. With the increasing demands for environmental protection and safety, scientists have developed methoxylated, ethoxylated or propoxylated alcohol acrylates to improve the above problems, but such problems still remain. Low-molecular (meth) acrylates having a functionality of 2 or more can satisfy the requirements of low viscosity, low odor, less irritation and high reactivity, such as 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, octapentanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, etc. However, when such a substance is used in actual ink or coating, problems such as too high crosslinking density, hard and brittle cured product, and poor adhesion to a substrate occur. Therefore, with the development of the photo-curing industry, a class of low-volatility, low-viscosity and high-reactivity reactive diluents is needed.
Disclosure of Invention
In view of the above, the present invention is designed based on finding a class of compounds with low volatility, low viscosity, high reactivity, and low odor, low irritation, etc., and using the compounds as a reactive diluent for photo-curing coatings, adhesives, and inks of radical polymerization.
Therefore, the invention aims to provide a (methyl) acrylate compound.
Another object of the present invention is to provide a method for producing the (meth) acrylic ester compound, which is efficient, convenient and practical.
In order to achieve the above object, the present invention provides a (meth) acrylate compound having the following formula:
in the formula, R1Is a hydrogen atom or a methyl group;
m is 0, 1 or 2; n is 1, 2, 3 or 4;
R2selected from the following groups:
(a)C4～C10aliphatic straight or branched alkanes, alkenes, or alkynes. Such as butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, isooctyl, ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, ethynyl, propynyl, butynyl, and the like;
(b)C3～C10an alkyl group. Such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, methylcyclopropyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 4-methylcyclohexyl, isobornyl, biscyclopentadienyl and the like;
(c) aryl, C1-C4 alkyl, aryl substituted by halogen or nitro, aryl alkyl (C)1～C4) And (4) a base. Such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, xylyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl and the like;
(d) a heterocyclic group, or a heterocyclic group containing oxygen or nitrogen. Such as: 2-tetrahydrofuryl, 3-tetrahydrofuryl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, tetrahydrofurfuryl, epoxypropyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, and the like;
(e) an ether group. R3Radicals C1-C4 alkyl ether radicals, e.g. -CH2OR3，-CH2CH2OR3，-CH2CH2CH2OR3，-CH2CH2CH2CH2OR3；R3There may be mentioned hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, epoxyethyl group, phenyl group and the like.
When m is 0, R3As above, priority R3Hydrogen atom, methyl, ethyl, propyl, phenyl, etc.; when m is
When not equal to 0, R3Is a hydrogen atom.
The preparation of the compounds of the invention can be described as follows:
in the presence of a catalyst, a polymerization inhibitor and an organic solvent, formula H2C＝CR1R of C (O) OM1The molar ratio of the substituted acrylate to the halogenated organic acid ester is 0.5-2: 1 and the weight ratio of the catalyst to the halogenated organic acid ester is 0.0001-0.1: 1, reacting for 1-50 hours at room temperature-reflux temperature to obtain:
wherein R is1The substituted acrylate has the formula H2C＝CR1C(O)OM，
The halogenated organic acid ester has the formula [ X (CH)2)m CH(R3)COO]n R2，
The catalyst is quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, trihydrocarbylphosphine, crown ether or polyethylene glycol,
the polymerization inhibitor is a common polymerization inhibitor such as hydroquinone, p-methoxyphenol, p-benzoquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, phenothiazine, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, cuprous chloride, ferric chloride and the like, and can be used alone or in combination. Preferably hydroquinone, p-methoxyphenol, p-benzoquinone, cuprous chloride, phenothiazine, and 2,2,6, 6-tetramethylpiperidine-N-oxyl, alone or in combination.
Wherein X is a halogen, and M is a monovalent or divalent alkali metal ion, such as potassium (meth) acrylate, sodium (meth) acrylate, lithium (meth) acrylate, calcium (meth) acrylate, and magnesium (meth) acrylate, with potassium (meth) acrylate and sodium (meth) acrylate being preferred. R1，R2As mentioned above, m is 0, 1 or 2, R3Is hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, epoxyethyl group, phenyl group or the like, and is preferably hydrogen atom, methyl group, ethyl group, propyl group or phenyl group.
