CN117658914A - Naphthalimide photoinitiator, photopolymerizable liquid composition, method and application - Google Patents

Naphthalimide photoinitiator, photopolymerizable liquid composition, method and application Download PDF

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CN117658914A
CN117658914A CN202311625695.8A CN202311625695A CN117658914A CN 117658914 A CN117658914 A CN 117658914A CN 202311625695 A CN202311625695 A CN 202311625695A CN 117658914 A CN117658914 A CN 117658914A
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naphthalimide
photoinitiator
general formula
liquid composition
substituted
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樊江莉
潘庆泽
陈鹏忠
彭孝军
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Dalian University of Technology
Ningbo Research Institute of Dalian University of Technology
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Dalian University of Technology
Ningbo Research Institute of Dalian University of Technology
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    • 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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a naphthalimide photoinitiator, which has a structure shown in the following general formula I: in the general formula I, R 1 The structure of (2) is shown as a general formula II, wherein in the general formula II, n is an arbitrary positive integer; r is R 2 Selected from Br, H, NH 2 One of substituted or unsubstituted phenyl, aziridine, azetidine, tetrahydropyrrole, morpholine, piperidine, hexamethyleneimine or dimethylamine; r is R 3 A substituent selected from the group consisting of an indefinite position on the benzene ring. The naphthalimide photoinitiator disclosed by the invention is based on diethylamino benzonaphthalimide crossed between spin orbit charge transfer systems, and can realize effective visible light polymerization under the condition of no heavy atoms.

Description

Naphthalimide photoinitiator, photopolymerizable liquid composition, method and application
Technical Field
The invention relates to the field of photo-curing materials, in particular to a naphthalimide photoinitiator, a preparation method and application thereof, and photo-polymerizable liquid containing the photoinitiator.
Background
Traditional curing techniques rely primarily on thermosetting techniques, typically carried out in autoclaves or high temperature ovens (-200 ℃), which are characterized by low energy efficiency. But pose significant challenges for the development of future cured materials due to size, energy and material cost constraints. Thus, there is a new need for environmentally friendly, efficient, space or time free curing techniques. The photocuring refers to the process that monomers or oligomers are converted into solid state from liquid state through a photoinitiator under the irradiation of light, and has the advantages of high efficiency, environmental protection, energy saving and the like, and has excellent space and time selectivity. Generally, the photo-curing process generally comprises a light source, a photo-initiator (PI) and a polymerizable medium. Visible Light Emitting Diodes (LEDs) with negligible radiation, no harm, low cost, and high efficiency have been more widely studied than conventional mercury lamps. However, absorption by PIs is difficult to match to the narrow wavelength range of LED lamps, resulting in low excitation efficiency. Furthermore, PI can be classified into radical type PI and cationic type PI according to the type of initiation mechanism. Compared with cationic PI, the free radical PI has the advantages of quick initiation, simple preparation, low price and the like. Thus, visible light-triggered radical initiators are more suitable for photocuring.
Free radical PI can be generally classified into type I and type II according to their mechanism of action on photopolymerization (FRP). The I-type initiator generates chemical bond homolytic cleavage under irradiation, and generates active free radicals for polymerization. In this process, such initiators inevitably produce toxic lysates, pungent odors and volatile substances, which have a detrimental effect on the environment. The hydrogen transfer mechanism of the II-type free radical photoinitiator avoids the possibility of cracking fragments generated by homolytic cracking of the I-type free radical photoinitiator, and is safer and more environment-friendly. However, type II photoinitiation is suffering from low hydrogen transfer efficiency. The electron/hydrogen extraction efficiency involved in the hydrogen transfer mechanism needs to be improved by increasing the excited state lifetime and shortening the donor-acceptor distance. To date, one common strategy is to add heavy atoms (e.g., pt, ir, ru, br and I) to chromophores to increase their efficiency in creating triplet excited states. However, this method results in low solubility of the initiator, poor photostability and large cytotoxicity, limiting practical applications. The intersystem crossing SOCT-ISC of spin-orbit charge transfer without heavy atoms can occur in molecules with significant Charge Transfer (CT) properties, which can also increase triplet yield. In view of the above, in order to improve intersystem crossing (ISC) efficiency, shorten donor-acceptor distance, and develop and design a high-efficiency photoinitiator free of heavy atoms and self-hydrogen to promote the processing of new materials is very necessary.
