CN114031622A - Coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, preparation method and application thereof - Google Patents

Coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, preparation method and application thereof Download PDF

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CN114031622A
CN114031622A CN202111261617.5A CN202111261617A CN114031622A CN 114031622 A CN114031622 A CN 114031622A CN 202111261617 A CN202111261617 A CN 202111261617A CN 114031622 A CN114031622 A CN 114031622A
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金明
郭新月
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Abstract

The invention provides a coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, a preparation method and application thereof, a chemical process preparation technology, application of the coumarin carbazole photosensitizer as a radiation curing photoinitiator, and application of the coumarin carbazole photosensitizer in radiation curing formula products, particularly in UV-Vis-LED photocuring paint or ink and other occasions. Wherein Y is selected from a cationic initiation photopolymerization group, and the large conjugated structure of the molecule enables the photosensitizer to absorb wavelength red shift, improves the absorption efficiency of light, and is further favorable for improving the photosensitivity of the formula product in which the photosensitizer participates. In addition, the photosensitizer has the advantages of low migration, low odor, photobleachability and the like because the photosensitizer has a large molecular weight and can participate in a photocuring system.

Description

Coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, preparation method and application thereof
Technical Field
The invention belongs to the technical field of new materials, organic chemicals, and particularly relates to a new photosensitive compound with coumarin carbazole as a core, a chemical preparation process technology, application of the photosensitive compound as a radiation curing photoinitiator, and application of the photosensitive compound in a radiation curing formula product, in particular to application of the photosensitive compound in UV-Vis-LED photocuring paint or ink and other occasions.
Background
The photocuring technology is a technology for forming a polymer by initiating a chain reaction by using a photoinitiator, has the advantages of energy conservation, environmental protection, high efficiency, rapidness, controllable time-space and the like, is widely applied to the traditional fields of coating, printing ink, adhesives and the like and high and new technical products of photoresist, 3D printing and the like, and has the advantages of capability of rapidly reacting at room temperature, capability of controlling the polymerization reaction to only occur in a radiation area, no emission of volatile organic compounds and the like. The photoinitiator is an important part in the photocuring system, and the wavelength tunability and the photoreactivity of the photoinitiator are the key points of the photocuring reaction process.
The photoinitiator is mainly classified into a radical photoinitiator and a cationic photoinitiator according to the type of active center (radical or cation) generated after the photoinitiator is excited, and the radical photoinitiator and the cationic photoinitiator respectively initiate radical polymerization and cationic polymerization. Compared with free radical curing, the cationic curing system (non-acrylate) has the advantages of difficult influence of oxygen inhibition, small curing shrinkage rate and the like, and expands the research and development range of the photocuring material. Under the action of ultraviolet-visible light, when the light energy is greater than the bond-breaking energy of the photoinitiator, the cationic photoinitiator generates protonic acid or Lewis acid to form a positive ion active center to initiate polymerization. This process requires that the absorption spectrum of the photoinitiator match the wavelength range of the light source. With the rapid development of industry, the requirements for energy saving and environmental protection are higher and higher, so that the mercury lamp conventionally used in photocuring is gradually replaced by the LED with high efficiency and energy saving, and the research and development of the high efficiency photoinitiator matched with the emission wavelength of the LED light source gradually become a hot spot.
Photosensitizers are compounds that sensitize other chemical species to photoreaction, promote chemical reactions by absorbing photons and transferring energy to molecules that do not absorb photons, but do not themselves participate in chemical reactions. The addition of the LED sensitive dye in the light curing component can effectively improve the polymerization rate of the formula under an LED light source. However, the photosensitizer cannot participate in the photocuring reaction, so that the small molecules after the system is cured have certain mobility and certain toxicity hazard in practical application, and therefore, the problem of solving the mobility of the photosensitizer is a great difficulty.