In the method, the feeding molar ratio of the (meth) acrylate to the halogenated organic acid ester is preferably 0.8-1.2: 1, optimally 0.8-1.2: 1.
in the preparation method, the amount of the polymerization inhibitor is preferably 0.0001-5% (wt%) of the theoretical yield of the corresponding (meth) acrylate compound. If the amount of the polymerization inhibitor is less than 0.0001% (wt%), stability of the product during the reaction cannot be ensured, and if the amount of the polymerization inhibitor is more than 5% (wt%), it is not expected to further improve the stability of the product, but rather may have adverse effects and is economically disadvantageous. The amount of the polymerization inhibitor to be used is more preferably 0.005 to 1% (wt%), further preferably 0.01 to 0.5% (wt%), based on the theoretical yield of the corresponding (meth) acrylate-based reactive diluent.
In the present invention, the halogenated organic acid ester may be prepared by reacting a halogenated organic acid having a molecular formula of X (CH) in an organic solvent at a temperature of 0 ℃ to reflux temperature2)m CH(R3) COOH and the formula R2-(OH)nThe alcohol is reacted for 1 to 5 hours, the halogenated organic acid and the molecular formula are R2-(OH)nThe molar ratio of (n-1-4) alcohol is 1-5: 1, and the halogenated organic acid can be omega-halogenated C2～C4Fatty acids, e.g. omega-halogenated C2～C4The fatty acid may be 2-halopropionic acid, 2-halobutyric acid, 2-halopentanoic acid, 2-halophenylacetic acid, etc.; recommends omega-chloro C2～C4Organic acids or omega-bromo C2～C4Organic acids, and the like.
Wherein n is 1-4, R2And R in the foregoing I2The same is true.
In some cases, the alkene may also be reacted with the above-mentioned halogenated organic acid to form an ester.
According to the (methyl) acrylate compound provided by the invention, a section of ester bond is inserted into a conventional acrylate structure, so that the molecular weight is increased, the boiling point of the product is improved, and the volatility of the product is reduced. Although the molecular weight is increased, the viscosity is not greatly increased, the dilutability is good, the irritation and the toxicity of the product are reduced, and the reactivity of the product is not greatly influenced.
The preparation method of the (methyl) acrylate compound provided by the invention is simple and convenient, the reaction condition is mild, and the product is simple in post-treatment and easy to purify.
The (methyl) acrylate compound is convenient to use in related photocuring printing ink, coating and adhesive, the obtained product has extremely low volatility, extremely low smell and extremely low irritation, and the photocuring reaction is quick, so that the product performance requirements of the final product can be met. Generally speaking, the photo-curing ink, paint and adhesive prepared by the compound has no volatile smell, and the composition polymerized with free radicals and with the viscosity of 50-10000cps can achieve the aim of improving the performance. The viscosity is about 50cps, jet ink and jet three-proofing glue can be prepared, gravure ink can be prepared when the viscosity is about 200cps, flexible ink, paint and the like can be prepared when the viscosity is about 1000cps, and two-component reactive acrylic structural glue and the like can be prepared when the viscosity is 10000-20000 cps.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, which are intended to facilitate the further understanding of the invention and are not intended to limit the scope of the invention.
Synthetic examples
The first embodiment is as follows: synthesis of t-butyl acryloyloxyethanoate
(1) Synthesis of t-butyl chloroacetate
36.5 g (0.49mol) of tert-butyl alcohol, 64.4 g (0.63mol) of triethylamine and 150 ml of dichloromethane are added into a dry three-neck flask, a salt bath is cooled to below 5 ℃ under stirring, a solution prepared by 60 g of chloroacetyl chloride (0.53mol) and 100 ml of dichloromethane is dropwise added, and the reaction temperature is controlled to be not higher than 5 ℃. After the chloroacetyl chloride addition was complete, the reaction was continued for 2 hours with stirring at 10 ℃. Suction filtration was carried out and the filter cake was washed with a small amount of dichloromethane. The filtrate and the washing solution were combined, washed with water and saturated brine, respectively, dried over anhydrous magnesium sulfate, filtered, and desolventized to obtain 76 g of brown liquid. Vacuum distilling, collecting the distillate 67.9 g at 46-48 deg.C/10 mmHg with 92.4% yield.