Disclosure of Invention
Aiming at the problems of dark toxicity increase, short tri-state service life and poor light stability caused by the fact that the photoinitiator depends on heavy atoms doped with noble metals or toxic halogens in the prior art, the invention provides a naphthalimide photoinitiator which is based on diethylaminobenzonaphthalimide crossed between spin orbit charge transfer systems and can realize efficient visible light polymerization under the condition of no heavy atoms.
In order to achieve the above object, the technical scheme of the present invention is as follows: a naphthalimide photoinitiator has a structure shown in a general formula I:
in the general formula I, the compound is shown in the specification,
R 1 the structure of (2) is shown as a general formula II, wherein in the general formula II, n is an arbitrary positive integer;
R 2 selected from Br, H, NH 2 One of substituted or unsubstituted phenyl, aziridine, azetidine, tetrahydropyrrole, morpholine, piperidine, hexamethyleneimine or dimethylamine;
R 3 a substituent selected from the group consisting of an indefinite position on the benzene ring.
Further, the methodThe substituents indicated in the substituted phenyl groups are selected from H, OH, SH, NH 2 、NO 2 、CN、COOH、C 1-8 Alkoxy, C 1-8 Alkylamino, C 1-8 Amide, halogen or C 1-8 One of the haloalkyl groups;
the substituents at the undetermined positions of the benzene rings are selected from H, OH, SH, NH 2 、NO 2 、CN、COOH、C 1-8 Alkoxy, C 1-8 Alkylamino, C 1-8 Amide, halogen or C 1-8 One of the haloalkyl groups.
Further, in formula II, n has a value of 1, 2 or 3;
the R is 2 Selected from aziridine, morpholine, piperidine or dimethylamine.
An initiator comprising said imide dye, said photopolymerizable liquid composition comprising 0.01 to 0.1 weight percent naphthalimide photoinitiator, the balance being tripropylene glycol diacrylate;
or consists of amine compounds, onium salt compounds and naphthalimide photoinitiators, wherein the weight of the naphthalimide photoinitiators is 0.1-5wt% of that of the initiators, the weight of the amine compounds is 1-10 times that of the naphthalimide photoinitiators, and the balance is the onium salt compounds.
Further, the amine compound is selected from one or a combination of any several of L-phenylglycine, N-phenylglycine, 2-amino-2-phenylacetic acid, N- (2-carboxyl) phenylglycine, N-phenyl-N-methylglycine, 4-dimethylaminoethyl benzoate, N-dimethylaniline, N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine and triisopropanolamine.
Further, the onium salt compound is selected from one or a combination of any of iodonium salt compounds and sulfonium salt compounds.
Still further, the iodonium salt compound is selected from one or a combination of any of diphenyl iodonium hexafluorophosphate, bis (tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, triaryliodonium salt, diaryl iodonium salt, alkyl iodonium salt;
the sulfonium salt compound is selected from one or a combination of any of triarylsulfonium salt, diaryl sulfonium salt and alkyl sulfonium salt.
The preparation method of the naphthalimide photoinitiator comprises the following steps:
(1) Will contain R under inert atmosphere 3 Substituted 4-bromo-1, 8-naphthalic anhydride and R-containing compounds 1 Reflux reaction of substituted aniline in organic solvent for 3-12 hr at 120 deg.c; the preferred time is determined according to different reaction processes;
(2) The compound obtained in the step (1) and the compound R are subjected to inert atmosphere 2 Reflux-reacting in a reaction solvent for 3-12h at 125 ℃ to obtain a target product;
the process is as follows:
further, R is contained in the step (1) 3 Substituted 4-bromo-1, 8-naphthalic anhydride and R-containing compounds 1 The molar ratio of the substituted aniline is 1:1-4; preferably in a molar ratio of 1:1-2;
the organic solvent is at least one of absolute ethyl alcohol, acetic acid or formic acid; ethanol is preferred.
