CN109970696A - A kind of cumarin oxime ester lightlike initiating agent - Google Patents

A kind of cumarin oxime ester lightlike initiating agent Download PDF

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CN109970696A
CN109970696A CN201910288916.4A CN201910288916A CN109970696A CN 109970696 A CN109970696 A CN 109970696A CN 201910288916 A CN201910288916 A CN 201910288916A CN 109970696 A CN109970696 A CN 109970696A
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alkyl
group
cumarin
oxime ester
alkenyl
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CN109970696B (en
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李治全
邱婉婉
李梦琦
刘仁
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • 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
    • 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
    • C08F222/00—Copolymers 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
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F222/00—Copolymers 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
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

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Abstract

The present invention provides a kind of cumarin oxime ester lightlike initiating agent and preparation method thereof, general formula of molecular structure such as formula (I).The photoinitiator causes photocuring under 360-450nm radiation wavelength, is applied to the fields such as single photon 3D printing, two-photon 3D printing, ink, photoresist.Photoinitiator provided by the present invention not only can be used as LED light initiator but also can be used as two-photon initiator, and all have good initiation activity, one dual-purpose to have saved manufacturing cost to a certain extent.

Description

A kind of cumarin oxime ester lightlike initiating agent
Technical field
The present invention relates to photoinitiator fields, a photoinitiator especially containing cumarin unit and oxime ester units and Preparation method.
Background technique
With becoming increasingly conspicuous for social environment and energy problem, photo-curing material because its in the curing process without or only The advantages of a small amount of solvent volatilization, by people's extensive concern.
Photoinitiator is essential component in photocuring technology, and vital work is played in Light Curing With playing a decisive role to the speed of photocuring, or even will affect the performance of photo-curing material.Photoinitiator is swashing in light source It gives, photolysis occurs, generate the free radical or ion with reactivity, and then cause the polymerization reaction of monomer, thus The polymer network structure for forming crosslinking has in fields such as coating, ink, 3D printings and is widely applied.
In recent years the 3D printing material based on photopolymerization (DLP 3D printing, two-photon 3D printing) because its with it is environmental-friendly, The advantages that precision is high, by more and more extensive concern.Wherein DLP 3D printing is with ultraviolet or visible LED lamp as light Source prepares three-dimensional structure, precision with higher by way of being successively superimposed.But since light scattering and initiator expand Factors, the technology such as scattered be not good enough in the precision of micro-nano structure manufacture view.And it is two-photon polymerized be by ultra-short pulse laser, Focal point double-photon optical initiator causes photocuring system polymerization, complicated three-dimensional micro-nano structure is formed by superposition, and have High precision.The deficiency in traditional DLP 3D printing is compensated for a certain extent, but two-photon printing is in focal point Realize solidification, print speed is relatively slow, therefore it is most important to develop high performance double-photon optical initiator.Up to the present, The two-photon polymerized of free radical type is mainly based upon intermolecular electron transport mechanism, such as dyestuff/amine system, i.e. two-photon excitation Under, dyestuff absorbs energy, then transfers an electron to amine molecule, generates reactive amines, then causes polymerization, but the system can deposit In inverted electron transfer, the deficiencies such as efficiency of initiation is low；Another mechanism is that photoinduction Direct Pyrolysis generates reactive species, such as Irgacure The photoinitiator of the commercializations such as 369 and TPO also has application in two-photon polymerized, because its two photon absorption cross section is smaller, double It is active and bad under photon laser, but its absorption cross-section is smaller.LED light initiator develops toward visible light at present, such as CN109305951A discloses a kind of coumarin kind compound and its preparation and application, makes as visible LED initiator With, but the class formation cannot achieve multi-functional (such as two-photon causes activity), efficient utilization.
Therefore, develop and a kind of all have the good initiator for causing performance under two-photon laser and under LED light source and have Important Economic meaning.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of long conjugation cumarin oxime ester lightlike initiating agents and preparation method thereof. Using the coumarin group of visible light as chromophore, extend conjugation chain lengths in its No. 7 positions to expand two photon absorption cross section, and Introduced on 3, No. 4 positions of cumarin can the oxime ester base group of rapid cleavage be used as activated centre, to obtain swashing in visible light and two-photon The dual-purpose photoinitiator of rapid cleavage under light.
