Patent Application
20250179006
The present application claims priority to Chinese Patent Application No. 202210217084.9, entitled “BENZOPHENONE DERIVATIVE, METHOD FOR PREPARING SAME, AND USE THEREOF”, and filed to the China National Intellectual Property Administration on Mar. 7, 2022, the entire contents of which are incorporated herein by reference.
The present application relates to the technical field of photocuring technique, in particular to a benzophenone derivative, a method for preparing same, and use thereof.
N,N,N,N-tetraethyl-4,4′-diaminobenzophenone, referred to as EMK, is a commonly used high-efficiency auxiliary photoinitiator, which is very important in inks, especially UV-LED curing inks. The synthesis methods of the compounds are reported in patent documents such as CN107686450A, CN112707830A, DE2226039A1 and DE44077C. In patents EP1078598A1, US2010081071A1, CN105974736A, CN104749882A, CN104710843A, etc., EMK is used as an auxiliary photoinitiator and in combination with a hydrogen abstraction photoinitiator in various combinations to achieve photopolymerization. However, its disadvantages are that it has a small molecular weight and a certain degree of toxicity, and it is easy to migrate out of the cured material, affecting the stability and safety of the product properties.
In patent CN101796015A, an acrylate-based derivatized aniline compound is reported as a polymerizable ammonia additive for use in radiation-curable liquid compositions for inkjet printing. Its disadvantages are small molecular weight, complex preparation process and high manufacturing cost. In patent CN102212151A, a 4-acrylamido-4′-dialkylaminobenzophenone compound is reported. It is reported that it can be used alone as a photoinitiator. The disadvantage is that the photoinitiation efficiency is not high and the preparation process is complicated.
In the actual use of photocurable inks, after people noticed the pollution problems of small molecular weight photoinitiators, the demand for low volatility and low mobility photoinitiators continued to increase with the expansion of the amount of coatings, such as requirements for low odor and low mobility inks are widely used in civilian fields such as paper and flooring, especially for food and drug packaging materials, more stringent testing standards limit the amount of substance that can migrate. Therefore, it is difficult to meet the strict mobility standard requirements and is not included in the list of allowed uses. It also makes many users lose efficient formula combinations. It is difficult to find alternative technologies that meet the standards for a while, which has become a problem for those skilled in the art.
The technical problem to be solved by the present application is to overcome the defect of high mobility amount of photoinitiator or auxiliary photoinitiator in the prior art, thereby providing a benzophenone derivative, a method for preparing same, and use thereof.
In order to solve the above technical problems, the present application adopts the following technical solutions:
A benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (1):
The term “substituted” means that any one or more hydrogen atoms on a specified atom are replaced by a substituent, as long as the substituted compound is stable. The term “optionally substituted” means that it may or may not be substituted. Unless otherwise specified, the type and number of substituents may be arbitrary on the basis that they can be chemically realized.
In the present application, the alkyl may be a linear alkyl or a branched alkyl.
In the present application, n1 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In an optional embodiment of the present application, n1 is an integer from 1 to 4.
In R1, examples of C1-C8 alkyls include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl or C1 alkyl. Preferably, R1 is a C1-C4 alkyl, further preferably-CH2CH3.
In an optional embodiment of the present application, R2 is H;
In an optional embodiment of the present application, R3 is
The present application also provides a benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (2):
In the present application, n2 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In an optional embodiment of the present application, n2 is an integer from 1 to 6.
In R1, examples of C1-C8 alkyls include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl or C1 alkyl. Preferably, R1 is a C1-C4 alkyl, further preferably-CH2CH3.
In an optional embodiment of the present application, R2 is H;
In an optional embodiment of the present application, R4 is
R2 and G2 have the same definitions as those in formula (2). In G2, examples of C1-C12 alkylene include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene and 3-methylpentylene.
The present application also provides a benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (3):
In the present application, n3 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In an optional embodiment of the present application, n3 is an integer from 1 to 6.