Further, in the step (2), the compound obtained in the step (1) and the compound R 2 The molar ratio of (2) is 1:1-1:1.5; an optimal molar ratio of 1:1.5;
the reaction solvent is at least one selected from dimethyl sulfoxide, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, acetonitrile, chlorobenzene, dichlorobenzene, anisole, petroleum ether, dioxane, tetrahydrofuran, pyridine, N-dimethylformamide, N-methylpyrrolidone, methyl tertiary butyl ether, ethylene glycol dimethyl ether, acetone, butanone, methanol, ethanol or propanol, and the most preferred solvent is ethylene glycol monomethyl ether.
The naphthalimide photoinitiator has low cytotoxicity when applied to the technical field of photo-curing, and is beneficial to promoting the application of coatings, printing ink or 3D printing and the like in the aspects of food packaging and biological medicine.
Further, the main material cured in the photo-curing technology is at least one selected from the group consisting of diethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate.
In summary, the invention has the following beneficial effects:
the first, the imine derivative provided by this application has D (electron donor) -T (conjugated electron bridge) -A (electron acceptor) structure, this application regards diethylamino as electron acceptor, take-Ph-R as electron donor, take-coumarin mother nucleus as bridge, through theoretical analysis of density function, know that HOMO electron is mainly distributed in-diethylamino, LUMO electron is mainly distributed in bridge and electron acceptor position, it can be stated that intramolecular charge transfer can take place, make its absorption peak red shift its absorption peak in the visible light region, adapt to LED light source;
secondly, as the hydrogen donor and the hydrogen acceptor are in a parent nucleus structure, the photoinitiation activity is high, and experiments prove that the polymerization rate of the acrylic ester monomer can be about 90 percent by only 0.05 weight percent;
thirdly, the polymerization can be initiated without adding auxiliary agent, which contains auxiliary initiation group;
fourth, the toxicity is low, green.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a graph of the ultraviolet-visible (UV-Vis) spectrum of the photoinitiators of examples 1-5 of the present disclosure, at concentrations of 1X 10 -5 mol/L, wherein the test system is acetonitrile solution;
FIG. 2 is a graph showing the absorbance change of the photoinitiator according to examples 1-5 of the present disclosure under irradiation of an LED having a wavelength of 405nm, wherein the concentration of the photoinitiator molecules is 1X 10 -5 mol/L, LED light intensity of 100mW/cm 2 ；
FIG. 3 is a schematic illustration of the thermal stability of the photoinitiators of examples 1-5 of the present disclosure under nitrogen protection;
FIG. 4 is a schematic representation of the cure conversion of a one-part photopolymerizable liquid containing photoinitiators of examples 1-5 according to the present disclosure;
FIG. 5 is a schematic representation of the cure conversion of a multi-component photopolymerizable liquid containing photoinitiators of examples 1-5 according to the present disclosure;
FIG. 6 is a graph of the kinetics of photopolymerization of a mixed NPG/IOD versus TPGDA monomer at optimum concentrations, where the initiator/co-initiator is measured in percent relative to the mass of the monomer. The irradiation wavelength was 405nm, and the optical density was 100mW/cm 2 。
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method for purifying the naphthalimide photoinitiator of the present invention is not particularly limited by adopting a conventional method. Usually, after completion, a small amount of solvent is added to precipitate.
The naphthalimide photoinitiator represented by the general formula I is described in detail below with reference to examples.
A naphthalimide photoinitiator has a structure shown in a general formula I:
in the general formula I, the compound is shown in the specification,
R 1 selected from the structures shown in the general formula II or-OC n H m N and m are arbitrary positive integers;
R 2 selected from Br, H, NH 2 One of substituted or unsubstituted phenyl, aziridine, azetidine, tetrahydropyrrole, morpholine, piperidine, hexamethyleneimine or dimethylamine;
R 3 a substituent selected from the group consisting of an indefinite position on the benzene ring.