The coumarin carbazole has a large plane conjugated structure, and the specific structure is shown as the following formula:
Figure BDA0003325667140000021
the conjugation of coumarin and carbazole enhances the delocalization of pi-electrons, so that electrons are easier to be excited; the substance containing coumarin carbazole group has good light absorption capacity in the wavelength range of more than 365 nm; meanwhile, the coumarin carbazole group also has good fluorescence and sensitization properties. In addition, the coumarin carbazole group has the advantages of simple synthetic process, high yield and low cost, and can be prepared by 4-hydroxy carbazole and ethyl acetoacetate buckle as described in patent publication No. CN 107163169A. If coumarin carbazole groups and polymerizable groups exist in molecules, the problem of migration of an initiator can be solved, the absorption spectrum can be effectively red-shifted, and meanwhile, the coumarin carbazole groups and the polymerizable groups can be compounded with the traditional initiator, so that the coumarin carbazole groups have good absorption on energy of an LED light source.
Disclosure of Invention
The invention aims to provide a novel coumarin carbazole photosensitizer capable of initiating polymerization by cations, which can be used independently or together with traditional sulfonium salt and iodonium salt photoinitiators to initiate a photocuring reaction; the photosensitizer has polymerizable groups, is combined with matrix resin after being cured, hardly migrates, and has strong application prospect in LED, particularly in light-cured coating or ink which can be excited by visible light LED and other occasions.
The second purpose of the invention is to provide a preparation method of the coumarin carbazole photosensitizer capable of being polymerized by cationic initiation.
The third purpose of the invention is to provide the application of the coumarin carbazole photosensitizer capable of carrying out cationic polymerization.
Specifically, the present invention provides the following scheme:
the coumarin carbazole photosensitizer which can be polymerized by cationic initiation and is shown in the formula (I) is a novel photosensitizer formed by further introducing substituted carbonyl and coumarin carbazole into a coumarin part, and the formula is as follows:
Figure BDA0003325667140000031
in the structure of the above compound of formula (I):
y is an epoxy group-containing polymerizable group: ethylene oxide alkyl or propylene oxide alkyl, optionally, one or more-CH in the alkyl group between the epoxy group and the carbazole structure2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted.
Further preferably, Y is selected from: c1-8 alkyl terminated with ethylene oxide or propylene oxide groups, optionally one or more-CH groups in the alkyl2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted and H in the oxirane or oxetane group may be replaced by C1-4Is substituted with an alkyl group.
Further preferably, Y may be selected from the following structures:
Figure BDA0003325667140000032
z is selected from C1-12Unsubstituted or substituted by 1 to 5R7Substituted phenyl, unsubstituted or substituted by 1 to 9R7Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R7Substituted aromatic heterocyclic radical, or unsubstituted or substituted by 1-8R7Substituted benzoaromatic heterocyclic groups;
R1，R2，R3，R4，R5，R6each independently selected from 1 to 4RaSubstituted C1-6Alkyl, -H, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、 -CO2Rb、-OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2Rb；
R7Each independently selected from unsubstituted or substituted by 1-5RaSubstituted C1-6Alkyl, -H, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、-CO2Rb、 -OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2RbUnsubstituted or substituted by 1 to 5RcSubstituted carbocyclic ring, unsubstituted or substituted by 1 to 5RdSubstituted heterocycle, OR, P (═ O) (OR)b)2；
RaEach independently selected from C1-6Alkyl group, (CH)2)rC3-6Cycloalkyl or- (CH)2)rA phenyl group;
Rbeach independently selected from H, unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted- (CH)2)rPh；
RcEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
RdEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
ReEach independently selected from-H, -F, -Cl, -Br, -I, -OH and-NO2、-CN，-CF3、-CF2CF3、 C1-4Alkyl radical, C1-4Alkoxy radical, C3-7Cycloalkyl, phenyl, benzyl, phenethyl, naphthyl, heterocyclic aryl, or, keto;
each r is independently 0, 1, 2, 3, or 4;
the invention provides a preparation method of the coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, which comprises the following synthetic route:
Figure BDA0003325667140000041
in the above-mentioned preparation method, the starting materials used are known compounds in the prior art, and can be commercially obtained or can be easily prepared by known synthetic methods. The preparation process of the compound comprises the following steps:
(1) preparation of intermediate (I) -a
By reaction with POCl3The oxidation reaction is carried out on the aldehyde group at the ortho position of the substituted 4-hydroxy carbazole under the reaction condition that DMF is used as a solvent and N is at 0 DEG C2Protecting, and reacting for 4h to obtain an intermediate (I) -a;
(2) preparation of intermediate (I) -b
Intermediate (I) -a is prepared through the reaction of Z-substituted ethyl formylacetate and the solution of alkali (preferably piperidine or mixture of piperidine and pyridine) in the presence of ethanol as solvent and at 80 deg.c and N2Protecting, and reacting for 2h to obtain an intermediate (I) -b;
(3) preparation of product (I)
The intermediate (I) -b reacts with a halide Y-X in the presence of a basic catalyst (preferably sodium methoxide, sodium tert-butoxide, potassium methoxide and the like) to form a product (I); wherein X represents a halogen (preferably F, Cl or Br). The reaction is carried out in a solvent system, and the type of solvent used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and DMSO, THF, and DMF are preferable. The reaction temperature is usually room temperature; the reaction time varies slightly depending on the kind of the raw material, and is usually 2 to 10 hours.