(2) Synthesis of t-butyl acryloyloxyethanoate
In a dry three-neck flask, 45 g (0.3mol) of tert-butyl chloroacetate, 31 g (0.33mol) of sodium acrylate and 200 ml of tetrahydrofuran are added, the mixture is stirred uniformly, 1.5 g of benzyltriethylammonium chloride and 0.8 g of p-methoxyphenol are added, and the mixture is heated and refluxed for 10 hours (GC detects that the tert-butyl chloroacetate is reacted completely). Cooling to room temperature, suction filtering, washing the filter cake with 50 ml tetrahydrofuran, merging the filtrate and the washing liquid, and rotary evaporating to recover tetrahydrofuran to obtain 61.2 g yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 45 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering, and spin-drying mother liquor to obtain 56 g of light yellow liquid. Vacuum rectifying, collecting fraction at 50-52 deg.C/5 mmHg, total 49.1 g, yield 88.0%. The product is a colorless, odorless, transparent liquid having a viscosity of 5.5cps (25 deg.C).1H NMR(400MHz,CDCl3)：δ6.60-6.45(d,1H,＝CH2)，6.23-6.15(dd,1H,＝CH)，5.91-5.88(d,1H,＝CH2)，4.57(s,2H,-CH2-)，1.47(s,9H,-C(CH3)3)。
Example two: synthesis of Acryloyloxy benzyl acetate
(1) Synthesis of benzyl chloroacetate
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. 100 g (0.93mol) of benzyl alcohol, 92.6 g (0.98mol) of chloroacetic acid, 2 g of p-toluenesulfonic acid and 100 ml of toluene are added into a reaction bottle, reflux reaction is carried out under stirring for dehydration to a theoretical value (about 4 hours), and the end point of the reaction is determined by GC analysis that the content of the benzyl alcohol is less than 0.5%. Cooling to room temperature, washing the reaction product with water, saturated sodium bicarbonate water solution and water, drying with anhydrous magnesium sulfate, filtering, and washing the filter cake with toluene. The filtrate and the washing solution were combined and desolventized to obtain 183 g of brown liquid. Vacuum distillation was carried out, and 162.5 g of a 110-.
(2) Synthesis of acryloyloxy benzyl acetate
In a dry three-neck flask, 51.6 g (0.28mol) of benzyl chloroacetate, 29 g (0.31mol) of sodium acrylate and 200 ml of tetrahydrofuran were added, stirred uniformly, 1.5 g of benzyltriethylammonium chloride and 0.8 g of p-methoxyphenol were added, and the mixture was heated under reflux for 10 hours (GC detected that the benzyl chloroacetate had reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 70 ml of tetrahydrofuran, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the tetrahydrofuran to obtain a yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 45 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor to obtain 61.4 g of light yellow liquid. Vacuum rectification is carried out, the collected fraction 124-. The product is a colorless, odorless, transparent liquid having a viscosity of 12.5cps (25 deg.C).1H NMR(400MHz,CDCl3)：δ7.42-7.34(m,5H,-C6H5)，6.66-6.45(d,1H,＝CH2)，6.28-6.21(dd,1H,＝CH-)，5.98-5.94(d,1H,＝CH2)，5.23(s,2H,-CH2C6H5)，4.74(s,2H,-CH2-)。
Example three: synthesis of Acryloyloxy tetrahydrofurfuryl acetate
(1) Synthesis of tetrahydrofurfuryl chloroacetate
Adding 50 g (0.49mol) of tetrahydrofurfuryl alcohol, 64.4 g (0.63mol) of triethylamine and 100 ml of methyl tertiary ether into a dry three-neck flask, cooling to below 10 ℃ by stirring in an ice salt bath, dropwise adding a solution prepared from 60 g of chloroacetyl chloride (0.53mol) and 100 ml of methyl tertiary ether, controlling the reaction temperature to be not higher than 10 ℃ and adding after about 3 hours. After the chloroacetyl chloride addition was complete, the reaction was continued for 2 hours with stirring at 20 deg.C (reaction end point was reached when the tetrahydrofurfuryl alcohol content was less than 0.5% as monitored by GC). Suction filtration was carried out and the filter cake was washed with a small amount of methyl tert-ether. The filtrate and the washing solution were combined, washed with water and saturated brine, respectively, the phases were separated, the organic phase was dried over anhydrous magnesium sulfate, filtered and desolventized to obtain 96 g of brown liquid. Vacuum distillation is carried out, the fraction is collected at 104 ℃/5mmHg, the total amount is 80.5 g, and the yield is 92%.
