CN117142994A - Amphiphilic polyether alpha-ketone (hetero) arylthioester compound for LED photopolymerization and preparation and application thereof - Google Patents

Amphiphilic polyether alpha-ketone (hetero) arylthioester compound for LED photopolymerization and preparation and application thereof Download PDF

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CN117142994A
CN117142994A CN202311102500.1A CN202311102500A CN117142994A CN 117142994 A CN117142994 A CN 117142994A CN 202311102500 A CN202311102500 A CN 202311102500A CN 117142994 A CN117142994 A CN 117142994A
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孙芳
贾伟
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HUBEI GURUN TECHNOLOGY CO LTD
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
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    • C07C327/00—Thiocarboxylic acids
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    • C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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Abstract

The invention discloses an amphiphilic polyether alpha-ketone (hetero) arylthio ester compound for LED photopolymerization, a preparation method and application thereof. The amphiphilic polyether alpha-ketone (hetero) arylthio ester compound can be used as an initiator for LED photopolymerization, has good absorption performance in a visible light region of more than 400nm, particularly has good initiation performance under an LED light source of 405nm, can effectively initiate the photopolymerization reaction of water-based or oil-based photopolymerizable monomers, particularly water-based or oil-based (methyl) acrylic ester monomers, and simultaneously avoids the use of noble metal catalysts, has a simple synthetic route and low synthetic cost, thereby having extremely high practical value.

Description

Amphiphilic polyether alpha-ketone (hetero) arylthioester compound for LED photopolymerization and preparation and application thereof
Technical Field
The invention belongs to the technical field of photopolymerization, and relates to amphiphilic polyether alpha-ketone (hetero) arylthio ester compounds which can be used as photoinitiators, and are particularly suitable for LED photopolymerization. The invention also relates to preparation and application of the amphiphilic polyether alpha-ketone (hetero) arylthioester compound.
Background
With the continuous development of LED photopolymerization technology, in order to meet the wide application requirements of LED photopolymerization technology, development of photoinitiators suitable for LED light sources is required. Some such photoinitiators are known in the art, for example CN104817653a discloses a coumarin aldoxime ester compound suitable for UV-LED light source curing, CN102492059a discloses substituted diphenyl sulfide ketoxime ester photoinitiators and the like. However, the LED photoinitiator reported at present generally contains a group with a great degree of conjugation in a molecular structure, so that the steps required for synthesizing the photoinitiator are complex, which brings inconvenience to practical production and application.
In addition, the unique property of the aqueous photoinitiation system with numerous advantages such as low toxicity, environmental protection, safety and the like becomes one of the research hot spots in the field of photopolymerization in recent years, however, most of the current aqueous photoinitiation molecules are salts containing metal ions, and the introduction of the metal ions can bring a certain hazard to the performance of the photocuring material.
In view of this, research and development of novel amphiphilic photoinitiators useful for LED light sources, structures and synthetic routes that are simple remains one of the core efforts in this field. In addition, since photopolymers, particularly poly (meth) acrylates, have excellent mechanical properties, good reworkability and weather resistance, are widely used in biomedical materials and the like, development of a water-oil amphiphilic photoinitiator that can effectively polymerize aqueous or oily photopolymerizable monomers, particularly aqueous or oily (meth) acrylate monomers, is also urgently needed in the photopolymerization field.
Disclosure of Invention
In order to promote the development of the LED photopolymerization technology, the inventor is constantly working on the popularization and application research work of the LED photopolymerization technology, and particularly, more photoinitiators suitable for the LED photopolymerization light source are continuously researched and developed. In particular, in view of the problems of the prior art, the present inventors have conducted extensive and intensive studies on photoinitiators suitable for use in LED photopolymerization, in order to find a novel efficient water-oil amphiphilic photoinitiator capable of effectively initiating photopolymerization of aqueous or oily photopolymerizable monomers, particularly aqueous or oily (meth) acrylate monomers, while avoiding the use of noble metal catalysts and having a simple synthetic route.
The inventors have surprisingly found that a class of polyether alpha-ketone (hetero) arylthioesters of novel structure are synthesized by introducing alpha-carbonyl ketone and aryl or heteroaryl thioester groups into one molecule simultaneously and performing etherification. The prepared initiator has good absorption performance in the visible light region of more than 400nm and can be well matched with the wavelength of an LED light source. Particularly, the photoinitiator provided by the invention has good initiation performance under an LED light source of 405nm, can effectively initiate photopolymerization of water-based or oil-based photopolymerizable monomers, particularly water-based or oil-based (methyl) acrylic ester monomers, and simultaneously avoids the use of noble metal catalysts, and has the advantages of simple synthesis route, low synthesis cost and extremely high practical value.
The object of the present invention has been achieved based on the above findings.
Therefore, an object of the present invention is to provide an amphiphilic polyether α -ketone (hetero) arylthio-ester compound, whose absorption wavelength is suitable for the polymerization of LED light sources, especially for effectively initiating the photopolymerization of aqueous or oily (meth) acrylate monomers, and whose synthetic route is simple, while avoiding the use of noble metal catalysts.
It is another object of the present invention to provide a process for preparing the amphiphilic polyether α -ketone (hetero) arylthioesters of the present invention.
It is a further object of the present invention to provide the use of the amphiphilic polyether α -ketone (hetero) arylthioesters of the present invention as photoinitiators in LED photopolymerization.