In R1, examples of C1-C8 alkyls include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl or C1 alkyl. Preferably, R1 is a C1-C4 alkyl, further preferably-CH2CH3.
In an optional embodiment of the present application, R2 is H;
In an optional embodiment of the present application, R5 is
R2, G2 and G3 have the same definitions as those in formula (3). In G3, examples of C1-C12 alkylene include but are not limited to, methylene, ethylene, propylene, butylene, pentylene and 3-methylpentylene.
In an optional embodiment of the present application, G2 and G3 are each independently —CH2CH2—, —CH2CH2CH2CH2—, —CH2CH2OCH2CH2— or —CH2CH2OCH2CH2OCH2CH2—.
The present application also provides a method for preparing the benzophenone derivative having the structure of formula (1) as described above, comprising:
wherein a molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is in a range from 1:1 to 1:2, and R1, R2 and G1 have the same definitions as those in formula (1).
In an optional embodiment of the present application, the reaction temperature is in a range from 40° C. to 120° C. and the reaction time is in a range from 10 h to 100 h.
In the above reaction, when at least one of the hydroxyl groups at both ends of the compound represented by formula (4) is fully added, the reaction is completed. The reaction can be carried out under stirring conditions.
In an optional embodiment of the present application, after the reaction is completed, the obtained reaction liquid is washed and the solvent is recovered to obtain a benzophenone derivative with the structure of formula (1).
An exemplary washing method is: first washing with 1-5% dilute weak alkaline aqueous solution, and then washing with water. The weak alkaline aqueous solution can be an aqueous solution of sodium bicarbonate or sodium carbonate or ammonium carbonate.
An exemplary method for recovering the solvent is distillation to recover the solvent.
Optionally, the method for preparing the benzophenone derivative with the above formula (1) structure comprises the following steps:
Optionally, the reaction temperature is in a range from 40° C. to 120° C. and the reaction time is in a range from 10 h to 100 h. Optionally, it can be detected by HPLC until the compound represented by formula (4) reacts completely and the monoaddition product reacts completely.
Optionally, the polymerization inhibitor is at least one selected from the group consisting of polyphenols, substituted phenol polymerization inhibitors, quinone polymerization inhibitors and diarylamine polymerization inhibitors. Preferably, the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and/or phenothiazine.
Optionally, the amount of the polymerization inhibitor is 0.001% to 10% of the mass of the compound represented by formula (5), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Optionally, the catalyst is one or more of organic sulfonic acid, strongly acidic cation exchange resin or organic sulfonates, preferably p-aminobenzene sulfonic acid or poly-4-vinylpyridine p-toluenesulfonic acid salt. The amount of the catalyst is 0.1% to 20% of the mass of the compound represented by formula (4).
Optionally, the solvent is an organic solvent immiscible with water, preferably toluene. The amount of the solvent can be added according to actual needs to ensure that the raw materials are dissolved. Optionally, the amount of the solvent is 0.5-100 times the mass of the compound represented by formula (4).
Optionally, the amount of the alkaline solution added can be 1-100 times the amount of catalyst. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1% to 10%.
Optionally, after the reaction is completed, the temperature is lowered to 20° C. to 40° C.
Optionally, the content of effective groups in the benzophenone derivative of formula (1) is 30% to 60%, where the effective group refers to the molecular group
The present application also provides a method for preparing a benzophenone derivative having a structure of formula (2) as described above, comprising:
wherein a molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is in a range from 1:1 to 1:2, and a molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is in a range from 1:0.5 to 1:3, and R1, R2 and G2 have the same definitions as those in formula (2).
In an optional embodiment of the present application, the reaction temperature is in a range from 40° C. to 120° C. and the reaction time is in a range from 10 h to 100 h.
The reaction can be carried out under stirring conditions.