A kind of cumarin oxime ester lightlike initiating agent has following general formula of molecular structure:
Wherein,
R1Including
R3Represent hydrogen atom, C1-C20Alkyl, C3-C20Naphthenic base or C2-C20Alkenyl；
Wherein hydrogen atom above-mentioned, C1-C20Alkyl, C3-C20Naphthenic base or C2-C20Alkenyl optionally by one or Multiple groups independently selected from the group below replace: halogen, nitro, cyano, hydroxyl, list (C1-C6Alkyl) amino, two (C1-C6Alkane Base) amino, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
R2Represent C1-C20Alkyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C4-C20Cycloalkyl-alkyl, C2-C20 Alkenyl, C3-C20Cycloalkenyl, C4-C20Alkylcycloalkenyl, C4-C20Cycloalkenyl alkyl, C6-C20Aryl or C7-C20's Aralkyl；
Wherein aforementioned R2In C1-C20Alkyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C4-C20Naphthenic base alkane Base, C2-C20Alkenyl, C3-C20Cycloalkenyl, C4-C20Alkylcycloalkenyl, C4-C20Cycloalkenyl alkyl, C6-C20Aryl Or C7-C20Aralkyl be optionally independently selected by one or more from the following group group replace: halogen, list (C1-C6Alkyl) Amino, two (C1-C6Alkyl) amino, nitro, cyano, hydroxyl, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
R4Represent hydrogen atom, C1-C20Alkyl, C2-C20Alkenyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C2- C20Alkenyl, C6-C20Aryl or C7-C20Aralkyl.
Preferably, a kind of cumarin oxime ester lightlike initiating agent,
The R3Represent hydrogen atom, C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl；
Its aforementioned R3In C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl optionally by one Or multiple groups independently selected from the group below replace: halogen, nitro, cyano, hydroxyl, list (C1-C6Alkyl) amino, two (C1-C6 Alkyl) amino, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
The R3Represent hydrogen atom, C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl；
The R2、R3、R4Structure in, arbitrary CH2Replace for unsubstituted group or by O, S, C=O or NH Group, arbitrary CH be the arbitrary C of group that unsubstituted group is perhaps replaced by N be unsubstituted group or by Si or The group that Ge replaces, arbitrary H are unsubstituted group or the group replaced by halogen, nitro, hydroxyl, cyano or amino.
Preferably, the R2Represent C1-C12Alkyl, C4-C10Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C10Chain Alkenyl, C3-C12Cycloalkenyl, C4-C12Cycloalkenyl alkyl or alkylcycloalkenyl, C6-C10Aryl, C7-C10Aralkyl；
Wherein C above-mentioned1-C12Alkyl, C4-C10Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C10Alkenyl, C3-C12 Cycloalkenyl, C4-C12Cycloalkenyl alkyl or alkylcycloalkenyl, C6-C10Aryl, C7-C10Aralkyl optionally by one A or multiple groups independently selected from the group below replace: halogen, list (C1-C6Alkyl) amino, two (C1-C6Alkyl) amino, nitre Base, cyano, hydroxyl, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
The R2In structure, arbitrary CH2For unsubstituted group or the group replaced by O, S, C=O or NH, appoint The CH of meaning is that unsubstituted group is perhaps unsubstituted group by the arbitrary C of group that N replaces or is replaced by Si or Ge Group；Arbitrary H is unsubstituted group or the base replaced by halogen, phenyl, nitro, hydroxyl, sulfonic group, cyano or amino Group.
Preferably, the R4Represent hydrogen atom, C1-C10Alkyl, C2-C4Alkenyl, C3-C10Heteroaryl, C6-C10 Aryl or C7-C12Aralkyl.
Preferably, the photoinitiator is selected from following:
A kind of method of cumarin oxime ester lightlike initiating agent, includes the following steps:
(1) synthesis of A: a and ethyl acetoacetate obtain A under the effect of the catalyst, a and ethyl acetoacetate Molar ratio is 1:1~1:3, and the molar ratio of preferably a and catalyst is 1:0.1~1:2, and the catalyst is yttrium nitrate, described A be amino-phenol, preferably 3- amino-phenol；
(2) synthesis of B: A reacts under strong acid environment, cryogenic conditions with sodium nitrite, and product is then anti-with M It answers, obtains B, the molar ratio of the A and sodium nitrite is that the molar ratio of 1:1~1:5, A and M are 1:2~1:10；M is halogenation Object, including potassium iodide, potassium bromide, preferably potassium iodide；X represents any one of Br or I；
(3) it the synthesis of C: in organic solvent by 3- halobenzene phenol and anhydrous magnesium chloride, triethylamine and paraformaldehyde dispersion, obtains To C；X represents any one of Br or I；
(4) synthesis of D: in the presence of fatty amine, C reacts to obtain D, C and acetoacetate with ethyl acetoacetate at room temperature The molar ratio of ethyl ester is 1:1~1:3；
(5) synthesis of E: in the presence of selenium dioxide, B is oxidized to E, and the molar ratio of the B and selenium dioxide is 1:1~1:5；
(6) synthesis of F: in the presence of catalyst and acid binding agent, by D or E and d dispersion, reaction obtains F in organic solvent, The molar ratio of the D or E and d is that the ratio of 1:1~1:3, D or E and catalyst is 1:0.01~1:1, and the d is R1Corresponding knot Structure, preferably 4- lignocaine phenylacetylene and 4- diethylin styrene；The R1、R3、R4Such as any one of claim 1-4 It is defined；
(7) synthesis of G: in the presence of acid binding agent, F and hydroxylamine hydrochloride react in ethanol solution, obtain G, described The molar ratio of middle F and hydroxylamine hydrochloride is 1:1~1:5；The R1、R4As any one of claim 1-4 is defined；
(8) synthesis of photoinitiator: in the presence of acid binding agent, G and e reacts in organic solvent, obtains the perfume (or spice) Legumin oxime ester photoinitiator formula (I), raw material e are chloride compounds, corresponding R2Structure, the molar ratio of the G and e are 1:1 The molar ratio of~1:3, G and acid binding agent is 1:1~1:3.