Preferably, R 2 Selected from-N (CH) 3 ) 2 ,-N(CH 2 CH 3 ) 2 ,-NCH 3 C 4 H 8 CH 3 ,-Ph-OCH 3 or-Ph-OC 3 H 7 ；
Specific examples of the compounds represented by the general formula I are given below, but the present invention is not limited to these specific examples.
The general synthetic process of the compound shown in the general formula I is as follows:
the compounds of the present invention represented by the general formula I can be synthesized by the following methods
Examples
Example 1
The N-Br naphthalimide photoinitiator has the following structural formula:
the preparation method comprises the following steps:
4-bromo-1, 8-naphthaiic anhydride (3.26 g,11.78 mmol) was added to a 100mL double bottle and dissolved in 25mL ethanol. N, N-diethyl-p-phenylenediamine (2.52 g,15.5 mmol) was added with stirring for 10 min. Subsequently, the mixture was refluxed under nitrogen atmosphere for 2.5 hours. After the mixture was cooled overnight, a large number of needle crystals precipitated and were washed with water several times to give a tan solid, 4.6g, 93.6% yield, designated N-Br.
The nuclear magnetic hydrogen spectrum data of the photoinitiator N-Br are as follows:
1 HNMR(400MHz,CDCl3)δ8.70(dd,J＝7.3,1.1Hz,1H),8.61(dd,J＝8.5,1.1Hz,1H),8.46(d,J＝7.8Hz,1H),8.06(d,J＝7.8Hz,1H),7.87(dd,J＝8.5,7.3Hz,1H),7.14–7.06(m,2H),6.81–6.74(m,2H),3.40(q,J＝7.1Hz,4H),1.20(t,J＝7.0Hz,6H).
mass spectrum data of photoinitiator N-Br were: c of m/z calculation 19 H 18 BrNO 2 [M+H] + 422.0630, test 423.03.
Example 2
One class of N-PD naphthalimide photoinitiators has the following structural formula:
the preparation method comprises the following steps:
NP-Br (4.22 g,10 mmol) prepared in example 1 was placed in a 100mL two-necked flask, 40mL of ethylene glycol monomethyl ether was added as a solvent, and 0.5mL of piperidine was added. Subsequently, the mixture was refluxed under a nitrogen atmosphere for 3 hours. After the completion of the reaction, purification by petroleum ether/dichloro column chromatography gave the objective product, designated N-PD,3.98g, 93.2% yield. And carrying out structural identification through mass spectrum and nuclear magnetic resonance spectrum;
the nuclear magnetic hydrogen spectrum data of the photoinitiator N-PD is as follows:
1 HNMR(400MHz,CDCl 3 )δ8.61(d,J＝7.3Hz,1H),8.53(d,J＝8.1Hz,1H),8.42(d,J＝8.4Hz,1H),7.69(t,J＝7.8Hz,1H),7.20(d,J＝8.1Hz,1H),7.10(d,J＝8.4Hz,2H),6.76(d,J＝8.4Hz,2H),3.39(q,J＝7.1Hz,4H),3.24(q,J＝6.4Hz,4H),1.90(p,J＝5.5Hz,4H),1.74(d,J＝6.6Hz,2H),1.19(t,J＝7.0Hz,6H).
mass spectrum data of photoinitiator N-PD were: c of m/z calculation 27 H 29 N 3 O 2 [M+H] + 427.2260, test 428.2339.