(2) Synthesis of acryloyloxy tetrahydrofurfuryl acetate
60 g (0.33mol) of tetrahydrofurfuryl chloroacetate, 33.2 g (0.35mol) of sodium acrylate and 200 ml of tetrahydrofuran are added into a dry three-neck flask, stirred uniformly, 1.5 g of crown ether and 0.8 g of p-methoxyphenol are added, and the mixture is heated and refluxed for reaction for 10 hours (TLC detects that the tetrahydrofurfuryl chloroacetate is reacted completely). Cooling to room temperature, suction filtering, washing the filter cake with 50 ml tetrahydrofuran, merging the filtrate and the washing liquid, and rotary evaporating to recover tetrahydrofuran to obtain 78 g yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 50 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor. Vacuum rectification is carried out, 60.5 g of 115-fold 118 ℃/5mmHg fraction is collected, and the yield is 86.0 percent. The product is colorless transparent liquid, and the viscosity is as follows: 17cps (25 ℃ C.). Nuclear magnetic analysis results:1H NMR(400MHz,CDCl3)：δ6.44-6.33(d,1H,＝CH2)，6.17-6.04(dd,1H,＝CH-)，5.87-5.78(d,1H,＝CH2)，4.65(s,2H,-CH2-)，4.17-4.08(m,1H,-CH)，4.06-3.87(m,2H,-CH2-)，3.73-3.61(m,2H,-CH2-)，1.84-1.74(m,2H,-CH2-)，1.93-1.46(m,2H,-CH2-)。
example four: synthesis of methacryloyloxyacetic acid cyclohexyl ester
(1) Synthesis of cyclohexyl chloroacetate
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. 32.4 g (0.32mol) of cyclohexanol, 33.6 g (0.36mol) of chloroacetic acid, 1 g of p-toluenesulfonic acid and 100 ml of toluene were added into a reaction flask, and reflux reaction was performed with stirring to dehydrate to a theoretical value (about 4 hours), and the reaction end point was determined by GC analysis that the cyclohexanol content was less than 0.5%. Cooling to room temperature, washing the reaction product with water, saturated sodium bicarbonate water solution and water, drying with anhydrous magnesium sulfate, filtering, and washing the filter cake with toluene. The filtrate and washings were combined and desolventized to give 64 g of brown liquid. Vacuum distilling, collecting fraction 52.0 g at 70-72 deg.C/5 mmHg with yield 92.0%.
(2) Synthesis of cyclohexyl methacryloyloxyacetate
In a dry three-neck flask, 52 g (0.29mol) of cyclohexyl chloroacetate, 33.5 g (0.31mol) of sodium methacrylate and 350 ml of tetrahydrofuran are added, the mixture is stirred uniformly, 1.5 g of benzyltriethylammonium chloride and 0.8 g of p-methoxyphenol are added, and the mixture is heated and refluxed for 10 hours (GC detects that benzyl chloroacetate is reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 70 ml of tetrahydrofuran, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the tetrahydrofuran to obtain a yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 45 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor to obtain 61.2 g of light yellow liquid. Vacuum rectifying, collecting distillate 94-95 deg.C/5 mmHg, total 56.3 g, yield 85.9%. The product is colorless, tasteless and transparent liquid, and has the following viscosity: 14cps (25 ℃ C.). The nuclear magnetic data of the nuclear magnetic material,1H NMR(400MHz,CDCl3)δ6.23(d,1H,＝CH2)，5.65(s,1H,＝CH2)，4.90-4.83(m,1H,-CH)，4.66(s,2H,-CH2-),1.99(s,3H,-CH3)，1.87-1.83(m,2H,-CH2-)，1.74-1.69(m,2H,-CH2-)，1.60-1.22(m,6H,-CH2CH2CH2-)。
example five: synthesis of tetrahydrofurfuryl 2-acryloyloxy propionate
(1) Synthesis of 2-tetrahydrofurfuryl chloropropionate
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. 37.3 g (0.365mol) of tetrahydrofurfuryl alcohol, 40 g (0.37mol) of 2-chloropropionic acid, 1 g of p-toluenesulfonic acid and 100 ml of toluene are added into a reaction bottle, and the reaction is refluxed and dehydrated to a theoretical value (about 5 hours) under stirring, and the reaction end point is shown by that the content of tetrahydrofurfuryl alcohol is lower than 0.5% by GC analysis. Cooling to room temperature, washing the reaction product with water, saturated sodium bicarbonate water solution and water, drying with anhydrous magnesium sulfate, filtering, and washing the filter cake with toluene. The filtrate and the washing solution were combined and desolventized to obtain 65.8 g of brown liquid. Vacuum distilling, collecting 59.0 g of 58-62 ℃/1mmHg fraction, the yield is 83.6%.