Further, the reaction temperature of the step (1) is 70~100 DEG C, and the reaction time is 1~10 hour.
Further, step (2) low temperature is -20~20 DEG C, the reaction time is 1~10 hour.
Further, in the step (3), the additive amount of paraformaldehyde, magnesium chloride and triethylamine is 3-10 equivalent, reaction temperature Degree is 70~200 DEG C, is reacted 24 hours.
Further, in the step (4), the fatty amine includes piperidines, and reaction temperature is 0~50 DEG C, the reaction time 1 ~10 hours.
Further, in the step (5), reaction temperature is 50~200 DEG C, and the reaction time is 20~60 hours.
Further, in the step (6), used catalyst be it is following any one or more: cuprous iodide, bi triphenyl Phosphine dichloride palladium, acid chloride, triphenylphosphine, bi triphenyl phosphine dichloride nickel；Reaction is under anaerobic；Reaction temperature be 20~ 200℃。
Further, in the step (7), the molar ratio of intermediate F and acid binding agent is 1:0.5~1:5, reaction temperature 20 ~100 DEG C.
Root is further, and in the step (8), reaction temperature is 0~30 DEG C, and the reaction time is 0.5~5 hour.
Further, the acid binding agent includes one or more of: triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, Sodium hydroxide, sodium hydride, sodium acetate, piperidines.
Further, the organic solvent includes any of the following or a variety of: methylene chloride, chloroform, methanol, ethyl alcohol, Toluene, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, dimethylbenzene, paraxylene, acetonitrile, triethylamine.
Described formula (I) compound can be used as photoinitiator application, application field such as light solidifying coating, 3D printing, highly dense Degree optical information storage, the processing of micro-nano optical device, microfluidic device or biological support are constructed.
In above-mentioned preparation method, the raw material used is known compound in the prior art, can be by commercially available.
The present invention is beneficial to be had the technical effect that
(1) cumarin oxime ester photoinitiator of the invention causes active height in visible-range, and curing rate is fast, can There is good application prospect in terms of light-exposed polymerization forming.
(2) prepared by the present invention that there is larger two photon absorption cross section, it is a kind of good double-photon optical initiator, micro- Micro-nano structure manufacture view has a good application prospect.
(3) photoinitiator provided by the present invention not only can be used as LED light initiator but also can be used as two-photon initiator, And good initiation activity is all had, it is one dual-purpose to have saved manufacturing cost to a certain extent.
(4) threshold value of photoinitiator provided by the present invention is lower, can not only be energy saving, can also promote process velocity simultaneously, It improves efficiency；In addition, being conducive to laser beam splitter processing, efficiency is further increased.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its Its purpose, feature and advantage will be apparent.
Fig. 1 is the UV-visible absorption spectrum of compound H1 and H2 in the embodiment of the present invention 3；
Fig. 2 is the REAL TIME INFRARED THERMAL IMAGE conversion ratio figure of double bond in acrylatcs systems in the embodiment of the present invention 4；
Fig. 3 is the digital photograph figure of 3D printing molding structure in the embodiment of the present invention 5；
Scanning electron microscope (SEM) photograph of the Fig. 4 for molding circular microstructure in the embodiment of the present invention 6；
Scanning electron microscope (SEM) photograph of the Fig. 5 by forming 24 face body structures in the embodiment of the present invention 6；
Fig. 6 is the energy profile of the two-photon of H2 and the M2CMK of comparison structure printing in comparative example of the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is It can be with conventional products that are commercially available.
Embodiment 1
The preparation of cumarin oxime ester lightlike initiating agent H1, specific preparation process is as follows:
(1) synthesis of A1
In the single necked round bottom flask of 50ml, 3.37g (30.9mmol) 3- amino-phenol, six nitric hydrate of 1.25g is added Yttrium (Y (NO3)3·6H2O) (3.3mmol) and 4.82g (37.1mmol) ethyl acetoacetate, reacts 2 hours at 90 DEG C, then It is cooled to room temperature, dissolves reactant with 50ml ethyl alcohol, be then poured into a large amount of water, suction filtration obtains yellow solid, at 40 DEG C Vacuum oven in it is dry, obtain 2.58g final product, yield 50%.