Example 3
One class of N-ML naphthalimide photoinitiators has the following structural formula:
the only difference from example 2 is that the solvent R 2 Different from each other, in particular,
NP-Br (4.22 g,10 mmol) provided in example 1 was placed in a 100mL two-necked flask, 40mL of ethylene glycol monomethyl ether was added as a solvent, and 0.5mL of morpholine was added. Subsequently, the mixture was refluxed under a nitrogen atmosphere for 3 hours. After completion of the reaction, purification by petroleum ether/dichloro column chromatography gave the desired product, designated N-ML,3.79g, in 88.3% yield. And carrying out structural identification through mass spectrum and nuclear magnetic resonance spectrum;
the nuclear magnetic hydrogen spectrum data of the photoinitiator N-ML are as follows:
1 HNMR(400MHz,CDCl 3 )δ8.63(d,J＝7.2Hz,1H),8.57(d,J＝8.0Hz,1H),8.46(d,J＝8.4Hz,1H),7.73(t,J＝7.8Hz,1H),7.24(d,J＝7.8Hz,1H)7.10(d,J＝8.4Hz,2H),6.77(d,J＝8.4Hz,2H),4.04(t,J＝4.5Hz,4H),3.40(q,J＝7.1Hz,4H),3.29(t,J＝4.5Hz,4H),1.20(t,J＝7.0Hz,6H).
mass spectrum data of photoinitiator N-ML were: c of m/z calculation 26 H 27 N 3 O 3 [M+H] + 427.2260, test 428.2339.
Example 4
One class of NP-ML naphthalimide photoinitiators has the following structural formula:
the preparation method comprises the following steps:
(1) 4-bromo-1, 8-naphthaiic anhydride (3.26 g,11.78 mmol) was added to a 100mL double flask and dissolved in 25mL ethanol. Aniline (1.457 g,15.5 mmol) was added with stirring for 10 min. Subsequently, the mixture was refluxed under nitrogen atmosphere for 2.5 hours. After the mixture was cooled overnight, a large number of needle crystals precipitated and were washed with water several times to give a tan solid, designated NP-Br,4.05g, 96% yield.
(2) The NP-Br (3.51 g,10 mmol) obtained in the step (1) was placed in a 100mL two-necked flask, 40mL of ethylene glycol monomethyl ether was added as a solvent, and 0.5mL of morpholine was added. Subsequently, the mixture was refluxed under a nitrogen atmosphere for 3 hours. After completion of the reaction, purification by petroleum ether/dichloro column chromatography gave the objective product, designated NP-ML,3.16g, 88.3% yield. And carrying out structural identification through mass spectrum and nuclear magnetic resonance spectrum;
the nuclear magnetic hydrogen spectrum data of the photoinitiator NP-ML is:
1 HNMR(400MHz,DMSO)δ8.56(dd,J＝8.5,1.3Hz,1H),8.49(dd,J＝7.3,1.2Hz,1H),8.42(d,J＝8.1Hz,1H),7.85(dd,J＝8.5,7.2Hz,1H),7.56–7.49(m,2H),7.48–7.42(m,1H),7.40(d,J＝8.1Hz,1H),7.38–7.33(m,2H),3.93(t,J＝4.5Hz,4H),3.30–3.22(m,4H).
mass spectrum data of photoinitiator NP-ML were: c of m/z calculation 22 H 18 N 2 O 3 [M+H] + 358.1317, test 359.1393.
Example 5
A class of NOP-ML naphthalimide photoinitiators has the following structural formula:
the preparation method comprises the following steps:
(1) 4-bromo-1, 8-naphthaiic anhydride (3.26 g,11.78 mmol) was added to a 100mL double bottle and dissolved in 25mL ethanol. P-methoxyaniline (1.922 g,15.5 mmol) was added with stirring for 10 min. Subsequently, the mixture was refluxed under nitrogen atmosphere for 2.5 hours. After the mixture was cooled overnight, a large number of needle crystals precipitated and were washed with water several times to give a tan solid, designated NOP-Br,3.95g, with a yield of 88%.