The technical scheme for achieving the aim of the invention can be summarized as follows:
1. an amphiphilic polyether α -ketone (hetero) arylthioester compound of the general formula (I):
wherein:
m represents C 6 -C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy,
-NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 Alkylaryl thio or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein mono (C 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkyl groupCycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
l represents
Wherein R is 15 Is H or C 1 -C 4 Alkyl, preferably methyl;
n is an integer from 0 to 10, preferably from 0 to 4,
m is an integer from 1 to 4, preferably from 1 to 2.
2. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to claim 1, wherein: m represents C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O,
wherein C is 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy,
-NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio or C 7 -C 20 An alkylaryl group; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio or C 7 -C 20 Alkylaryl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
More preferably C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy group、C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 。
3. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to claim 1 or 2, wherein:
m represents C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O,
wherein C is 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.
4. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to any one of claims 1 to 3, wherein:
M represents
Wherein R is 1 Selected from O, S or-NR 10 -；
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 An alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
R 10 Represents hydrogen, C 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C is 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acidA group, a carboxylate group or an amino group.
5. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to item 4, wherein M representsWherein R is 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 As defined in item 4.
6. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to claim 4 or 5, wherein:
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 ；
Most preferably, the first and second regions are,
R 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 9 identical and H; r is R 4 Is methyl or methoxy.
7. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to any one of items 1 to 6, wherein:
R 10 represents hydrogen, C 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C is 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.
8. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to any one of claims 1 to 7, wherein:
R 15 is methyl;
n is 2;
m is 1.
9. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to any one of items 1 to 8, which is:
10. a method of preparing the amphiphilic polyether α -ketone (hetero) arylthioester compound of any one of claims 1 to 9, comprising:
(a) Make the following stepsAnd->Reaction to obtain intermediate->And
(b) Make the following stepsAnd->Reaction to obtain
Wherein M, M, n and R 15 As defined in any one of claims 1 to 9.
11. The method according to item 10, wherein the molar ratio of M-SH and oxalyl chloride is 1:1.1-1:2, preferably 1:1.2-1:2, more preferably 1:1.2-1:1.8.
12. The process according to item 10 or 11, wherein the molar ratio of intermediate (A) to starting material (C) is from 1:1.1 to 1:3, preferably from 1:1.1 to 1:2, more preferably from 1:1.2 to 1:2.
13. The process according to any one of claims 10 to 12, wherein the reaction of step (b) is carried out in the presence of one or more catalysts selected from the group consisting of: 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine, preferably 4-dimethylaminopyridine; and/or the molar amount of catalyst is 1 to 10%, preferably 5 to 10%, of the intermediate product (A).
14. The process according to any one of claims 10 to 13, wherein the reaction of step (b) is carried out in the presence of one or more dehydrating agents selected from the group consisting of: dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, preferably dicyclohexylcarbodiimide; and/or the molar amount of dehydrating agent is 100-150%, preferably 120-140% of the intermediate product (A).
15. A photopolymerizable composition comprising:
(A) At least one monomer or oligoolefin unsaturated photopolymerizable compound, and
(B) At least one amphiphilic polyether α -ketone (hetero) arylthioester compound as defined in any of items 1 to 9 or obtainable by a process according to any of items 10 to 14.
16. Use of an amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any of claims 1-9 or obtained according to the method of any of claims 10-14 as a photoinitiator in photopolymerization.
17. Use of an amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any of claims 1-9 or obtained according to the method of any of claims 10-14 for the preparation of a biopolymer material.
Drawings
FIG. 1 is a schematic illustration of the initiation mechanism of a photoinitiator provided by the present invention;
FIG. 2 is an ultraviolet-visible absorption spectrum of the photoinitiator MO-TGTE of example 2;
FIG. 3 is a graph of the photopolymerization kinetics of the photoinitiator MO-TGTE of example 2 for initiating polymerization of the oily monomer tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and the aqueous monomer polyethylene glycol (400) diacrylate (PEG (400) DA) under a 405nm LED light source.
Detailed Description
The first aspect of the present invention provides an amphiphilic polyether α -ketone (hetero) arylthioester compound of the general formula (I):
Wherein:
m represents C 6 -C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy,
-NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 Alkylaryl thio or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein mono (C 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
L represents
Wherein R is 15 Is H or C 1 -C 4 Alkyl, preferably methyl;
n is an integer from 0 to 10, preferably from 0 to 4,
m is an integer from 1 to 4, preferably from 1 to 2.
In the present invention, the prefix "C n -C m "in each case means that the number of carbon atoms contained in the radical is from n to m.
"halogen" refers to fluorine, chlorine, bromine and iodine and combinations thereof. In the present invention, preferably halogen includes F, cl or a combination thereof.
The term "C" as used herein n -C m Alkyl "means a saturated hydrocarbon radical having n to m, for example 1 to 20, preferably 1 to 12, more preferably 1 to 8, particularly preferably 1 to 6, particularly preferably 1 to 4, carbon atoms, which may be branched or unbranched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, isomers thereof, and the like. C (C) 1 -C 6 The alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl and the like. C (C) 1 -C 4 The alkyl group may be methyl, ethyl, propyl, butyl and isomers thereof, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Herein, a textThe term "C" is used 3 -C m Cycloalkyl "means a saturated alicyclic monocyclic group having 3 to m, for example 3 to 10, preferably 3 to 8, more preferably 5 to 6, ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C 4 -C m Cycloalkylalkyl "means alkyl substituted by cycloalkyl and contains in total 4 to m carbon atoms, for example 4 to 20 carbon atoms, preferably 4 to 12, more preferably 4 to 10, most preferably 4 to 8 carbon atoms. Alkyl and cycloalkyl are defined herein, examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl and the like.