In an optional embodiment of the present application, after all the double bonds in the vinyl group in the compound represented by formula (8) are added, the reaction is completed, and the resulting reaction liquid is washed and the solvent is recovered to obtain a benzophenone derivatives with the structure of formula (2).
An exemplary washing method is: first washing with a dilute weak alkaline aqueous solution, and then washing with water.
An exemplary method of recovering the solvent is distillation to recover the solvent.
Optionally, the method for preparing the benzophenone derivative with the structure of formula (2) comprises the following steps: mixing the compound represented by formula (6), the compound represented by formula (7), a polymerization inhibitor, a catalyst and a solvent to obtain a mixture, performing a heating reaction under nitrogen or an inert atmosphere; after the reaction is completed, adding the compound represented by formula (8), continuing to carry out the reaction under heat preservation until the content of the compound represented by formula (8) no longer decreasing, stopping the reaction, lowing the temperature, and then adding an alkaline solution for washing, then washing with water until neutral, removing the solvent to obtain the benzophenone derivative with the structure of formula (2);
wherein a molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is in a range from 1:1 to 1:2, and a molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is in a range from 1:0.5 to 1:3, and R1, R2 and G2 have the same definitions as those in formula (2).
Optionally, the heating reaction temperature is 40-120° C., and the heating reaction time is 10-100 h. Optionally, it can be detected by HPLC until the compound represented by formula (6) reacts completely and the monoaddition product reacts completely.
Optionally, the polymerization inhibitor is at least one selected from the group consisting of polyphenols, substituted phenol polymerization inhibitors, quinone polymerization inhibitors and diarylamine polymerization inhibitors. Preferably, the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and/or phenothiazine.
Optionally, the amount of polymerization inhibitor is 0.001% to 10% of the mass of the compound represented by formula (7), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Optionally, the catalyst is one or more of organic sulfonic acid, strongly acidic cation exchange resin or organic sulfonates, preferably p-aminobenzene sulfonic acid or poly-4-vinylpyridine p-toluenesulfonic acid salt. The amount of catalyst is 0.1% to 20% of the mass of the compound represented by formula (6).
Optionally, the solvent is an organic solvent immiscible with water, preferably toluene. The amount of solvent can be added according to actual needs to ensure that the raw materials are dissolved. Optionally, the amount of solvent is 0.5-100 times the mass of the compound shown in formula (6).
Optionally, the amount of alkaline solution added can be 1-100 times the amount of catalyst. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1% to 10%.
Optionally, after the reaction is completed, the temperature is lowered to 20° C. to 40° C.
Optionally, the content of effective groups in the benzophenone derivative of formula (2) is 30% to 60%, where the effective group refers to the molecular group
The present application also provides a method for preparing a benzophenone derivative having a structure represented by formula (3) as described above, comprising:
wherein a molar ratio of the compound represented by formula (9) and the compound represented by formula (10) is 1:1 to 1:2, and the molar ratio of the compound represented by formula (9) and the compound represented by formula (11) is 1:1 to 1:3, and R1, R2, G2 and G3 have the same definitions as those in formula (3).
The reaction can be carried out under stirring conditions.
In an optional embodiment of the present application, the reaction temperature is in a range from 40° C. to 120° C. and the reaction time is in a range from 10 h to 100 h.
In an optional embodiment of the present application, after all the double bonds in the vinyl group in the compound represented by formula (11) are added, the reaction is completed, and the resulting reaction liquid is washed and the solvent is recovered to obtain a benzophenone derivatives with the structure of formula (3).
An exemplary washing method is: first washing with a dilute weak alkaline aqueous solution, and then washing with water.
An exemplary method of recovering the solvent is distillation to recover the solvent.