(2) Synthesis of 2-acryloxy propionic acid tetrahydrofurfuryl alcohol ester
56 g (0.29mol) of tetrahydrofurfuryl 2-chloropropionate, 33.5 g (0.31mol) of sodium acrylate and 200 ml of acetonitrile are added into a dry three-neck flask, the mixture is stirred uniformly, 1.5 g of benzyltriethylammonium chloride and 0.8 g of p-methoxyphenol are added, and the mixture is heated and refluxed for reaction for 24 hours (GC detects that the tetrahydrofurfuryl 2-chloropropionate is reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 70 ml of acetonitrile, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the acetonitrile to obtain a yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 45 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering, and spin-drying mother liquor to obtain 59 g of light yellow liquid. Vacuum rectifying, collecting fraction 72-74 deg.C/1.5 mmHg, total 53.5 g, yield 80.9%. The product is colorless, tasteless and transparent liquid, and has the following viscosity: 15.7cps (25 ℃ C.). The nuclear magnetic data of the nuclear magnetic material,1H NMR(400MHz,CDCl3)：δ6.51-6.46(d,1H,＝CH2)，6.23-6.16(dd,1H,＝CH-)，5.92-5.89(d,1H,＝CH2)，5.22-5.16(m,1H,-CH-)，4.24-4.19(m,1H,-CH-)，4.15-4.09(m,2H,-CH2-)，3.88-3.78(m,2H,-CH2-)，2.04-1.97(m,1H,-CH2-)，1.96-1.84(m,2H,-CH2-)，1.73-1.60(m,1H,-CH2-)，1.62-1.55(d,3H,-CH3)。
example six: synthesis of bis (methacryloyloxyacetic acid) neopentyl glycol ester
(1) Synthesis of neopentyl glycol bis (chloroacetate)
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. To the reaction flask were added 52 g (0.5mol) of neopentyl glycol, 113.4 g (1.2mol) of chloroacetic acid, 1.65 g of p-toluenesulfonic acid and 250 ml of cyclohexane, and the reaction was refluxed with stirring to dehydrate to the theoretical value (about 4 hours) and judged by TLC to be at the end of the reaction. Cooling to room temperature, separating cyclohexane, adding 200 ml dichloromethane into the ester layer, stirring uniformly, washing with water, saturated sodium bicarbonate water solution and water respectively, drying over anhydrous magnesium sulfate, filtering, and washing the filter cake with a small amount of dichloromethane. The filtrate and the washing liquid were combined and desolventized to obtain 112 g of a colorless liquid. Nuclear magnetic analysis confirmed the structure.