A1 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 7.39 (dd, J=2.3,1.2Hz, 1H), 6.61 (d, J=2.3Hz, 1H), 6.59 (d, J=1.2Hz, 1H), 6.05 (q, J=1.2Hz, 1H), 4.17 (s, 2H), 2.38 (d, J= 1.2Hz,3H)。
(2) synthesis of B1
3.25g (18.6mmol) A1 is dispersed in the water of 90ml, the 7ml concentrated sulfuric acid is added dropwise, then to reaction temperature When being down to -10~-5 DEG C, 1.54g (22.6mmol) NaNO is added dropwise2(being dissolved with 12ml water) and 5.43g (32.7mmol) KI (being dissolved with 12ml water), reacts 4 hours at room temperature；Then reaction solution is extracted with ethyl acetate, first with the Na of 25% (W/V)2S2O3 Washing, then 1N HCl, 2N NaOH and saturated common salt water washing are used respectively, finally use anhydrous Na2SO4Dry, revolving removes solvent, Crude product purified by silica gel column chromatography separating-purifying obtains 1.66g final product, yield 31%.
B1 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 7.74 (d, J=1.6Hz, 1H), 7.65 (dd, J =8.3,1.7Hz, 1H), 7.32 (d, J=8.3Hz, 1H), 6.34 (q, J=1.3Hz, 1H), 2.44 (d, J=1.2Hz, 3H).
(3) synthesis of E1
In the single necked round bottom flask of 250ml, 2.80g (9.8mmol) B1 and 2.22g (20.0mmol) selenium dioxide is dissolved In the paraxylene of 150ml, reacted 48 hours at 140 DEG C；It is cooled to room temperature to reaction solution, is filtered to remove solid impurity, so After rotate to obtain crude product, finally use silica gel column chromatography separating-purifying, obtain 1.2g final product, yield 35%.
E1 nuclear-magnetism characterization:1H NMR(400MHz,Chloroform-d)δ10.11(s,1H),8.33(s,1H),7.81(d, J=1.6Hz, 2H), 7.71 (s, 1H), 6.94 (s, 1H).
(4) synthesis of F1
Under nitrogen protection, 400.2mg (1.3mmol) E1,11.3mg Pd (P (Ph are added in the reaction flask of 50ml3)4Cl2 (0.02mmol), 7.3mg CuI (0.04mmol) and 250.5mg (1.72mmol) 4- acetenyl-n,N-Dimethylaniline, then 8ml anaerobic tetrahydrofuran and 2ml anaerobic triethylamine is added, is reacted 5 hours at 53 DEG C；It then cools to room temperature, by reaction solution It pours into a large amount of water, is extracted with dichloromethane 3~5 times, merge organic phase, use anhydrous Na2SO4, rotate and remove solvent, finally use Silica gel column chromatography separating-purifying crude product obtains 245mg final product, yield 57%.
F1 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 10.14 (s, 1H), 8.55 (d, J=8.3Hz, 1H), 7.51-7.45 (m, 4H), 6.87 (s, 1H), 6.77 (d, J=8.3Hz, 2H), 3.06 (s, 6H).
(5) synthesis of G1
In the single necked round bottom flask of 50ml, by 133.3mg (0.42mmol) F1,62.2mg (0.9mmol) hydroxylamine hydrochloride and 80mg (0.98mmol) sodium acetate is dispersed in 18ml ethanol solution, is reacted 2 hours at 80 DEG C；Reaction solution is cooled to room Temperature is subsequently poured into a large amount of water, is extracted with dichloromethane 3 times, then use anhydrous Na2SO4Dry, revolving removes solvent, finally uses silicon Gel column chromatography separating-purifying crude product obtains 121mg final product, yield 87%.
G1 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 8.31 (s, 1H), 8.20 (d, J=8.4Hz, 1H), 8.09 (s, 1H), 7.48 (s, 3H), 7.42 (d, J=9.4Hz, 1H), 6.74 (d, J=8.2Hz, 2H), 6.60 (s, 1H), 3.05(s,6H)。
(6) synthesis of H1
In the single necked round bottom flask of 25ml, 123mg (0.39mmol) G1 and 13mg (0.54mmol) sodium hydride is dissolved In 15ml anhydrous tetrahydro furan, 30min is stirred at 0 DEG C in nitrogen atmosphere, 62 microlitres of chlorobenzoyl chlorides are added, continue to stir 20min；Then with 5% sodium bicarbonate solution quenching reaction, then be extracted with dichloromethane, anhydrous Na2SO4It is dry, rotate red Color solid finally carries out column chromatography for separation purification, obtains 210mg final product, yield 74%.