Optionally, the method for preparing the benzophenone derivative with the structure of formula (3) comprises the following steps: mixing the compound represented by formula (9), the compound represented by formula (10), a polymerization inhibitor, a catalyst and a solvent, and performing a heating reaction under nitrogen or an inert atmosphere; after the reaction is completed, adding the compound represented by formula (11), continuing to carry out the reaction under heat preservation until the content of the compound represented by formula (11) no longer decreasing, stopping the reaction, lowing the temperature, adding an alkaline solution for washing, then washing with water until neutral, removing the solvent to obtain the benzophenone derivative with the structure of formula (2);
wherein a molar ratio of the compound represented by formula (9) and the compound represented by formula (10) is 1:1 to 1:2, and the molar ratio of the compound represented by formula (9) and the compound represented by formula (11) is 1:1 to 1:3, and R1, R2, G2 and G3 have the same definitions as those in formula (3).
Optionally, the reaction temperature is in a range from 40° C. to 120° C. and the reaction time is in a range from 10 h to 100 h. Optionally, it can be detected by HPLC until the compound represented by formula (9) reacts completely and the monoaddition product reacts completely.
Optionally, the polymerization inhibitor is at least one selected from the group consisting of polyphenols, substituted phenol polymerization inhibitors, quinone polymerization inhibitors and diarylamine polymerization inhibitors. Preferably, the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and/or phenothiazine. Optionally, the amount of the polymerization inhibitor is 0.001% to 10% of the mass of the compound represented by formula (10), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Optionally, the catalyst is one or more of organic sulfonic acid, strongly acidic cation exchange resin or organic sulfonates, preferably p-aminobenzene sulfonic acid or poly-4-vinylpyridine p-toluenesulfonic acid salt. The amount of the catalyst is 0.1% to 20% of the mass of the compound represented by formula (9).
Optionally, the solvent is an organic solvent immiscible with water, preferably toluene. The amount of solvent can be added according to actual needs to ensure that the raw materials are dissolved. Optionally, the amount of the solvent is 0.5-100 times the mass of the compound shown in formula (9).
Optionally, the amount of the alkaline solution added can be 1-100 times the amount of catalyst. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1% to 10%. Optionally, after the reaction is completed, the temperature is lowered to 20° C. to 40° C.
Optionally, the content of effective groups in the benzophenone derivative of formula (3) is 30% to 60%, where the effective group refers to the molecular group
The preparation of the compound represented by formula (1), formula (2) or formula (3) of the present application is preferably carried out in the presence of a polymerization inhibitor, a catalyst and a solvent.
Optionally, the polymerization inhibitor is at least one selected from the group consisting of polyphenols, substituted phenol polymerization inhibitors, quinone polymerization inhibitors and diarylamine polymerization inhibitors. Preferably, the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and/or phenothiazine. Optionally, the amount of the polymerization inhibitor is 0.001% to 10% of the mass of the compound represented by formula (5), formula (8) or formula (11), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Optionally, the catalyst is one or more of organic sulfonic acid, strongly acidic cation exchange resin or organic sulfonates, preferably p-aminobenzene sulfonic acid or poly-4-vinylpyridine p-toluenesulfonic acid salt. The amount of the catalyst is 0.1% to 20% of the mass of the compound represented by formula (4), formula (6) or formula (9).
Optionally, the solvent is an organic solvent immiscible with water, preferably toluene.
According to another aspect of the present application, a photoinitiator composition is provided, wherein the photoinitiator composition comprises a photoinitiator for free radical polymerization and the benzophenone derivative as described above.
According to another aspect of the present application, a photocurable composition is provided, wherein the photocurable composition comprises a photoinitiator component and a radically polymerizable ethylenically unsaturated compound, wherein the photoinitiator component comprises the photoinitiator composition as described above.
In an optional embodiment of the present application, the photocurable composition comprises: (a) the benzophenone derivative as described above; (b) a photoinitiator for free radical polymerization; and (c) a free-radically polymerizable ethylenically unsaturated compound.
The photocurable composition including the aforementioned photoinitiator composition has low mobility.
In an optional embodiment of the present application, the component (a) is added in an amount ranging from from 0.1% to 20% of the total weight of the photocurable composition, such as 1%, 5%, 10%, 15% or 20%.