The application of the coumarin carbazole photosensitizer capable of initiating polymerization by cations as a radiation curing photoinitiator. In particular, their use as photoinitiators or other functional additive components, and as intermediates or starting materials or reagents in chemical synthesis.
The light radiation curing formula system is characterized in that:
(1) contains at least one compound described by general formula (I) and at least one photoinitiator of any kind which are used alone or in combination as the photoinitiation component in the formula system;
(2) containing at least one polymerizable compound containing epoxy or oxetane.
(3) The content of the photoinitiator shown in the formula (I) is 0.5-20 parts by weight calculated by 100 parts by weight of the total amount of the polymerizable components in the system.
Preferably, the light source of the radiation curing photoinitiator generates light having a wavelength selected from one or more of ultraviolet light and visible light.
Preferably, the light source of the radiation curing photoinitiator is selected from one or more of a mercury lamp, an LED light source, and an LDI light source, which can emit ultraviolet light, visible light.
Actually, the radiation-curable photoinitiator may contain, in addition to the coumarin carbazole-based photosensitizer capable of initiating polymerization by cationic polymerization and the polymerizable component, any component such as an inorganic filler, an organic filler, a colorant, other additives, and a solvent, as required.
Wherein the colorant is selected from pigments or dyes.
Other additives include ultraviolet absorbers, light stabilizers, flame retardants, leveling agents, or defoamers.
The method comprises the following specific steps: (1) according to the monomer and resin: photoinitiator (2): the mass ratio of the auxiliary agent is 100: 0.5-1: 0-4.5 of raw materials; (2) stirring to fully dissolve; (3) irradiating the polymerization system by light sources with different wavelengths or different light intensities; wherein: the light source in step (3) can be a mercury lamp (high pressure, medium pressure and low pressure), and LEDs with the emission wavelength of 365-.
Examples of the monomer having an epoxy group include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, and aliphatic epoxy compounds.
Examples of the monofunctional glycidyl ether include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and 2-methyloctyl glycidyl ether.
Examples of the polyfunctional aliphatic glycidyl ether include 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
Examples of the polyfunctional aromatic glycidyl ethers include bisphenol a glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol a glycidyl ether, biphenol glycidyl ether, tetramethylbiphenol glycidyl ether, and resorcinol glycidyl ether.
Examples of the glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.
Examples of the aliphatic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, 3, 4-epoxycyclohexylethyl-3, 4-epoxycyclohexyl formate, ethylene cyclohexenyl dioxide, propylene cyclohexenyl dioxide, and 3, 4-epoxy-4-methylcyclohexyl-2-propenyl oxide.
In the photocurable composition of the present invention, the polymerizable component may be in the form of a polymer such as an oligomer or a prepolymer, or a copolymer formed from at least one of a monomer, an oligomer, and a prepolymer. In addition, it may be in the form of an aqueous dispersion.
As the aforementioned epoxy group-containing polymer, for example, an epoxy group-containing polymer or resin such as bisphenol a epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, aliphatic type epoxy resin, and the like can be cited.
The epoxy monomer, oligomer, prepolymer, or copolymer is well known to those skilled in the art and is not particularly limited.