H1 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 8.69 (s, 1H), 8.51 (d, J=8.8Hz, 1H), 8.19 (d, 2H), 7.72-7.67 (m, 1H), 7.56 (t, J=7.8Hz, 2H), 7.51-7.46 (m, 4H), 6.72 (d, J= 1.9Hz,2H),6.70(s,1H),3.05(s,6H)。
Embodiment 2
The synthesis of H2, the specific steps are as follows:
(1) synthesis of C1
In the reaction flask of 100ml, 1.5g (6.8mmol) 3- iodophenol and 2g (21.1mmol) anhydrous magnesium chloride are dissolved In 50ml anhydrous acetonitrile and 6ml (43.2mmol) triethylamine solution, 2g (66.7mmol) paraformaldehyde is then added, in 85 DEG C Lower reaction 24 hours；The reaction is cooled to room temperatures, are then neutralized with 1N HCl solution, and methylene chloride extracts three times, anhydrous Na2SO4 It is dry, crude product is rotated to obtain, finally obtains 0.69g product, yield 40% with silica gel column chromatography separating-purifying.
C1 nuclear-magnetism characterization:1H NMR(400MHz,Chloroform-d)δ11.05(s,1H),9.87(s,1H),7.46(s, 1H), 7.42 (dd, J=8.1,1.5Hz, 1H), 7.26 (d, J=8.1Hz, 1H).
(2) preparation of D1
In the single necked round bottom flask of 50ml, 0.67g (2.7mmol) C1 is dissolved in 20ml dehydrated alcohol, is then added Enter 0.5ml (3.7mmol) ethyl acetoacetate, temperature is then cooled to 0 DEG C, 50 microlitres of (0.5mmol) piperidines, room temperature is added Lower reaction 4 hours；Reaction solution is poured into a large amount of water, is filtered, is dried in a vacuum drying oven, obtain the yellowish solid of 0.54g, is produced Rate 60%.
D1 nuclear-magnetism characterization:1H NMR(400MHz,Chloroform-d)δ8.46(s,1H),7.80(s,1H),7.71(dd, J=8.2,1.6Hz, 1H), 7.36 (d, J=8.2Hz, 1H), 2.74 (s, 3H).
(3) synthesis of F2
In the reaction flask of 50ml, by 488mg (1.56mmol) D1,269mg (1.86mmol) 4- acetenyl-N, N- diformazan Base aniline, 13.4mg (0.02mmol) Pd (PPh3)4Cl2After being dissolved in 15ml deoxygenation with 9.3mg (0.05mmol) cuprous iodide In tetrahydrofuran, then be added 2ml deoxygenation at after triethylamine, reacted 5 hours at 53 DEG C；It is cooled to room temperature wait react, it will It is poured into a large amount of water, is extracted with dichloromethane 3 times, anhydrous Na2SO4Dry, revolving removes solvent, finally uses silica gel column chromatography Method separating-purifying obtains 439mg red solid, yield 86%.
F2 nuclear-magnetism characterization:1H NMR (400MHz, Chloroform-d) δ 8.50 (s, 1H), 7.59 (d, J=8.1Hz, 1H),7.49–7.41(m,4H),6.70(d,2H),3.05(s,6H),2.75(s,3H)。
(4) synthesis of G2
In the single necked round bottom flask of 50ml, by 196mg (0.59mmol) F2,85mg (1.23mmol) hydroxylamine hydrochloride and 97mg (1.18mmol) sodium acetate is dispersed in 10ml ethyl alcohol, reacts 2 hours at 80 DEG C, reaction system is then cooled to room Temperature, to a large amount of water are entered, three times with the extraction of 80ml methylene chloride, organic phase anhydrous Na2SO4It is dry, crude product is rotated to obtain, finally 75mg target product, yield 37% are obtained by silica gel column chromatography separating-purifying.
G2 nuclear-magnetism characterization:1H NMR (400MHz, DMSO-d6) δ 11.48 (s, 1H), 8.11 (s, 1H), 7.80 (d, J= 8.1Hz, 1H), 7.50 (s, 1H), 7.47-7.38 (m, 3H), 6.74 (d, J=8.9Hz, 2H), 2.98 (s, 6H), 2.09 (s, 3H)。
(5) synthesis of H2
It is in the single necked round bottom flask of 25ml, 68.4mg (0.2mmol) G2 and 12.8mg (0.53mmol) sodium hydride is molten Solution stirs 30min at 0 DEG C under nitrogen protection in 4ml anhydrous tetrahydro furan, and 34 microlitres of (0.37mmol) benzene first are then added Acyl chlorides continues to stir 20min；The sodium bicarbonate solution quenching reaction first with 5% is post-processed, then is extracted with dichloromethane, it is anhydrous Na2SO4It is dry, red solid is rotated to obtain, column chromatography for separation purification is finally carried out, obtains 60.7mg final product, yield 67%.