(2) NOP-Br (3.81 g,10 mmol) provided in step (1) was placed in a 100mL two-necked flask, 40mL of ethylene glycol monomethyl ether was added as a solvent, and 0.5mL of morpholine was added. Subsequently, the mixture was refluxed under a nitrogen atmosphere for 3 hours. After completion of the reaction, purification by petroleum ether/dichloro column chromatography gave the objective product, designated NOP-ML,3.58g, 92.3% yield. And carrying out structural identification through mass spectrum and nuclear magnetic resonance spectrum;
the nuclear magnetic hydrogen spectrum data of the photoinitiator NOP-ML are as follows:
1 HNMR(400MHz,DMSO)δ8.55(dd,J＝8.4,1.2Hz,1H),8.48(dd,J＝7.3,1.1Hz,1H),8.42(d,J＝8.1Hz,1H),7.85(dd,J＝8.4,7.3Hz,1H),7.40(d,J＝8.1Hz,1H),7.28–7.22(m,2H),7.08–7.03(m,2H),3.97–3.89(m,4H),3.83(s,3H),3.25(t,J＝4.5Hz,4H).
mass spectrum data of the photoinitiator NOP-ML were: c of m/z calculation 23 H 20 N 2 O 4 [M+H] + 388.1423, test 389.1495.
Test case
Test example 1
In order to prove the application of the naphthalimide photoinitiators prepared in the examples 1-5 in the field of photo-curing technology, the naphthalimide photoinitiators prepared in the examples 1-5 have low cytotoxicity and are beneficial to promoting the application of coatings, printing ink or 3D printing and the like in food packaging and biological medicine, the naphthalimide photoinitiators prepared in the examples 1-5 are prepared into 1X 10 by adopting methylene dichloride -5 The mol/L naphthalimide solution was used for the following tests:
(1) Absorption test
The absorbance of the solutions of the compounds of examples 1 to 5 was measured with an ultraviolet spectrophotometer, and the measurement results are shown in fig. 1.
As can be seen from FIG. 1, the absorption range of N-Br is 250-375 nm, while the absorption peaks of N-PD, N-ML, NP-ML, NOP-ML cover 350-475 nm, to illustrate that changing the group at position 2 affects the change in absorption, and when an electron donating group is introduced, the absorption is red-shifted. The change of the first-order group does not cause a significant change of the initiator in comparison with the N-ML, NP-ML and NOP-ML.
(2) Steady state photolytic testing
2mL of naphthalimide dichloromethane solution was placed in a cuvette and irradiated with light from different LED light sources (light intensity 100 mW/cm) 2 ) The change in absorbance of the solution was measured with an ultraviolet spectrophotometer at various times, and the test results are shown in fig. 2.
As can be seen from FIG. 2, the absorption peak of the photoinitiator molecule gradually decreases with increasing illumination time, and N-PD, N-ML are degraded slowly compared with NP-ML, NOP-ML, indicating that R is changed 1 The group is favorable for regulating the light stability of the photoinitiator, and the N-PD and the N-ML have better light stability and are favorable for photoinitiation.
(3) Photo-induced thermal stability test
The thermal stability of the synthetic dye is evaluated by adopting a thermogravimetry, the synthetic dye is heated to 600 ℃ from 50 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, and the thermal decomposition temperature of the synthetic dye is determined by taking the weight loss of 5wt% as a standard. Heating from 50deg.C to 100deg.C at 10deg.C/min, maintaining the temperature for 10min, and continuing to heat up to 600deg.C at 10deg.C/min. The test results are shown in FIG. 3.
As can be seen from FIG. 3, the temperature of 5wt% of the N-PD, N-ML, NP-ML, and NOP-ML is about 400 ℃, and the temperature of the N-PD, N-ML, NP-ML, and NOP-ML is 450 ℃ when the thermal weight loss is 50wt%, so that the developed initiator has good thermal stability and is convenient to store and transport.
Test example 2
To demonstrate that the naphthalimide photoinitiator prepared in examples 2-5 was used as a photoinitiator to initiate polymerization in the environment without the addition of an auxiliary agent under the irradiation of a 405nm LED light source; the initiation activity is higher than that of the existing photoinitiator such as benzophenone, naphthalimide and the like.