The term "C 4 -C m Alkylcycloalkyl "means cycloalkyl substituted by alkyl and contains in total 4 to m carbon atoms, for example 4 to 20 carbon atoms, preferably 4 to 12, more preferably 4 to 10, most preferably 4 to 8 carbon atoms. Alkyl and cycloalkyl are defined herein, examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl and the like.
The term "C" as used herein 6 -C m Aryl "means a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 18, preferably 6 to 10 carbon atoms. As C 6 -C m Examples of aryl groups which may be mentioned are phenyl, azulenyl, cycloheptatrienyl, biphenyl, dicyclopentadiene-phenyl, fluorenyl, phenanthryl, terphenyl, pyrenyl, tetracenyl,Group, anthracenyl, indenyl, pentalenyl and naphthyl.
"5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O" is understood to mean a group having 5-18 ring members, such as 5-16, 5-14, 5-10 or 5-8, or 8-14,9-14 or 9-13 ring members, wherein at least one ring atom is a heteroatom selected from N, O and S, more preferably N. Heteroaryl groups preferably have 1 to 3, for example 1 or 2 heteroatoms. More preferably heteroaryl is a ring system having two or three fused rings, with 8-14,9-14 or 9-13 ring members. Examples of heteroaryl groups include thienyl, benzo [ b ] ]Thienyl, naphtho [2,3-b ]]Thienyl, thianthrenyl, furyl, dibenzofuranyl, benzofuranyl, chromene, xanthenyl, thioxanthenyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, phenanthridinyl, acridinyl, naphthyridine, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoindolylAzolyl, furazanyl, pheno->Oxazinyl, 7-phenanthryl, anthraquinone-2-yl (= 9, 10-dioxo-9, 10-dihydro-anthracene-2-yl), 3-benzo [ b ]]Thienyl, 5-benzo [ b ]]Thienyl, 2-benzo [ b ]]Thienyl, 4-dibenzofuranyl, 4-7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, pheno->Thioyl, 2, 7-pheno ∈ ->Thienyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazinyl Oxazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5, 6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1, 5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2, 7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl 2-quinolinyl, 6-quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2-methoxy-6-quinolinyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1, 4-dimethoxy-6-phthalazinyl, 1, 8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2, 3-dimethyl-6-quinoxalinyl, 2, 3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6, 7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, beta-carbolin-3-yl, 1-methyl-beta-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-naphthas-m-diazenyl, 1-methyl-5-naphthas-m-diazenyl, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isothiazolyl Azolyl, 4-Iso->Azolyl, 5-Iso->Azolyl, 4-methyl-3-furazanyl, 2-pheno +.>Oxazinyl, 10-methyl-2-pheno ∈ ->Oxazinyl, and the like.
The term "C 7 -C m Aralkyl "means an alkyl group substituted by an aryl group and containing 7 to m, for example 7 to 20 carbon atoms, preferably 7 to 12 carbon atoms in total. Alkyl and aryl are defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.
The term "C 7 -C m Alkylaryl "means aryl substituted by alkyl and contains a total of 7 to m, such as 7-20 carbon atoms, preferably 7-12 carbon atoms. Alkyl and aryl groups are defined herein, examples of which include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthyl, ethylnaphthyl and the like.
The term "C n -C m Alkoxy "means at C n -C m Open chain C corresponding to alkyl n -C m C having an oxygen atom bound to any carbon atom of the alkane as a linking group n -C m Alkyl radicals, e.g. C 1 -C 20 Alkoxy, preferably C 1 -C 12 Alkoxy, more preferably C 1 -C 8 Alkoxy, particularly preferably C 1 -C 6 An alkoxy group. Examples may be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isomers thereof and the like. C (C) 1 -C 4 The alkoxy group may be methoxy, ethoxy, propoxy, butoxy and isomers thereof, particularly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and the like.
The term "C 4 -C m Cycloalkylalkoxy "refers to an alkoxy group substituted with a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4 to 20, preferably 4 to 12, more preferably 4 to 10 carbon atoms. Wherein cycloalkyl is as defined herein. Examples include cyclopropylmethoxyCyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.
The term "C" as used herein 6 -C m Aryloxy "means at C 6 -C m C corresponding to aryl 6 -C m C having an oxygen atom bound to any aromatic carbon atom of the aromatic hydrocarbon as a linking group 6 -C m Aryl groups such as phenoxy, tolyloxy, naphthyloxy, and the like.
The term "C" as used herein 7 -C m Aralkyloxy "means at C 7 -C m C having an oxygen atom bound to a carbon atom of the alkyl radical corresponding to the aralkyl radical as a linking group 7 -C m Aralkyl groups such as benzyloxy, phenethyl, naphthylmethoxy, naphthylethoxy and the like.
The term "C 7 -C m Alkylaryl "means at C 7 -C m C having an oxygen atom bound to a carbon atom of the aryl radical corresponding to the alkylaryl radical as a linking group 7 -C m Examples of the alkylaryl group include methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, methylnaphthoxy, ethylnaphthoxy and the like.