H2 nuclear-magnetism characterization: 1H NMR (400MHz, Chloroform-d) δ 8.19 (s, 1H), 8.18-8.14 (m, 2H), 7.69-7.63 (m, 1H), 7.54 (dd, J=6.8,1.3Hz, 2H), 7.52 (s, 1H), 7.46 (d, J=8.8Hz, 3H), 7.43 (dd, J=8.0,1.5Hz, 1H), 6.71 (d, J=8.5Hz, 2H), 3.04 (s, 6H), 2.59 (s, 3H)
Embodiment 3
The compound H1 and compound H2 prepare to embodiment 1 and embodiment 2 carries out performance measurement respectively, by it is ultraviolet- It is 360-450nm that visible spectrophotometer, which measures its absorption bands, and ultraviolet-visible absorption spectroscopy is shown in Fig. 1, it can be found that its Maximum absorption wavelength matches in the wavelength of the LED light of 405nm or so and the 405nm of longest.
Embodiment 4
Solidified resin infrared conversion ratio of the long conjugation cumarin oxime ester photoinitiator of the present invention in resin system
Under the conditions of being protected from light, the solidified resin of acrylatcs systems (acrylate): 10mg compound H1 and H2 is prepared respectively It is added in 1g TMPTA/TMP3EOTA (molar ratio 1:1) monomer and dissolves completely, wherein comparative sample TPO (is bought from Suzhou Tai Yang Chemical inc) concentration is identical, its double bond conversion rate result such as Fig. 2 is measured with the LED light irradiation of 450nm, discovery exists Under the LED light of 450nm, the initiation performance for the long conjugation oxime ester photoinitiator that the present invention reports is better than the TPO being commercialized.System institute It is as follows with the structural formula of monomer:
Embodiment 5
Application of the long conjugation cumarin oxime ester photoinitiator of the present invention in 3D printing
Under the conditions of being protected from light, 900mg compound H2,45g trimethylolpropane are added in the glass container equipped with stirrer Triacrylate and 45g ethoxylated trimethylolpropane triacrylate, stirring oscillation for 24 hours, make compound H2 dissolution completely, The photo-curing material for 3D printing can be obtained, be poured into printer resin storage tank, printer optical source wavelength is 405nm, recalls the 3D model to be printed, and printer automatic printing goes out stereochemical structure, such as Fig. 3, it was demonstrated that the length that the present invention designs Conjugation cumarin oxime ester initiator prints good stereochemical structure under visible LED lamp.
Embodiment 6
Application of the long conjugation cumarin oxime ester photoinitiator of the present invention in structure processing
The preparation of double-photon optical photoresist: under the conditions of being protected from light, 5mg embodiment 1 is added in the glass container equipped with stirrer In three acrylic acid of compound H2,500mg trimethylolpropane trimethacrylate and 500mg ethoxylated trimethylolpropane Ester, stirring oscillation make compound H2 dissolution completely for 24 hours, double-photon optical photoresist can be obtained；
Micro-structure processing: above-mentioned double-photon optical photoresist is applied on glass slide, femtosecond laser, 80fs in 800nm wavelength The femtosecond laser of pulse, 100 μm/s print speed under processing micro structure, processed structure be round matrix, obtain precision compared with Good micro-structure (most narrow linewidth is about 150nm, most wide to be no more than 300nm), such as Fig. 4；Fig. 4 is part-circular shape scanning electron microscope Figure, energy range 8-30mW, 100 μm/s of process velocity.
Stereochemical structure processing: in manuscript 4 when microstructure, laser spot is focused in resin, fixes an energy, Row's circular configuration is processed, then improves laser energy, sets up another a row, processes circular configuration, and so on, from the bottom to top, energy It gradually rises, measures the threshold value of initiator；In addition, having formed 24 increasingly complex face body structures, such as Fig. 5 more than threshold value；Fig. 5 For 24 face bulk microstructures, energy is 15mW, 100 μm/s of process velocity at this time.
Thus illustrate that the threshold value of long conjugation cumarin oxime ester photoinitiator provided by the invention is lower, threshold value 8mW, threshold value It is low can not only energy conservation, process velocity can also be promoted simultaneously, improved efficiency；In addition, Low threshold is conducive to laser beam splitter processing, into one Step improves efficiency.Further illustrate that photoinitiator stability and photonasty of the invention are good, efficiency of initiation is high.