(2) Synthesis of neopentyl glycol bis (methacryloyloxyacetate)
In a dry three-neck flask, 52 g (0.20mol) of neopentyl glycol bis (chloroacetate), 46 g (0.43mol) of sodium methacrylate and 500 ml of tetrahydrofuran were added, stirred uniformly, 2.1 g of benzyltriethylammonium chloride and 1.1 g of p-methoxyphenol were added, and the mixture was heated under reflux for 10 hours (GC detected that benzyl chloroacetate had reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 100 ml of tetrahydrofuran, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the tetrahydrofuran to obtain a yellow liquid. Adding 21 ml of saturated sodium bicarbonate aqueous solution and 63 ml of water, stirring uniformly, extracting twice by using 150 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor to obtain 69.8 g of light yellow liquid with viscosity: 84cps (25 ℃). The nuclear magnetic data of the nuclear magnetic material,1H NMR(400MHz,CDCl3)δ6.23(d,2H,＝CH2)，5.66(d,2H,＝CH2)，4.70(s,4H,-CH2-)，3.97(s,4H,-CH2-)，1.99(s,3H,-CH3)，0.96(s,3H,-CH3)。
example seven: synthesis of diethylene glycol bis (methacryloyloxyacetate)
(1) Synthesis of diethylene glycol bis (chloroacetate)
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. 53.1 g (0.5mol) of diethylene glycol, 113.4 g (1.2mol) of chloroacetic acid, 1.65 g of p-toluenesulfonic acid and 250 ml of cyclohexane were added to a reaction flask, and the reaction was refluxed to dehydrate to the theoretical value (about 4 hours) with stirring, and the end point of the reaction was judged by TLC. Cooling to room temperature, separating cyclohexane, adding 200 ml dichloromethane into the ester layer, stirring uniformly, washing with water, saturated sodium bicarbonate water solution and water respectively, drying over anhydrous magnesium sulfate, filtering, and washing the filter cake with a small amount of dichloromethane. The filtrate and the washing liquid were combined and desolventized to obtain 123.7 g of a colorless transparent liquid. Nuclear magnetic analysis confirmed the structure.
(2) Synthesis of diethylene glycol bis (methacryloyloxyacetate)
In a dry three-neck flask, 52 g (0.20mol) of diethylene glycol bis (chloroacetate), 46 g (0.43mol) of sodium methacrylate and 500 ml of tetrahydrofuran were added, stirred uniformly, 2.1 g of benzyltriethylammonium chloride and 1.1 g of p-methoxyphenol were added, and the mixture was heated under reflux for 10 hours (GC detected that benzyl chloroacetate had reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 100 ml of tetrahydrofuran, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the tetrahydrofuran to obtain a yellow liquid. Adding 21 ml of saturated sodium bicarbonate aqueous solution and 63 ml of water, stirring uniformly, extracting twice by using 150 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor to obtain 71 g of light yellow liquid with viscosity: 87cps (25 ℃ C.). The nuclear magnetic data of the nuclear magnetic material,1H NMR(400MHz,CDCl3)δ6.19(d,2H,＝CH2)，5.64(d,2H,＝CH2)，4.70(s,4H,-CH2-)，4.33-4.28(m,4H,-CH2-)，3.70-3.67(m,4H,-CH2-)，1.95(s,6H,-CH3)。
example eight: synthesis of Trimethylol propane Tri (Methacryloyloxy acetic acid)
(1) Synthesis of tri (chloroacetic acid) trimethylolpropane ester
A dry three-neck flask was connected with a thermometer, a water separator and mechanically stirred. 44.7 g (0.33mol) of diethylene glycol, 113.4 g (1.2mol) of chloroacetic acid, 1.65 g of p-toluenesulfonic acid and 250 ml of cyclohexane were added to a reaction flask, and the reaction was refluxed to dehydrate to the theoretical value (about 4 hours) with stirring, and the end point of the reaction was judged by TLC. Cooling to room temperature, separating cyclohexane, adding 200 ml dichloromethane into the ester layer, stirring uniformly, washing with water, saturated sodium bicarbonate water solution and water respectively, drying over anhydrous magnesium sulfate, filtering, and washing the filter cake with a small amount of dichloromethane. The filtrate and the washing liquid were combined and desolventized to obtain 119.6 g of colorless liquid. Nuclear magnetic analysis confirmed the structure.