The term "C n -C m Alkylthio "means at C n -C m Open chain C corresponding to alkyl n -C m C having a sulfur atom bound to any carbon atom of the alkane as a linking group n -C m Alkyl radicals, e.g. C 1 -C 20 Alkylthio, preferably C 1 -C 12 Alkylthio, more preferably C 1 -C 8 Alkylthio, particularly preferably C 1 -C 6 Alkylthio groups. Examples may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthioThio, isooctylthio and isomers thereof. C (C) 1 -C 4 Alkylthio groups may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, t-butylthio and the like.
The term "C 4 -C m Cycloalkyl alkylthio "refers to alkylthio substituted by cycloalkyl and contains a total of 4 to m carbon atoms, for example 4 to 20, preferably 4 to 12, more preferably 4 to 10 carbon atoms. Wherein cycloalkyl and alkylthio are as defined herein. Examples include cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio and the like.
The term "C" as used herein 6 -C m Arylthio "means at C 6 -C m C corresponding to aryl 6 -C m C having a sulfur atom bound to any aromatic carbon atom of the aromatic hydrocarbon as a linking group 6 -C m Aryl groups such as phenylthio, tolylthio, naphthylthio and the like.
The term "C" as used herein 7 -C m Aralkylthio "means at C 7 -C m C having a sulfur atom bound to a carbon atom of the alkyl radical corresponding to the aralkyl radical as a linking group 7 -C m Aralkyl groups such as benzylthio, phenethylthio, naphthylmethylthio, naphthylethylthio and the like.
The term "C 7 -C m Alkylarylthio "means at C 7 -C m C having a sulfur atom bound to a carbon atom of the aryl radical corresponding to the alkylaryl radical as a linking group 7 -C m Examples of the alkylaryl group include a methylthio group, a dimethylbenzylthio group, a trimethylphenylthio group, an ethylphenylthio group, a diethylphenylthio group, a triethylphenylthio group, a methylnaphthylthio group, an ethylnaphthylthio group and the like.
“C 1 -C 20 Haloalkyl "includes C 1 -C 12 Haloalkyl group,C 1 -C 8 Haloalkyl, C 1 -C 6 Haloalkyl, C 1 -C 4 A haloalkyl group. Halogen and alkyl in haloalkyl are as defined herein for halogen and alkyl.
“C 1 -C 20 Haloalkoxy "includes C 1 -C 12 Haloalkoxy, C 1 -C 8 Haloalkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 4 Haloalkoxy groups. Halogen and alkoxy in haloalkoxy are defined herein for halogen and alkoxy.
“C 1 -C 20 Haloalkylthio "includes C 1 -C 12 Haloalkylthio, C 1 -C 8 Haloalkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 4 Haloalkylthio. Halogen and alkylthio in haloalkylthio are defined herein for halogen and alkoxy.
In a preferred embodiment of the present invention,
m represents C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O,
wherein C is 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy,
-NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy radical,C 7 -C 20 Aralkylthio or C 7 -C 20 An alkylaryl group; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio or C 7 -C 20 Alkylaryl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
more preferably C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of:
halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
Further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 ；
Most preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.
In a preferred embodiment of the present invention,
m represents
Wherein R is 1 Selected from O, S or-NR 10 -；
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 An alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkyl alkoxyRadical, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
R 10 represents hydrogen, C 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C is 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.
In a preferred embodiment of the present invention,
M representsWherein:
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 An alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl,Sulfonic acid groups, carboxylic acid ester groups, or amino groups.
In a more preferred embodiment of the present invention,
m representsWherein:
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino; it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 、
-CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 ；
Most preferably, the first and second regions are,
R 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 9 identical and H; r is R 4 Is methyl or methoxy.
In a preferred embodiment of the present invention,
R 10 represents hydrogen, C 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroatom containing one or more heteroatoms selected from N, S and OAn aryl group; wherein C is 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.
In a preferred embodiment of the invention, M isWherein R is 2 、R 3 、R 5 And R is 6 Identical and H; r is R 4 Is methyl or methoxy.
In a further preferred embodiment of the invention, M is Wherein R is 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 9 Identical and H.
In a particularly preferred embodiment of the invention, R 15 Is methyl; n is 2; m is 1.
As specific examples of amphiphilic polyether alpha-ketone (hetero) arylthioesters of the general formula (I) mention may be made of
The second aspect of the present invention relates to a process for preparing the amphiphilic polyether α -ketone (hetero) arylthioesters of the general formula (I) of the present invention, comprising:
(a) Make the following stepsAnd->Reaction to obtain intermediate->And +.>
(b) Make the following stepsAnd->Reaction to obtain
Wherein M, M, n and R 15 As defined above.
In step (a) of the process of the invention, the molar ratio of M-SH to oxalyl chloride is from 1:1.1 to 1:2, preferably from 1:1.2 to 1:2, more preferably from 1:1.2 to 1:1.8.
Step (a) of the process of the invention is generally carried out in a solvent, preferably an organic solvent. The choice of the type of solvent is not particularly limited as long as each reactant can be dissolved and is chemically inert to the reaction, i.e., does not participate in the reaction. As examples of the solvent, methylene chloride, ethyl acetate, tetrahydrofuran, N-dimethylformamide are generally used. Preferably, the reaction of step (a) is carried out in tetrahydrofuran.