Comparative example
The long conjugation cumarin oxime ester photoinitiator of the present invention and the comparison of reported high-performance two-photon initiator (M2CMK)
Under the conditions of being protected from light, the compound H2,500mg tri- in 5mg embodiment 1 is added in the glass container equipped with stirrer Hydroxymethyl-propane triacrylate and 500mg ethoxylated trimethylolpropane triacrylate, stirring oscillation make compound for 24 hours Completely, same condition prepares the M2CMK system with H2 same concentrations, tests its two-photon absorption energy range, such as H2 dissolution Fig. 6, wherein the polymerization threshold values of H2 is 10mW, process window 10-30mW, and the process window of M2CMK is 12mW, process window For 12-32mW, in contrast, the long conjugation oxime esters double-photon optical initiator for illustrating that the present invention designs can be real at lower energy Now it polymerize, is a kind of more efficient double-photon optical initiator.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill Many modifications and changes are obvious for the those of ordinary skill in art field.

Claims (17)

1. a kind of cumarin oxime ester lightlike initiating agent, it is characterised in that the photoinitiator has following general formula of molecular structure:
Wherein,
R1Including
R3Represent hydrogen atom, C1-C20Alkyl, C3-C20Naphthenic base or C2-C20Alkenyl；
Wherein hydrogen atom above-mentioned, C1-C20Alkyl, C3-C20Naphthenic base or C2-C20Alkenyl it is optionally one or more Group independently selected from the group below replaces: halogen, nitro, cyano, hydroxyl, list (C1-C6Alkyl) amino, two (C1-C6Alkyl) ammonia Base, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
R2Represent C1-C20Alkyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C4-C20Cycloalkyl-alkyl, C2-C20Alkene Base, C3-C20Cycloalkenyl, C4-C20Alkylcycloalkenyl, C4-C20Cycloalkenyl alkyl, C6-C20Aryl or C7-C20Aralkyl Base；
Wherein aforementioned R2In C1-C20Alkyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C4-C20Cycloalkyl-alkyl, C2-C20Alkenyl, C3-C20Cycloalkenyl, C4-C20Alkylcycloalkenyl, C4-C20Cycloalkenyl alkyl, C6-C20Aryl or C7-C20Aralkyl be optionally independently selected by one or more from the following group group replace: halogen, list (C1-C6Alkyl) ammonia Base, two (C1-C6Alkyl) amino, nitro, cyano, hydroxyl, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2- C6Alkenyl；
R4Represent hydrogen atom, C1-C20Alkyl, C2-C20Alkenyl, C3-C20Naphthenic base, C4-C20Alkyl-cycloalkyl, C2-C20's Alkenyl, C6-C20Aryl or C7-C20Aralkyl.
2. a kind of cumarin oxime ester lightlike initiating agent according to claim 1, which is characterized in that
The R3Represent hydrogen atom, C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl；
Its aforementioned R3In C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl optionally by one or more A group independently selected from the group below replaces: halogen, nitro, cyano, hydroxyl, list (C1-C6Alkyl) amino, two (C1-C6Alkyl) Amino, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
The R3Represent hydrogen atom, C1-C12Alkyl, C4-C10Cycloalkyl-alkyl, C2-C10Alkenyl；
The R2、R3、R4Structure in, arbitrary CH2For unsubstituted group or the group replaced by O, S, C=O or NH, Arbitrary CH is that unsubstituted group is perhaps unsubstituted group by the arbitrary C of group that N replaces or is replaced by Si or Ge Group, arbitrary H is unsubstituted group or the group that is replaced by halogen, nitro, hydroxyl, cyano or amino.
3. a kind of cumarin oxime ester lightlike initiating agent according to claim 1, which is characterized in that the R2Represent C1-C12 Alkyl, C4-C10Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C10Alkenyl, C3-C12Cycloalkenyl, C4-C12Cycloalkenyl Alkyl or alkylcycloalkenyl, C6-C10Aryl, C7-C10Aralkyl；
Wherein C above-mentioned1-C12Alkyl, C4-C10Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C10Alkenyl, C3-C12Ring Alkenyl, C4-C12Cycloalkenyl alkyl or alkylcycloalkenyl, C6-C10Aryl, C7-C10Aralkyl optionally by one or Multiple groups independently selected from the group below replace: halogen, list (C1-C6Alkyl) amino, two (C1-C6Alkyl) amino, nitro, cyanogen Base, hydroxyl, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl；
The R2In structure, arbitrary CH2For unsubstituted group or the group replaced by O, S, C=O or NH, arbitrarily CH is unsubstituted group perhaps by the arbitrary C of group that N replaces is unsubstituted group or is replaced by Si or Ge base Group；Arbitrary H is unsubstituted group or the base replaced by halogen, phenyl, nitro, hydroxyl, sulfonic group, cyano or amino Group.
4. a kind of cumarin oxime ester lightlike initiating agent according to claim 1, which is characterized in that the R4Represent hydrogen original Son, C1-C10Alkyl, C2-C4Alkenyl, C3-C10Heteroaryl, C6-C10Aryl or C7-C12Aralkyl.