(1) Preparing a single-component photosensitive liquid containing naphthalimide photoinitiator, wherein the single-component photosensitive liquid comprises the following components in proportion:
a tripropylene glycol diacrylate (99.99% -99.90% by mass)
The initiator comprises 0.01 to 0.1 weight percent of naphthalimide photoinitiator
(2) Preparing a composite component photosensitive liquid containing naphthalimide photoinitiator, wherein the ratio of the photosensitive liquid is as follows:
the initiator consists of an amine compound, an onium salt compound and a naphthalimide photoinitiator, wherein the weight of the naphthalimide photoinitiator accounts for 0.05wt% of that of the initiator, the weight of the amine compound is 1-10 times that of the naphthalimide photoinitiator, the weight of the onium salt compound is 1-10 times that of the naphthalimide photoinitiator, and the balance is TPGDA monomer. Preferably, the amine compound is selected from the amine N-phenylglycine and the onium salt compound is selected from diphenyliodonium hexafluorophosphate.
(3) Photoinitiation capability test of single-component photosensitive liquid
Tripropylene glycol diacrylate of (1) was mixed with the above-mentioned compounds (0.03 wt%,0.05wt%,0.1 wt%) prepared in examples 1 to 5, respectively, and a uniform resin mixture was obtained by ultrasonic vibration and mechanical agitation to prepare a photocurable formulation. Based on the FRP process, the resins studied were coated on thin KBr sheets (thickness=2 mm). And then covered with another glass sheet for photopolymerization. After irradiation, the decrease in TPGDA double bond content was monitored using a Nicolet5700FT-IR spectrometer. The test results are shown in fig. 4, 5 and 6.
FIG. 4 is a schematic diagram of the curing conversion rate in the step (3), which is aimed at illustrating that the single-component N-ML still has ultra-high photoinitiating capability, and it can be seen from FIG. 4 that the N-PD/N-ML alone can initiate curing only by 0.03wt%, and the conversion rate of the acrylic ester double bond can reach 85% when the curing conversion rate is continuously increased to 0.05 wt%. When increased to 0.1wt%, the conversion was approximately ninety percent.
FIG. 5 is a schematic view of the cure conversion of examples 1-5, which is intended to demonstrate the excellent effect of the developed initiator, in an amount of only 0.05wt% over the commercially available type II BP photoinitiator (0.3%, an Naiji, 99% pure).
As can be seen from FIG. 6, if N-PD/N-ML (0.05 wt%) is used in conjunction with a commercially available NPG/IOD (0.3 wt%) (NPG: N-phenylglycine, 98% pure, an Naiji; IOD: diphenyliodohexafluorophosphate, 97% pure, an Naiji), the acrylate double bond conversion can be up to 90%. After the auxiliary agent is added, the conversion rate of the double bonds of the acrylic ester is not greatly improved, but only the polymerization rate is improved, so that the developed single-component initiator is proved to preferentially perform intramolecular hydrogen absorption for initiation in the hydrogen absorption process, intermolecular hydrogen absorption is used as supplement, and the effectiveness of single-component photoinitiation is verified again.
NAPTH-43/Iod (0.5%/2%, w/w) in page 18 table 7 of the prior non-patent literature (Recent advances on naphthalic anhydrides and 1, 8-nanoshalimide-based photoinitiators of polymerization, guillaume Noirbent, friedel Dumur, european Polymer Journal,132,109702,2020. (https:// doi.org/10.1016/j.eurpolymj.2020.109702.)) was found at 405nm,110Mw/cm 2 The conversion rate under irradiation is only about 60%, and it can be seen that the photoinitiator provided in the prior art has a large amount, high optical density and low conversion rate, and the initiation capability of the naphthalimide photoinitiator disclosed in the application is better than that of the existing naphthalimide photoinitiator, and the naphthalimide photoinitiator disclosed in the application still has a high conversion rate under the conditions of lower amount and lower optical density.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A naphthalimide photoinitiator is characterized by having a structure shown in a general formula I:
in the general formula I, the compound is shown in the specification,
R 1 the structure of (2) is shown as a general formula II, wherein in the general formula II, n is an arbitrary positive integer;
R 2 selected from Br;
R 3 a substituent selected from the group consisting of an indefinite position on the benzene ring.