Exemplary compounds conforming to the structure of formula (I) are listed below:
Figure BDA0003325667140000071
Figure BDA0003325667140000081
due to the adoption of the scheme, the invention has the beneficial effects that:
the coumarin carbazole photosensitizer capable of initiating polymerization by cations is used as a radiation curing photoinitiator and applied to a radiation curing formula product, in particular to the application of UV-Vis-LED excitable photocuring paint or ink and other occasions. The large conjugated system of the coumarin carbazole molecules enables electrons to be delocalized, and absorption peaks of the molecular structures are red-shifted to a near ultraviolet-visible light region, so that the emission wavelength of the coumarin carbazole molecules is more overlapped with that of the current commercial LED light source, and the excitation efficiency is improved. The coumarin carbazole photosensitizer capable of being polymerized by cationic initiation has high photoinitiation efficiency and good solubility, is combined with matrix resin after being cured, hardly migrates, has a photobleaching effect, and has a very strong application prospect.
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FIG. 1 UV-VISIBLE ABSORPTION SPECTRUM OF FORMULATION 1 OF EXAMPLE 6 WITH 405nm LED EXCITATION
Detailed Description
The invention provides a coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, and a preparation method and application thereof.
The present invention will be further described with reference to the following examples.
Example 1:
the preparation method of the coumarin carbazole photosensitizer (I) -1 capable of initiating polymerization by cations in the embodiment comprises the following steps:
Figure BDA0003325667140000091
step (a): adding POCl at 0-5 deg.C3(4.9mL, 52.00mmol) was added dropwise to DMF (17 mL, 219.53mmol) and stirred at 0-5 ℃ for 30 min. 4-Hydroxycarbazole (10g, 47.00mmol) dissolved in 20mL of DMF was added dropwise over 30min, maintaining the temperature between 0-5 ℃. Stirring was then continued for 20-30min, then the reaction mixture was warmed to room temperature and heated at 70-75 ℃ for 1 h. Completion of the reaction was monitored by TLC, and the resulting reaction mass was poured into crushed ice and stirred well and neutralized with sodium bicarbonate. The resulting precipitate was filtered off and dried, followed by toluene as eluent and purification through silica gel column to give (I) -1 a. The yield was 52.6%.
Step (b): (I) -1a (4g,18mmol) prepared in the previous step and ethyl acetoacetate (1.3g,20mmol) were dissolved in 100mL ethanol, and a catalytic amount of piperidine was added and refluxed for 2h to precipitate a bright yellow crystalline compound. Completion of the reaction was monitored by TLC. The reaction mass was filtered and washed with ethanol to give (I) -1 b. Yield: 91 percent.
Step (c): the flask was charged with (I) -1b (4.15g,15mmol), potassium carbonate (3.92g,28.4mmol) and small amounts of potassium iodide and 18-crown-6 as catalyst and 100mL of DMF as solvent. Nitrogen was passed, then epichlorohydrin (1.47g,16mmol) was slowly added dropwise over 0.5h, reacted in an oil bath at 100 ℃ with stirring, and the completion of the reaction was monitored by TLC. And pouring the reaction liquid into deionized water, stirring, extracting a product by using normal hexane, drying a normal hexane product solution by using anhydrous magnesium sulfate, removing the normal hexane by rotary evaporation, and recrystallizing by using methanol to obtain a light yellow solid product (I) -1. Yield: 88 percent. HR-MS (C)20H15NO4): 333.1161 for m/e; the experimental results are as follows: 334.1248(M + H +).
Figure BDA0003325667140000101
Example 2: preparation of Compounds (I) -2 to (I) -12
These compounds can be prepared in substantially the same manner as in (I) -1 except that ethyl formylacetate substituted in the step (b) is used, and ethyl formylacetate (1), ethyl formylmethoxyacetate (2), ethyl furoylacetate (2), ethyl 2-thenoylacetate (3), ethyl 2-thenoylacetate (4), ethyl 2-pyrroloylacetate (5), ethyl benzoylacetate (6), ethyl benzoylacetate (7), ethyl 4-fluorobenzoylacetate (8), ethyl 4-chlorobenzoylacetate (9), ethyl 4-nitrobenzoylacetate (10), ethyl 4-trifluoromethylbenzoylacetate (11), ethyl 3- (4-methoxyphenyl) -3-oxopropanoate, the prepared intermediate is subjected to the same reaction steps to prepare the target product.