(2) Synthesis of tris (methacryloyloxyacetic acid) trimethylolpropane ester
37 g (0.10mol) of tris (chloroacetic acid) trimethylolpropane, 35 g (0.32mol) of sodium methacrylate and 350 ml of tetrahydrofuran are added into a dry three-neck flask, stirred uniformly, added with 1.5 g of benzyltriethylammonium chloride and 0.8 g of p-methoxyphenol and heated to reflux for 10 hours (GC detects that benzyl chloroacetate is reacted completely). Cooling to room temperature, carrying out suction filtration, washing a filter cake with 70 ml of tetrahydrofuran, combining a filtrate and a washing liquid, and carrying out rotary evaporation to recover the tetrahydrofuran to obtain a yellow liquid. Adding 15 ml of saturated sodium bicarbonate aqueous solution and 45 ml of water, stirring uniformly, extracting twice by using 75 ml of dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, filtering by suction, and spin-drying mother liquor to obtain 49.6 g of light yellow liquid with viscosity: 845cps (25 ℃ C.). The nuclear magnetic data of the nuclear magnetic material,1H NMR(400MHz,CDCl3)δ6.23(d,3H,＝CH2)，5.69(d,3H,＝CH2)，4.71(s,6H,-CH2-)，4.10(s,6H,-CH2-)，1.99(s,9H,-CH3)，1.51-1.39(m,2H,-CH2-)，0.92-0.97(m,3H,-CH3)。
application examples
Example nine: LED-UV light curing white ink
The components are prepared into ink by a conventional method such as mixing or grinding, and the white ink can be cured by ultraviolet lamp irradiation at 395nm and 385nm in a nitrogen atmosphere. The ink has no odor, and little odor after photocuring, thereby meeting the requirements of gravure flexible package ink. Under the same condition, the ink prepared by replacing the tetrahydrofurfuryl acrylate with the tetrahydrofurfuryl acryloxyacetate has stronger pungent smell after photocuring.
Example ten: low-odor acrylate structural adhesive (AB adhesive)
The component A comprises:
the component B comprises:
and (3) mixing A and B as 1:1, and curing the mixture into the acrylate structural adhesive at room temperature for 5-8 minutes.
The methacrylate ester of the invention, such as methacryloxycyclohexyl acetate, methacryloxytetrahydrofurfuryl acetate or isobornyl methacrylate, can be used to replace the commonly used phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate and isobornyl methacrylate. Under the same condition, compared with the structural adhesive prepared by adopting the traditional methacrylate in the prior art, the structural adhesive adopting the methacryloxyacetic ester has better performance and lower odor.
Claims (13)
1. A (methyl) acrylate compound:
in the formula, R1Is a hydrogen atom or a methyl group;
m is 0, 1 or 2; n is 1, 2, 3 or 4;
R2selected from the following groups:
(a)C4～C10alkyl radical, C4～C10An alkyl alkenyl or alkyl alkynyl group;
(b)C3～C10a cycloalkyl group;
(c) aryl radical, C1～C4Alkyl, halogen or nitro substituted aryl, aryl substituted (C)1～C4) An alkyl group;
(d) heterocyclic groups, heterocyclic groups containing oxygen or nitrogen;
(e) ether group of formula-CH2～C4H8OR3；R3Is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, epoxyethyl or phenyl;
when m is 0, R3Is hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, epoxyethyl or phenyl; when m ≠ 0, R3Is a hydrogen atom.
2. The compound of claim 1, wherein C is4～C10Alkyl radical, C4～C10The alkyl alkenyl hydrocarbon or alkyl alkynyl olefin is butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, isooctyl, ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, ethynyl, propynyl or butynyl.
3. The compound of claim 1, wherein C is3～C10Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, methylcyclopropyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 4-methylcyclohexyl, isobornyl or biscyclopentadienyl.
4. A compound according to claim 1, characterized in that the heterocyclic group or the heterocyclic group containing oxygen or nitrogen is 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, tetrahydrofurfuryl, epoxypropyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl.