More specifically, in step (a) of the method of the present invention, M-SH is dissolved in a proper amount of solvent and then added into a reaction vessel, and then oxalyl chloride is dissolved in the same solvent and transferred into a dropping funnel, and dropped into the reaction vessel, and stirred and reacted at-10 to 20℃under the condition of ice water bath for 2 to 12 hours, preferably 4 to 10 hours; adding proper deionized water into the reaction system, continuously stirring vigorously for 0.5-4 hours, preferably 1-3 hours, separating out water phase after the reaction is finished, removing solvent by reduced pressure distillation to obtain crude product, and separating by silica gel column chromatography to obtain intermediate product (A)
Step (b) of the process of the invention is carried out in a solvent in the presence of a dehydrating agent and a catalyst. Suitable dehydrating agents are, for example, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; suitable catalysts are, for example, 4-Dimethylaminopyridine (DMAP), piperidine, 3-methylpiperidine or triethylamine.
In step (b) of the process of the invention, the molar amount of catalyst may be intermediate (A)From 1 to 10%, preferably from 5 to 10%. The molar amount of dehydrating agent is 100-150%, preferably 120-140% of M-SH. The molar ratio of intermediate (A) to starting material (C) is from 1:1.1 to 1:3, preferably from 1:1.1 to 1:2, more preferably from 1:1.2 to 1:2.
Step (b) of the process of the present invention is generally carried out in a solvent, preferably an organic solvent. The choice of the type of solvent is not particularly limited as long as each reactant, dehydrating agent and catalyst can be dissolved and are chemically inert to the reaction, i.e., do not participate in the reaction. As examples of the solvent, dimethyl sulfoxide, methylene chloride, ethyl acetate, tetrahydrofuran, N-dimethylformamide are generally used. Preferably, the reaction is carried out in methylene chloride.
More specifically, in step (b) of the process of the present invention, intermediate (A) is prepared Raw material (C)/(Suo)>And a catalyst is added into a reaction vessel after being dissolved in a proper amount of solvent, then a dehydrating agent is dissolved in the same solvent and transferred to a dropping funnel, and then the dehydrating agent is dripped into the reaction vessel, and the reaction is continued with stirring at-20 ℃ to 40 ℃, preferably-10 ℃ to 30 ℃, and the reaction time can be 0.5 to 10 hours, preferably 1 to 8 hours. Removing the solvent by distillation under reduced pressure to obtain a crude product, and separating the crude product by silica gel column chromatography to obtain a product (B)/(B)>
The amphiphilic polyether alpha-ketone (hetero) arylthio ester compound with the general formula (I) is used as an initiator for LED photopolymerization, has good absorption performance in a visible light region of more than 400nm, and can be well matched with the wavelength of an LED light source. Particularly, the photoinitiator provided by the invention has good initiation performance under an LED light source of 405nm, can effectively initiate photopolymerization of water-based or oil-based photopolymerizable monomers, particularly water-based or oil-based (methyl) acrylic ester monomers, and simultaneously avoids the use of noble metal catalysts, and has the advantages of simple synthesis route, low synthesis cost and extremely high practical value.
Thus, according to a third aspect of the present invention there is provided a photopolymerizable composition comprising:
(A) At least one monomer or oligoolefin unsaturated photopolymerizable compound, and
(B) At least one amphiphilic polyether alpha-keto (hetero) arylthioester of the general formula (I) as defined above
A compound.
The amount of amphiphilic polyether alpha-ketone (hetero) arylthioester compounds of the general formula (I) according to the present invention is generally from 0.01 to 10% by weight, preferably from 0.05 to 6% by weight, such as from 0.1 to 5% by weight, based on the total weight of the photopolymerizable composition.
The unsaturated compounds (a) may contain, for example, one or more ethylenically unsaturated double bonds, which have a low molecular weight (monomers) or a relatively high molecular weight (oligomers).
Suitable oligomers may be epoxy (meth) acrylic resins, polyurethane (meth) acrylic resins, polyester (meth) acrylic resins, polyether (meth) acrylic resins or acrylated poly (meth) acrylic resins.
Suitable monomers may be monofunctional compounds as follows: (meth) acrylic acid and salts thereof; (meth) acrylic esters, for example alkyl esters such as methyl, ethyl, 2-chloroethyl, N-dimethylaminoethyl, N-butyl, isobutyl, pentyl, hexyl esters, hydroxyalkyl esters such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl esters, epoxyalkyl esters such as glycidyl, 2, 3-epoxybutyl, 3, 4-epoxybutyl, 2, 3-epoxycyclohexyl, 10, 11-epoxyundecyl esters; (meth) acrylamides, N-substituted (meth) acrylamides, such as N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-phenylmethacrylamide, N- (4-hydroxyphenyl) acrylamide and N- (4-hydroxyphenyl) methacrylamide; (meth) acrylonitrile; unsaturated anhydrides such as itaconic anhydride, maleic anhydride, 2, 3-dimethylmaleic anhydride, 2-chloromaleic anhydride; unsaturated esters, such as maleates; styrene such as methyl styrene, chloromethyl styrene and o-, m-and p-hydroxystyrene, divinylbenzene; vinyl ethers such as isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether and phenyl vinyl ether; vinyl and allyl esters, such as vinyl acetate, vinyl acrylate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl chloride and vinylidene chloride; isocyanurate, such as triallyl isocyanurate and tris (2-acryloylethyl) isocyanurate; n-vinyl heterocyclic compounds, for example N-vinylpyrrolidone or substituted N-vinylpyrrolidone, N-vinylcaprolactam or substituted N-vinylcaprolactam, N-vinylcarbazole or N-vinylpyridine.