(I) -2, three step overall yield: 65%, HR-MS: 349.1317 for m/e; the experimental results are as follows: 350.1394(M + H)+)。
(I) -3, total yield of three steps: 64%, HR-MS: 385.1474 for m/e; the experimental results are as follows: 386.1562(M + H)+)。
(I) -4, three step overall yield: 70%, HR-MS: 401.1630 for m/e; the experimental results are as follows: 402.1707(M + H)+)。
(I) -5, total yield of three steps: 68%, HR-MS: 384.1943 for m/e; the experimental results are as follows: 385.2020(M + H)+)。
(I) -6, total yield of three steps: 65%, HR-MS: 395.1474 for m/e; the experimental results are as follows: 396.1561(M + H)+)。
(I) -7, total yield of three steps: 65%, HR-MS: 405.1524 for m/e; the experimental results are as follows: 406.1661(M + H)+)。
(I) -8, total yield in three steps: 65%, HR-MS: 413.1317 for m/e; the experimental results are as follows: 414.1394(M + H)+)。
(I) -9, total yield of three steps: 64%, HR-MS: 429.1214 for m/e; the experimental results are as follows: 430.1782(M + H)+)。
(I) -10, total yield in three steps:70%, HR-MS: 440.1630 for m/e; the experimental results are as follows: 441.1707(M + H)+)。
(I) -11, total yield of three steps: 68%, HR-MS: 463.1943 for m/e; the experimental results are as follows: 464.2020(M + H)+)。
(I) -12, total yield in three steps: 65%, HR-MS: 425.1474 for m/e; the experimental results are as follows: 426.1561(M + H)+)。
Example 3: preparation of Compounds (I) -13 to (I) -24
The preparation of these compounds is exactly the same as the first two steps of the corresponding compounds (I) -1 to (I) -12, except that 3- (bromomethyl) -3-ethyloxetane is used in step (c) instead of epichlorohydrin to prepare the desired product.
(I) -13, three step overall yield: 64%, HR-MS: 375.1693 for m/e; the experimental results are as follows: 376.1764(M + H)+)。
(I) -14, total yield of three steps: 65%, HR-MS: 391.2006 for m/e; the experimental results are as follows: 392.2078(M + H)+)。
(I) -15, total yield of three steps: 70%, HR-MS: 427.1563 for m/e; the experimental results are as follows: 428.1647(M + H)+)。
(I) -16, total yield of three steps: 65%, HR-MS: 443.1787 for m/e; the experimental results are as follows: 444.1868(M + H)+)。
(I) -17, total yield of three steps: 62%, HR-MS: 426.2100 for m/e; the experimental results are as follows: 427.2720(M + H)+)。
(I) -18, total yield of three steps: 69%, HR-MS: 437.1630 for m/e; the experimental results are as follows: 438.1160(M + H)+)。
(I) -19, total yield of three steps: 63%, HR-MS: 451.1943 for m/e; the experimental results are as follows: 452.1124(M + H)+)。
(I) -20, total yield in three steps: 59%, HR-MS: 455.2256 for m/e; the experimental results are as follows: 456.2234(M + H)+)。
(I) -21, total yield of three steps: 61%, HR-MS: 471.1787 for m/e; the experimental results are as follows: 472.1867(M + H)+)。
(I) -22, total yield of three steps: 65%, HR-MS: 482.1536 for m/e; the experimental results are as follows: 483.1628(M + H)+)。
(I) -23, total yield of three steps: 62%, HR-MS: 505.1849 for m/e; the experimental results are as follows: 506.1920(M + H)+)。
(I) -24, total yield in three steps: 69%, HR-MS: 467.1380 for m/e; the experimental results are as follows: 468.1460(M + H)+)。
< experiment >
The following experiments were carried out with the products of the above examples, respectively.