In an optional embodiment of the present application, the component (b) is a commonly used compound in the industry that is commercially or laboratory-available, and is selected from the group consisting of benzophenones (except benzophenones and derivatives other than those in the present application), thioxanthone compounds, α-hydroxyketone compounds, α-aminoketones compounds, acyl phosphine oxide compounds, oxime lipid compounds, and any combination thereof; preferably, at least one of benzophenone, 2-isopropylthiaxanthone, 2-dimethylamino-2-(4-methyl benzyl)-1-(4-morpholinylphenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910 and photoinitiator Omnipol TP. Optionally, the photoinitiator Omnipol TX, photoinitiator Omnipol 910 or photoinitiator Omnipol TP is selected from the macromolecular photoinitiator series products Omnipol TX, Omnipol 910 or Omnipol TP of IGM Resin Company.
In an optional embodiment of the present application, the component (b) is added in an amount ranging from 0.1% to 10% of the total weight of the photocurable composition, such as 0.1%, 2%, 4%, 6%, 8% or 10%.
Ethylenically unsaturated compounds represent ethylenically unsaturated monomers, oligomers, prepolymers and mixtures thereof, which are capable of free radical polymerization.
In an optional embodiment of the present application, the component (c) is at least one selected from the group consisting of epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin, and acrylate resin, polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound, acrylate monomer and methacrylate monomer. The acrylate monomer or methacrylate monomer is independently monofunctional, difunctional or polyfunctional. These free-radically polymerizable ethylenically unsaturated compounds are readily available commercially or in the laboratory to those skilled in the art.
The photocurable composition may also contain other additives to meet performance requirements, such as pigments, fillers, leveling aids, polymerization inhibitors, solvents, etc.
According to another aspect of the present application, there is provided a use of the photocurable composition as described above in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing and advertising printing.
According to another aspect of the present application, a photocurable product is provided, which is formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition as described above, preferably, the photocurable product is selected from any one of coatings, adhesives, and printing inks.
According to another aspect of the present application, a method for curing a photocurable composition is provided, comprising coating the photocurable composition as described above on a substrate; and curing the photocurable composition by using a light source with an emission band in the UV-visible light region.
The substrate is selected from the group consisting of wood, paper, plastic, coating and metal. The coating method is selected from the group consisting of offset printing, gravure printing, flexographic printing, inkjet printing and 3D printing.
Optionally, after coating on the substrate, the photocurable composition is cured by irradiating with UV-visible light having a wavelength ranging from 200 nm to 425 nm, preferably the photocurable composition is cured by irradiating with UV-visible light having a wavelength ranging from 365 nm to 405 nm.
Compared with EMK, the bis(dialkylamino)benzophenone compound with an acrylate group side chain provided by the present application has a remarkably increased molecular weight and contains a polymerizable double bond, showing remarkably lower mobility.
The benzophenone derivative can be used as an important co-initiator in UV light-curing formulas to initiate photopolymerization of unsaturated carbon-carbon double bond compounds together with other photoinitiators. The compound has very low mobility due to its large molecular weight and is suitable to replace N,N,N,N-tetraethyl-4,4′-diaminobenzophenone in the fields of food packaging, printing formulations, and the like.