Suitable monomers may also be difunctional or higher functionality compounds, such as diacrylates, for example 1, 6-Hexane Diol Diacrylate (HDDA), ethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate, hexamethylene glycol diacrylate and bisphenol a diacrylate; trimethylolpropane triacrylate (TMPTA), trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate; tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trilactate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoesters and methacrylates, glycerol di-and tri-acrylates, 1, 4-cyclohexane diacrylate, di-and di-methacrylates of polyethylene glycols having a molecular weight of 200-1500; or a mixture thereof.
In particular, the amphiphilic polyether α -ketone (hetero) arylthio compounds of the general formula (I) according to the invention are suitable for photopolymerizing (meth) acrylic compounds, preferably epoxy (meth) acrylic resins, polyurethane (meth) acrylic resins, polyester (meth) acrylic resins, polyether (meth) acrylic resins, acrylated poly (meth) acrylic resins, or monofunctional, difunctional or higher functional (meth) acrylates as defined above.
In addition to the photoinitiator, the photopolymerizable composition may include various additives. Examples thereof are thermal inhibitors intended to prevent premature polymerization, such as 2, 6-tetramethyl-4-hydroxypiperidine-1-oxyl radicals and derivatives thereof; an antistatic agent; flow improvers and tackifiers; photopolymerization accelerators, such as amines, in particular tertiary amines, for example tributylamine, triethanolamine, ethyl p-dimethylaminobenzoate, michler's ketone, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine, diazabicyclooctane (triethylenediamine), 18-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) and salts thereof; a chain transfer agent; photosensitizers for modifying or broadening the spectral sensitivity, such as aromatic carbonyl compounds, e.g. benzophenone derivatives, thioxanthone derivatives, including in particular isopropylthioxanthone, anthraquinone derivatives and 3-acylcoumarin derivatives, terphenyl, styryl ketone and 3- (aroylmethylene) thiazolines, camphorquinone and eosin, rhodamine and erythrosine dyes; a filler; or a pigment.
The photopolymerizable compositions of the invention can be used for various purposes, for example as printing inks (for example screen printing inks, offset or flexographic printing inks, inkjet inks, single-sheet printing inks, electrophotographic inks, intaglio inks), as clear coats, white coats or pigmented coats, for photographic reproduction processes, for holographic recording materials, for image recording processes or for producing printing plates which can be developed using organic solvents or using aqueous alkaline media, for producing masks for screen printing, as tooth-filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etching resists or permanent resists, as photostructurable dielectrics and as soldering masks for electronic circuits, as resists for producing color filters for any type of display screen or for producing structures during the production of plasma displays and electroluminescent displays, for producing optical switches, gratings, for producing three-dimensional articles by mass polymerization or according to stereolithography, for producing composites of gel coats and thick-layer compositions, for coating or sealing electronic components or as coatings for optical fibers. The composition is also suitable for producing optical lenses (e.g. contact lenses or fresnel lenses) and for manufacturing medical devices, aids or implants.
In another aspect of the invention there is provided the use of the amphiphilic polyether alpha-ketone (hetero) arylthioester compounds of the general formula (I) according to the invention as photoinitiators in photopolymerisation.
The amphiphilic polyether alpha-ketone (hetero) arylthio-ester compound with the general formula (I) has excellent biocompatibility, so that the amphiphilic polyether alpha-ketone (hetero) arylthio-ester compound is suitable for preparing biological high polymer materials. Suitable biopolymer materials may be those obtained from the photopolymerizable compositions described above.
Thus, in a further aspect of the present invention there is provided the use of an amphiphilic polyether alpha-ketone (hetero) arylthio-ester compound of general formula (I) according to the invention in the preparation of a biopolymer material.
The invention has the beneficial effects that: compared with the traditional photoinitiator, the amphiphilic polyether alpha-ketone (hetero) arylthio-ester compound with the general formula (I) can be well matched with the wavelength of an LED light source. Particularly, the photoinitiator provided by the invention has good initiation performance under an LED light source of 405nm, can effectively initiate photopolymerization of water-based or oil-based photopolymerizable monomers, particularly water-based or oil-based (methyl) acrylic ester monomers, and simultaneously avoids the use of noble metal catalysts, and has the advantages of simple synthesis route, low synthesis cost and extremely high practical value.
Examples
The invention will be further illustrated with reference to specific examples, which should not be construed as limiting the scope of the invention.
Example 1: synthesis of intermediate MO-TEA
The synthesis route of MO-TEA is as follows:
4-Methoxythiophenol (1.40 g,10 mmol) was added to a 100mL single-necked flask, and 20mL of tetrahydrofuran was added thereto to dissolve it completely, then the flask was placed in an ice-water bath at 0℃and oxalyl chloride (1.51 g,12 mmol) was dissolved in 30mL of tetrahydrofuran and then added to an atmospheric dropping funnel, followed by dropping oxalyl chloride into the above-mentioned single-necked flask at a rate of 1-2 drops per second, and the reaction temperature in the flask was maintained at 0℃all the time. After the dripping is finished, the reaction system is kept in an ice water bath environment to be continuously stirred for 10 hours, and the reaction is finished. Tetrahydrofuran was then distilled off under reduced pressure, then 30mL of methylene chloride was added to the flask, 10mL of deionized water was added dropwise to the above reaction system under stirring at 25℃followed by vigorous stirring for 1 hour, and the reaction was terminated. The solvent was distilled off under reduced pressure, and the product was purified by silica gel column chromatography to give MO-TEA as an intermediate.