Example 4: LED photocuring experiment and coating property test
Sample systems containing epoxy groups and oxetane groups were prepared according to the following formulations (in weight percent)
Monofunctional epoxy monomer (CHO): 21 percent of
Difunctional oxetane monomer (DOX): 76 percent of
Iodonium salt (Iod): 2 percent of
Photosensitizers (examples 1, 2, 3 provide (I) -1-24): 1 percent of
The mixture of the above formulation examples was applied to a cardboard to form a coating of about 30-35 microns using an LED light source (3 cm wide and 80 cm long) from Wako having an emission wavelength of 405nm as an excitation light source and a power of 64mW/cm2And is placed on a variable speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cured efficiently at a rate of greater than 30 m/min.
The compounds of the above examples initiate complete curing of the film layer, and particularly (I) -4, (I) -15, (I) -16 show more excellent initiating performance, and the curing speed can be increased to 40 m/min.
Example 5: LED photocuring experiment and mobility test
Photosensitive resin system for preparing epoxy group-containing sample
According to the specific proportion (in weight percentage) in table 1, the following formulas 1 to 3 and a comparative formula were prepared.
TABLE 1 photocurable System formulation
Formulation 1 Formulation 2 Formulation 3 Comparative formulation
EPOX 96％ 96％ 96％ 96％
Bis-aryl iodonium salts 2％ 2％ 2％ 2％
I-4 of example 2 2％
I-15 of example 3 2％
I-16 of example 3 2％
Isopropylthioxanthone ITX 2％
Respectively injecting the above formula into 30mm × 4mm × 1mm silica gel pad mold, curing in UV curing box for 2min with light intensity of 65mW/cm2. The sample pieces were then pulverized, 0.1g each, and extracted with 15mL of acetonitrile at room temperature for 3 days. And finally, taking the same amount of extract liquor to perform ultraviolet absorption test. The relative mobilities of formulations 1, 2, 3 relative to the comparative formulations were obtained from formulas (1) and (2).
C ═ A/(ε × b) formula (1)
R＝CI-n/CITXX 100% formula (2)
Wherein C is the concentration (mol. L) of the initiator in the extract-1) (ii) a A is absorbance; epsilon is the molar extinction coefficient (L. mol)-1·cm-1) (ii) a b is the thickness (cm) of the sample cell; cI-nThe concentration of I-n provided for in the extract (n-1/8)/20)；CITXIs the ITX concentration in the extract; r is the relative mobility of the macroinitiator.
The test results are shown in table 2:
table 2 mobility test evaluation results
Formulation 1 Formulation 2 Formulation 3 Comparative formulation
Mobility ratio 8 13 9 100
Under the same conditions, the mobility of the composition is only 8-13% of that of the comparative example, and the content of the sensitizer which can be extracted from the cured film is greatly reduced, which shows that the photosensitizer capable of initiating polymerization by cations prepared by the invention can effectively reduce the migration of the initiator and hopefully further reduce the problems of toxicity, odor and the like which may be brought by the photosensitizer.
Example 6: LED photo-excitation light bleaching experiment
10 microliters of formulation 1 from example 5 was uniformly coated on a 10mm x 10mm quartz plate and the spectral change of the formulation was measured by a Maya 2000 fiber spectrometer. The light was excited for different times using a 405nm LED light source and the absorbance of the test was recorded on the spectrometer at different times. As shown in FIG. 1, it was found that the absorbance of the formulation in the visible light region, i.e., 400nm or more, was almost decreased to 0, the color of the formulation was changed from pale yellow to colorless, and the coated film was cured. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.