2. A class of naphthalimide photoinitiators according to claim 1, wherein said R in formula I 2 Can also be selected from H, NH 2 One of substituted or unsubstituted phenyl, aziridine, azetidine, tetrahydropyrrole, morpholine, piperidine, hexamethyleneimine or dimethylamine;
the substituents indicated in the substituted phenyl groups are selected from H, OH, SH, NH 2 、NO 2 、CN、COOH、C 1-8 Alkoxy, C 1-8 Alkylamino, C 1-8 Amide, halogen or C 1-8 One of the haloalkyl groups.
3. The naphthalimide photoinitiator according to claim 1, wherein the substituents at indefinite positions on the benzene ring are selected from H, OH, SH, NH 2 、NO 2 、CN、COOH、C 1-8 Alkoxy, C 1-8 Alkylamino, C 1-8 Amide, halogen or C 1-8 One of the haloalkyl groups;
the value of n is 1, 2 or 3.
4. A photopolymerizable liquid composition comprising a naphthalimide photoinitiator according to any one of claims 1-3, wherein the photopolymerizable liquid composition comprises 0.01-0.1wt% naphthalimide photoinitiator, the balance being tripropylene glycol diacrylate;
or consists of amine compounds, onium salt compounds and naphthalimide photoinitiators, wherein the weight of the naphthalimide photoinitiators accounts for 0.1-5wt% of the weight of the photopolymerizable liquid composition, the weight of the amine compounds is 1-10 times of the weight of the naphthalimide photoinitiators, and the balance is the onium salt compounds.
5. The photopolymerizable liquid composition of claim 4 wherein the amine compound is selected from the group consisting of L-phenylglycine, N-phenylglycine, 2-amino-2-phenylglycine, N- (2-carboxy) phenylglycine, N-phenyl-N-methylglycine, ethyl 4-dimethylaminobenzoate, N-dimethylaniline, N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine, triisopropanolamine, and combinations of any of the foregoing.
6. The photopolymerizable liquid composition according to claim 4, wherein the onium salt compound is selected from the group consisting of iodonium salt compounds and sulfonium salt compounds.
7. A process for the preparation of a naphthalimide photoinitiator according to any of claims 1 to 3, characterised in that it comprises the steps of:
will contain R under inert atmosphere 3 Substituted 4-bromo-1, 8-naphthalic anhydride and R-containing compounds 1 Reacting the substituted aniline in an organic solvent for 3-12h at 120 ℃ to obtain a target product;
the process is as follows:
8. the method for preparing a naphthalimide photoinitiator according to claim 7, further comprising the steps of:
under inert atmosphere, the target product and the compound R are prepared according to the mol ratio of 1:1-1:1.5 2 Reacting in a reaction solvent for 3-12h at 125 ℃ to prepare a photoinitiator containing naphthalimide derivatives;
the process is as follows:
9. the process for producing a naphthalimide photoinitiator according to claim 7 or 8, wherein R is contained 3 Substituted 4-bromo-1, 8-naphthalic anhydride and R-containing compounds 1 The molar ratio of the substituted aniline is 1:1-4;
the organic solvent is at least one of absolute ethyl alcohol, acetic acid or formic acid;
the reaction solvent is at least one selected from dimethyl sulfoxide, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, acetonitrile, chlorobenzene, dichlorobenzene, anisole, petroleum ether, dioxane, tetrahydrofuran, pyridine, N-dimethylformamide, N-methylpyrrolidone, methyl tertiary butyl ether, ethylene glycol dimethyl ether, acetone, butanone, methanol, ethanol or propanol.
10. Use of a naphthalimide photoinitiator according to any of claims 1-3 in the field of photocuring technology, characterized by applications in coatings, inks, 3D printing, biomedical applications.
CN202311625695.8A 2023-11-30 2023-11-30 Naphthalimide photoinitiator, photopolymerizable liquid composition, method and application Pending CN117658914A (en)

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