5. any cumarin oxime ester lightlike initiating agent described in -4 according to claim 1, which is characterized in that described light-initiated Agent is selected from following:
6. a kind of method for preparing a kind of cumarin oxime ester lightlike initiating agent as described in any in claim 1-4, feature It is, described method includes following steps:
(1) synthesis of A: a and ethyl acetoacetate obtain A, mole of a and ethyl acetoacetate under the effect of the catalyst Than for 1:1~1:3, the molar ratio of preferably a and catalyst is 1:0.1~1:2, the catalyst is yttrium nitrate, and a is Amino-phenol, preferably 3- aminobenzene phenolic ester；
(2) synthesis of B: A reacts under strong acid environment, cryogenic conditions with sodium nitrite, and product is then reacted with M, obtains To B, the molar ratio of the A and sodium nitrite is that the molar ratio of 1:1~1:5, A and M are 1:2~1:10；M is halide, packet Include potassium iodide, potassium bromide, preferably potassium iodide；X represents any one of Br or I；
(3) synthesis of C: in organic solvent by 3- halobenzene phenol and anhydrous magnesium chloride, triethylamine and paraformaldehyde dispersion, C is obtained； X represents any one of Br or I；
(4) synthesis of D: in the presence of fatty amine, C reacts to obtain D, C and ethyl acetoacetate with ethyl acetoacetate at room temperature Molar ratio be 1:1~1:3；
(5) synthesis of E: in the presence of selenium dioxide, B is oxidized to E, the molar ratio of the B and selenium dioxide be 1:1~ 1:5；
(6) synthesis of F: in the presence of catalyst and acid binding agent, by D or E and d dispersion, reaction obtains F in organic solvent, described The molar ratio of D or E and d is that the ratio of 1:1~1:3, D or E and catalyst is 1:0.01~1:1, and the d is R1Corresponding structure, Preferably 4- lignocaine phenylacetylene and 4- diethylin styrene；The R1、R3、R4As any one of claim 1-4 determines Justice；
(7) synthesis of G: in the presence of acid binding agent, F and hydroxylamine hydrochloride react in ethanol solution, obtain G, the middle F with The molar ratio of hydroxylamine hydrochloride is 1:1~1:5；The R1、R4As any one of claim 1-4 is defined；
(8) synthesis of photoinitiator: in the presence of acid binding agent, G and e reacts in organic solvent, obtains the cumarin Oxime ester photoinitiator formula (I), raw material e are chloride compounds, corresponding R2Structure, the molar ratio of the G and e are 1:1~1: 3, G and acid binding agent molar ratio be 1:1~1:3.
7. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (1) reaction temperature is 70~100 DEG C, and the reaction time is 1~10 hour.
8. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (2) low temperature is -20~20 DEG C, and the reaction time is 1~10 hour.
9. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 5, it is characterised in that the step (3) in, the additive amount of paraformaldehyde, magnesium chloride and triethylamine is 3-10 equivalent, and reaction temperature is 70~200 DEG C, and reaction 24 is small When.
10. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (4) in, the fatty amine includes piperidines, and reaction temperature is 0~50 DEG C, and the reaction time is 1~10 hour.
11. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (5) in, reaction temperature is 50~200 DEG C, and the reaction time is 20~60 hours.
12. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (6) in, used catalyst be it is following any one or more: cuprous iodide, bis-triphenylphosphipalladium palladium dichloride, acid chloride, triphen Base phosphine, bi triphenyl phosphine dichloride nickel；Reaction is under anaerobic；Reaction temperature is 20~200 DEG C.
13. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (7) in, the molar ratio of intermediate F and acid binding agent is 1:0.5~1:5, and reaction temperature is 20~100 DEG C.
14. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, it is characterised in that the step (8) in, reaction temperature is 0~30 DEG C, and the reaction time is 0.5~5 hour.
15. according to a kind of preparation method of cumarin oxime ester lightlike initiating agent of claim 6 or 12, which is characterized in that institute The acid binding agent stated includes one or more of: triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, sodium hydride, second Sour sodium, piperidines.
16. a kind of preparation method of cumarin oxime ester lightlike initiating agent according to claim 6, which is characterized in that described Organic solvent includes any of the following or a variety of: methylene chloride, chloroform, methanol, ethyl alcohol, toluene, tetrahydrofuran, N, N- diformazan Base formamide, dimethyl sulfoxide, dimethylbenzene, paraxylene, acetonitrile, triethylamine.
17. a kind of purposes of cumarin oxime ester lightlike initiating agent as described in claim 1, which is characterized in that described light-initiated Agent causes photocuring under 360-450nm radiation wavelength, is applied to single photon 3D printing, two-photon 3D printing, ink, photoresist Equal fields.
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