Claims (10)

1. A coumarin carbazole photosensitizer capable of initiating polymerization by cations is characterized in that the structure of the compound is shown as a general formula (I):
Figure FDA0003325667130000011
wherein:
y is a cationically initiated polymerizable group containing an epoxy group;
z is selected from C1-12Unsubstituted or substituted by 1 to 5R7Substituted phenyl, unsubstituted or substituted by 1 to 9R7Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R7Substituted aromatic heterocyclic radical, or unsubstituted or substituted by 1-8R7Substituted benzoaromatic heterocyclic groups;
R1，R2，R3，R4，R5，R6each independently selected from 1 to 4RaSubstituted C1-6Alkyl, -H, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、-CO2Rb、-OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2Rb；
R7Selected from unsubstituted or substituted by 1-5RaSubstituted C1-6Alkyl, -H, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、-CO2Rb、-OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2RbUnsubstituted or substituted by 1 to 5RcSubstituted carbocyclic ring, unsubstituted or substituted by 1 to 5RdSubstituted heterocycle, OR, P (═ O) (OR)b)2；
RaIs selected from C1-6Alkyl group, (CH)2)rC3-6Cycloalkyl or- (CH)2)rA phenyl group;
Rbselected from H or by 1-5ReSubstituted C1-6Alkyl or by 1-5ReSubstituted- (CH)2)rPh；
RcSelected from the group consisting of 1-5ReSubstituted C1-6Alkyl or by 1-5ReSubstituted (CH)2)rPh；
RdSelected from the group consisting of 1-5ReSubstituted C1-6Alkyl or by 1-5ReSubstituted (CH)2)rPh；
ReSelected from-H, -F, -Cl, -Br, -I, -OH, -NO2、-CN，-CF3、-CF2CF3、C1-4Alkyl radical, C1-4Alkoxy radical, C3-7Cycloalkyl, phenyl, benzyl, phenethyl, naphthyl, heterocyclic aryl, or, keto;
each r is independently 0, 1, 2, 3, or 4.
2. The cationically initiated polymerizable coumarinocazole-based photosensitizer according to claim 1, characterized in that: the Y group is selected from: ethylene oxide alkyl or propylene oxide alkyl, optionally, one or more-CH in the alkyl group between the epoxy group and the carbazole structure2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted.
3. The cationically initiated polymerizable coumarinocazole-based photosensitizer according to claim 2, characterized in that: the Y radical described is preferably C blocked by an oxirane or oxetane group1-8Optionally, one or more-CH's in the alkyl group2Each independently of the others by-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted and H in the oxirane or oxetane group is C1-4Alkyl of (a); specifically, selected from, but not limited to, the following structures:
Figure FDA0003325667130000021
4. the method according to claim 1, wherein the method comprises the following steps:
Figure FDA0003325667130000022
step (a): by reaction with POCl3Performing oxidation reaction to obtain an aldehyde group at the ortho position of the substituted 4-hydroxy carbazole to obtain an intermediate (I) -a;
step (b): the intermediate (I) -a and Z-substituted ethyl formylacetate are subjected to a ring-buckling reaction under the catalysis of alkali to obtain an intermediate (I) -b;
step (c): the intermediate (I) -b reacts with a halide Y-X in the presence of a catalyst to generate a product I; wherein X represents a halogen.
5. The use of the coumarin carbazole photosensitizer shown in the general formula (I) in claim 1 is characterized by being used as a photosensitizer or other functional additive components in a photocuring formula system and being used as an intermediate or a raw material or a reagent in chemical synthesis.
6. Use according to claim 5, characterized in that: the light source of the radiation curing photoinitiator is selected from ultraviolet or visible light or LED light or equivalent light sources.
7. Use according to claim 5, characterized in that the compounds of the general formula (I), the mixtures curable by light radiation; the light radiation curing formula system is characterized in that:
(1) comprises at least one compound described by the general formula (I) and at least one photosensitizer of any kind, which are used alone or in combination with commercial iodonium salt and sulfonium salt as photoinitiating components in a formula system;
(2) contains at least one unsaturated compound containing epoxy or oxetane.
8. The use as claimed in claim 7, characterized in that the ratio is: the content of the photosensitizer represented by the formula (I) is 0.5-20 parts by weight relative to 100 parts by weight of the total amount of the polymerizable components.
9. Use according to claim 7, characterized in that: the epoxy-containing or oxetane-containing unsaturated compound refers to a compound or a mixture of compounds which can be crosslinked by cationic polymerization.
10. The use according to claim 9, wherein: the above polymerizable component means a compound or a mixture which is crosslinked by cationic polymerization of epoxy or oxetane; the polymerizable compound and polymerizable component are monomers, oligomers or prepolymers, or mixtures or copolymers of the three.
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