5. A process for preparing a compound according to claim 1, wherein R is in the presence of a catalyst, a polymerization inhibitor and an organic solvent1The substituted acrylate and halogenated organic acid ester react for 1-50 hours at room temperature-reflux temperature to obtain:
wherein, R is1The substituted acrylate has the formula H2C＝CR1C(O)OM；
The halogenated organic acid ester has a molecular formula [ X (CH)2)m CH(R3)COO]nR2；
The catalyst is quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, trihydrocarbylphosphine, crown ether or polyethylene glycol,
the polymerization inhibitor is hydroquinone, p-methoxyphenol, p-benzoquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, phenothiazine, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, cuprous chloride or ferric chloride;
r mentioned above1The feeding molar ratio of the substituted acrylate to the halogenated organic acid ester is 0.5-2: 1;
the weight ratio of the catalyst to the halogenated organic acid ester is 0.0001-0.1: 1;
the amount of the polymerization inhibitor is 0.0001-5% of the theoretical yield of the (methyl) acrylate compound;
wherein X is halogen, M is a monovalent or divalent alkali metal ion, M is 1, 2, 3 or 4, X, R1And R2As in claim 1, wherein m is 0, 1 or 2, R3Hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl,cyclobutyl, epoxyethyl or phenyl.
6. The method according to claim 5, wherein the molar ratio of the R1-substituted acrylate to the halogenated organic acid ester is 0.8 to 1.2: 1.
7. a process for the preparation of a compound according to claim 5, characterized in that the halogenated organic acid is 2-chloroacetic acid, 2-bromoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid, 3-chloropropionic acid, 3-bromopropionic acid, 4-chlorobutyric acid or 4-bromobutyric acid.
8. The method according to claim 5, wherein the polymerization inhibitor is hydroquinone, p-methoxyphenol, p-benzoquinone, 2-t-butylhydroquinone, 2, 5-di-t-butylhydroquinone, 2, 6-di-t-butylphenol, 2, 4-di-t-butylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, phenothiazine, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl, cuprous chloride or ferric chloride.
9. The method according to claim 5, wherein the quaternary ammonium salt is tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltributylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, dodecylbenzyldimethylammonium chloride; the quaternary phosphonium salt is tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tributyl tetradecyl phosphonium chloride, tributyl tetradecyl phosphonium bromide, triphenyl dodecyl phosphonium chloride, triphenyl dodecyl phosphonium bromide, triphenyl hexadecyl phosphonium chloride and triphenyl hexadecyl phosphonium bromide; the tertiary amine is trimethylamine, triethylamine, tri-N-propylamine, tri-N-butylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, imidazole, 4-methylimidazole, 4-phenylimidazole, N-dimethylaniline and N, N-diethylaniline; the trivalent phosphine is triphenylphosphine, tri (p-tolyl) phosphine, tri-n-butylphosphine or tricyclohexylphosphine.
10. The method according to claim 5, wherein the product is purified by filtration and concentration.
11. The process according to claim 5, wherein the halogenated organic acid ester has the formula [ X (CH)2)m CH(R3)COO]n R2Is prepared from halogenated organic acid X (CH) in organic solvent at 0-reflux temp2)m CH(R3) COOH and the formula R2-(OH)nReacting alcohol for 1-5 hours to obtain; the molar ratio of the halogenated organic acid to the alcohol is 1-5: 1; wherein, X, m, R2Or n is as in claim 5.
12. The method according to claim 12, wherein the halogenated organic acid is 2-halopropionic acid, 2-halobutyric acid, 2-halopentanoic acid or 2-halophenylacetic acid.
13. Use of the (meth) acrylate compound according to claim 1 or 5 in photo-curable inks, coatings and adhesives.
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| WO2020045211A1 (en) * | 2018-08-29 | 2020-03-05 | 日東化成株式会社 | Anti-fouling coating material composition |
| WO2020218372A1 (en) * | 2019-04-23 | 2020-10-29 | 共栄社化学株式会社 | Thermosetting resin composition, cured film, and non-aqueous dispersion resin particles |
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| JPS55160747A (en) * | 1979-06-01 | 1980-12-13 | Mitsubishi Petrochem Co Ltd | Beta-acryloxypropionic acid ester |
| CN108693705A (en) * | 2017-03-31 | 2018-10-23 | 信越化学工业株式会社 | Resist lower layer membrane material, pattern forming method and resist lower membrane forming method |
| WO2020045211A1 (en) * | 2018-08-29 | 2020-03-05 | 日東化成株式会社 | Anti-fouling coating material composition |
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