Experimental raw materials and materials:
Omnipol TX is a photoinitiator of polybutylene glycol 250-bis(2-carboxy-
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-vinyloxyethoxyethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.44 g of the product of formula IX, with an effective group content of 55%. The effective group refers to the remaining residue in the HEMK structure after removing the hydrogen on the two hydroxyl groups.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-vinyloxyethoxyethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.11 mmol) of poly(4-vinylpyridine-p-toluenesulfonate) and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.40 g of the product of formula IX.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 2.00 g (10 mmol) of 2-vinyloxyethoxyethyl methacrylate (VEEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.51 g of the product of formula X.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-vinyloxyethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.91 g of the product of formula XI, with an effective group content of 55%.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-vinyloxyethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-toluenesulfonic acid and 12.0 g of dichloroethane were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.88 g of the product of formula XI.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.56 g (12 mmol) of 2-vinyloxyethyl methacrylate (VEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30° C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.07 g of the product of formula XII.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.86 g (12 mmol) of acrylic acid was added, and continue to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the acrylic acid content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.91 g of the product of formula XIII, with an effective group content of 40%.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 72 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.22 g (3 mmol) of acrylic acid was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the acrylic acid content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.58 g of the product of formula XIII.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.15 g of the product of formula XIV, with an effective group content of 40%.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 72 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.74 g of the product of formula XIV.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 2.02 g (10 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.66 g of the product of formula XV, with an effective group content of 40%
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.26 g (6.25 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 96 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.06 g of the product of formula XV.
To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 1,4-butanediol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55° C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30° C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.09 g of the product of formula XVI.
This Example provided a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula IX of Example 1, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
This Example provided a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula XI of Example 4, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIII of Example 7, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIV of Example 9, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XV of Example 11, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
This comparative example provided a photocurable composition, comprising the following components: 4.65 g of Photomer 4072, 4.65 g of Photomer 3316, 0.2 g of the Omnirad EMK, and 0.5 g of Omnipol TX.
The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60° C., and then cooled to room temperature to prepare a photocurable composition.
The hardness and curing mobility properties of the photocurable compositions prepared of Examples 14-18 and Comparative Example 1 were tested respectively:
Pendulum hardness test: a 25 μm wire rod was used to cure the above-mentioned photocurable compositions on a coated glass plate (under a 395 nm LED light) at a speed of 10 m/min, and the pendulum hardness after curing was tested.
Mobility test: a 25 μm wire rod was used to cure the above-mentioned photocurable composition on a paper with a coating length and width of 5×20 cm under a 395 nm LED lamp at a speed of 10 m/min. The 100 cm2 of cured paper was put into 100 g of acetic acid aqueous solution with a mass content of 3%, then it was placed at 40° C. for 10 days. Then HPLC was used to detect the photoinitiator component (the photoinitiator component refers to the product component of the formula IX of Example 1, the product component of Formula XI of Example 4, the product component of Formula XIII of Example 7, the product component of Formula XIV of Example 9, the product component of Formula XV of Example 11 or the component of Omnirad EMK) that migrates into the acetic acid aqueous solution. The EU model was used for calculation of the results, assuming that 1 kg of food is packaged in a 600 cm2 printing area, so the results can be converted into μg/kg, that is, μg of analyte per kg of food (the analyte refers to the product of formula IX of Example 1, the product of formula XI of Example 4, the product of formula XIII of Example 7, the product of formula XIV of Example 9, the product of formula XV of Example 11 or Omnirad EMK). The experimental results of hardness and mobility analysis were shown in Table 14.
It can be seen from the test data that using the bis(dialkylamino)benzophenone compound with an acrylate alkoxy side chain provided by the present application as a co-initiator of the photocurable composition, compared with the commonly used EMK as a co-initiator for photocurable compositions on the market, the hardness of the compounds provided in the present application after curing is similar to that of the control, indicating that they have a similar curing rate. However, because the compound provided by the application has a larger molecular weight and contains polymerizable double bonds, the mobility is significantly reduced. Therefore, the compounds provided in the present application are more suitable for use in food and drug packaging, children's toys and other applications that have strict requirements on substance mobility.
Obviously, the above examples are merely examples made for clear description, rather limiting the implementations. For those of ordinary skill in the art, other different forms of variations or modifications can also be made on the basis of the above-mentioned description. All embodiments are not necessary to be and cannot be exhaustively listed herein. In addition, obvious variations or modifications derived therefrom all fall within the scope of protection of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210217084.9 | Mar 2022 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2023/079796 | 3/6/2023 | WO |