1 H NMR (400 MHz, chloroform-d) delta 8.16 (s, 1H), 7.44-7.34 (m, 2H), 7.06-7.00 (m, 2H), 3.88 (s, 3H).
13 C NMR (100 MHz, chloroform-d) delta 187.15, 161.46, 158.66, 135.65, 115.46, 115.29, 55.47.
Example 2: synthesis of photoinitiator MO-TGTE
The synthetic route for MO-TGTE is as follows:
MO-TEA (2.12 g,10 mmol), triethylene glycol monomethyl ether (1.96 g,12 mmol) and 4-Dimethylaminopyridine (DMAP) (0.12 g,1 mmol) were added to a 100mL one-neck flask, and then 30mL of anhydrous methylene chloride was added to the flask to dissolve the mixture. Dicyclohexylcarbodiimide (DCC) (2.47 g,12 mmol) was dissolved in 20mL of anhydrous dichloromethane and added to an atmospheric dropping funnel, followed by dropping the dichloromethane solution of DCC into the above-mentioned one-necked flask at a rate of 1-2 drops per second. After the completion of the dropwise addition, the reaction system was allowed to continue to stir at 25℃for 1 hour. After the reaction is finished, white solid impurities are filtered, and the solution is reserved. The reaction system was then purified by silica gel chromatography to give the product MO-TGTE as a yellow oily liquid.
1 H NMR (400 MHz, chloroform-d) delta 7.36-7.32 (m, 2H), 6.99-6.95 (m, 2H), 4.50-4.46 (m, 2)H)，3.83(s，3H)，3.73-3.61(m，8H)，3.57-3.52(m，2H)，3.37(s，3H)。
13 C NMR (100 MHz, chloroform-d) delta 184.42, 161.18, 159.27, 135.85, 116.12, 115.22, 71.92, 70.77, 70.62, 70.58, 68.39, 66.39, 59.02, 55.39.
Example 3:
example 3 is intended to illustrate the light absorption properties of the photoinitiator MO-TGTE of example 2.
The photoinitiator MO-TGTE of example 2 was formulated at a concentration of 1X 10 -4 mol L -1 Is not present in the aqueous acetonitrile solution. The UV-visible absorption curves of such photoinitiators in anhydrous acetonitrile solutions were each tested using a UV spectrophotometer over the wavelength range of 200-500 nm.
The UV-visible absorption spectrum of the photoinitiator MO-TGTE is shown in FIG. 2; it can be seen that the photoinitiator MO-TGTE has a certain absorption capacity in the visible light region above 400nm (see the numerical values shown in the following table 1), and can be suitable for an LED light source.
TABLE 1
Examples 4-6:
examples 4-6 are directed to illustrate the effective initiation of photopolymerization of (meth) acrylate monomers by the photoinitiator MO-TGTE of example 2 upon irradiation with a 405nm LED light source.
1. Photosensitive resin is prepared
Three monomers of tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and aqueous monomer polyethylene glycol (400) diacrylate (PEG (400) DA) and the photoinitiator MO-TGTE of example 2 are respectively selected, and photosensitive liquid is prepared according to the following proportion:
example 4:
an appropriate amount of monomer tripropylene glycol diacrylate (TPGDA) and the photoinitiator MO-TGTE of example 2 are weighed respectively to prepare a photosensitive liquid, and the mass ratio of the photoinitiator to the monomer is: tpgda=1:100.
Example 5:
the appropriate amount of monomer trimethylolpropane triacrylate (TMPTA) and photoinitiator MO-TGTE of example 2 were weighed separately to prepare a uniform photosensitive solution, the mass ratio of photoinitiator to monomer was: tmpta=1:100.
Example 6:
the appropriate amount of aqueous monomer polyethylene glycol (400) diacrylate (PEG (400) DA) and the photoinitiator MO-TGTE of example 2 are respectively weighed to prepare photosensitive liquid, and the mass ratio of the photoinitiator to the monomer is: PEG (400) da=1:100.
2. Photopolymerization Performance test
The photosensitive liquid prepared in examples 4-6 was uniformly coated on a salt sheet made of KBr after a proper amount of the photosensitive liquid was taken out by capillary tubes, the thickness of the photosensitive liquid layer was about 30. Mu.m, then another layer of salt sheet was covered over the salt sheet, and the two salt sheets were gently pressed with tweezers to remove air in the middle, thereby eliminating the influence of oxygen in the air on polymerization as much as possible. The polymerization kinetics were tested by using a real-time infrared spectrometer (model Nicolet 5700, siemens technologies, USA) using a light source with an emission wavelength of 405nm and a light intensity of 60mW/cm 2 。
FIG. 3 is a graph of the photopolymerization kinetics of the ether chain-containing amphiphilic photoinitiator MO-TGTE for three monomers. Therefore, the amphiphilic polyether alpha-ketone (hetero) arylthio ester initiator prepared by the invention can effectively initiate the photopolymerization reaction of the water-based or oil-based photopolymerizable monomer, especially the water-based or oil-based (methyl) acrylic ester monomer under the irradiation of a 405nm LED light source, which shows that the photoinitiator has excellent initiation performance and applicability under an LED photopolymerization system.

Claims (17)

1. An amphiphilic polyether α -ketone (hetero) arylthioester compound of the general formula (I):
wherein:
m represents C 6 -C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl group,
C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 Alkylaryl thio or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein mono (C 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl group,
C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 AralkyloxyRadical, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl,
A sulfonic acid group, a carboxylic acid ester group or an amino group;
l represents
Wherein R is 15 Is H or C 1 -C 4 Alkyl, preferably methyl;
n is an integer from 0 to 10, preferably from 0 to 4,
m is an integer from 1 to 4, preferably from 1 to 2.
2. The amphiphilic polyether α -ketone (hetero) arylthioester compound of claim 1, wherein:
m represents C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O,
wherein C is 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy,
-NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl group,
C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio or C 7 -C 20 An alkylaryl group; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio or C 7 -C 20 Alkylaryl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
more preferably C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of:
halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy,
Mercapto, carboxyl, sulfonic acid, carboxylate or amino;
further preferably, C 6 -C 18 Aryl or a 5-18 membered heteroaryl group comprising one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl group,
C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 。
3. The amphiphilic polyether α -ketone (hetero) arylthioester compound of claim 1 or 2, wherein:
m represents C 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O,
wherein C is 6 -C 18 Aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.
4. The amphiphilic polyethylenated α -ketone (hetero) arylthioester compound of any one of claims 1-3, wherein:
m represents
Wherein R is 1 Selected from O, S or-NR 10 -；
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Independently of one another, hydrogen, halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl group
Amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl group,
C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 An alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl group
Amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl group,
C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy, C 6 -C 18 Arylthio, C 7 -C 20 Aralkyl, C 7 -C 20 Aralkyloxy, C 7 -C 20 Aralkylthio, C 7 -C 20 Alkylaryl, C 7 -C 20 Alkylaryl oxy, C 7 -C 20 The alkylaryl thio group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
R 10 represents hydrogen, C 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C is 1 -C 20 Alkyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Alkylcycloalkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.
5. The amphiphilic polyether α -ketone (hetero) arylthioester compound according to claim 4, wherein M representsWherein R is 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 As defined in claim 4.
6. The amphiphilic polyether α -ketone (hetero) arylthioester compound of claim 4 or 5, wherein:
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl group,
C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C 4 -C 20 Cycloalkylalkoxy, C 4 -C 20 Cycloalkyl alkylthio, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Haloalkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkylthio, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy or C 6 -C 18 Arylthio; wherein single (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 3 -C 10 Cycloalkyl, C 6 -C 18 Aryl, C 6 -C 18 Aryloxy and C 6 -C 18 Arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino;
it is further preferred that the composition comprises,
R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 independently of one another, hydrogen, halogen, hydroxy, -NO 2 -CN, -COOH, -CHO, amino, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, -CF 3 、-OCF 3 or-OC 6 H 5 ；
Most preferably, the first and second regions are,
R 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 9 identical and H; r is R 4 Is methyl or methoxy.
7. The amphiphilic polyethylenated α -ketone (hetero) arylthioester compound of any one of claims 1-6, wherein:
R 10 represents hydrogen, C 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C is 1 -C 20 Alkyl, C 6 -C 18 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl or a 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.
8. The amphiphilic polyethylenated α -ketone (hetero) arylthioester compound of any one of claims 1-7, wherein:
R 15 is methyl;
n is 2;
m is 1.
9. The amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any one of claims 1-8, which is:
10. a process for preparing an amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any of claims 1-9, comprising:
(a) Make the following stepsAnd->Reaction to obtain intermediate->And (b) causingAnd->Reaction to obtain->
Wherein M, M, n and R 15 As defined in any one of claims 1 to 9.
11. The process according to claim 10, wherein the molar ratio of M-SH to oxalyl chloride is from 1:1.1 to 1:2, preferably from 1:1.2 to 1:2, more preferably from 1:1.2 to 1:1.8.
12. The process according to claim 10 or 11, wherein the molar ratio of intermediate (a) to starting material (C) is from 1:1.1 to 1:3, preferably from 1:1.1 to 1:2, more preferably from 1:1.2 to 1:2.
13. The process according to any one of claims 10 to 12, wherein the reaction of step (b) is carried out in the presence of one or more catalysts selected from the group consisting of: 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine, preferably 4-dimethylaminopyridine; and/or the molar amount of catalyst is 1 to 10%, preferably 5 to 10%, of the intermediate product (A).
14. The process according to any one of claims 10 to 13, wherein the reaction of step (b) is carried out in the presence of one or more dehydrating agents selected from the group consisting of: dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, preferably dicyclohexylcarbodiimide; and/or the molar amount of dehydrating agent is 100-150%, preferably 120-140% of the intermediate product (A).
15. A photopolymerizable composition comprising:
(A) At least one monomer or oligoolefin unsaturated photopolymerizable compound, and
(B) At least one amphiphilic polyethylated α -ketone (hetero) arylthioester compound obtained according to any of claims 1-9 or according to the method of any of claims 10-14.
16. Use of an amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any of claims 1-9 or obtainable according to the method of any of claims 10-14 as a photoinitiator in photopolymerization.
17. Use of an amphiphilic polyethylenated α -ketone (hetero) arylthioester compound according to any of claims 1-9 or obtainable by a process according to any of claims 10-14 for the preparation of a biopolymer.
CN202311102500.1A 2023-08-30 2023-08-30 Amphiphilic polyether alpha-ketone (hetero) arylthioester compound for LED photopolymerization and preparation and application thereof Pending CN117142994A (en)

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