CN101941939B - Polyfunctional carbazole derivative oxime ester compound and preparation method and light polymerization initiator thereof - Google Patents
Polyfunctional carbazole derivative oxime ester compound and preparation method and light polymerization initiator thereof Download PDFInfo
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- CN101941939B CN101941939B CN 201010233220 CN201010233220A CN101941939B CN 101941939 B CN101941939 B CN 101941939B CN 201010233220 CN201010233220 CN 201010233220 CN 201010233220 A CN201010233220 A CN 201010233220A CN 101941939 B CN101941939 B CN 101941939B
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- following structure
- polynary
- carbazole
- oxime ester
- ester compound
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- -1 carbazole derivative oxime ester compound Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 title 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 150000001350 alkyl halides Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000005917 acylation reaction Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- DQQYORZGTHOZKE-UHFFFAOYSA-N 1-(6-nitro-9h-carbazol-3-yl)ethanone Chemical compound C1=C([N+]([O-])=O)C=C2C3=CC(C(=O)C)=CC=C3NC2=C1 DQQYORZGTHOZKE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001348 alkyl chlorides Chemical group 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- 230000010933 acylation Effects 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000003999 initiator Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 9
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- CNILDPCFXDESRI-UHFFFAOYSA-N 1-(9h-carbazol-3-yl)ethanone Chemical compound C1=CC=C2C3=CC(C(=O)C)=CC=C3NC2=C1 CNILDPCFXDESRI-UHFFFAOYSA-N 0.000 description 4
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- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 241000534944 Thia Species 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
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- 229940125797 compound 12 Drugs 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LKVNIMHCAHVWOZ-UHFFFAOYSA-N 1-sulfonylcarbazole Chemical compound S(=O)(=O)=C1C=CC=C2C3=CC=CC=C3N=C12 LKVNIMHCAHVWOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JGFJDDMRCMCZMU-UHFFFAOYSA-N 3-(trifluoromethyl)-9h-carbazole Chemical compound C1=CC=C2C3=CC(C(F)(F)F)=CC=C3NC2=C1 JGFJDDMRCMCZMU-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- CABSFELLEWZIAK-UHFFFAOYSA-N 3-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3NC2=C1 CABSFELLEWZIAK-UHFFFAOYSA-N 0.000 description 1
- IEUMYICVZHBVAV-UHFFFAOYSA-N 3-fluoro-9h-carbazole Chemical compound C1=CC=C2C3=CC(F)=CC=C3NC2=C1 IEUMYICVZHBVAV-UHFFFAOYSA-N 0.000 description 1
- OYIGWMXXIFYAGD-UHFFFAOYSA-N 3-iodo-9h-carbazole Chemical compound C1=CC=C2C3=CC(I)=CC=C3NC2=C1 OYIGWMXXIFYAGD-UHFFFAOYSA-N 0.000 description 1
- ZYNHZTIMNJKVLK-UHFFFAOYSA-N 3-nitro-9h-carbazole Chemical compound C1=CC=C2C3=CC([N+](=O)[O-])=CC=C3NC2=C1 ZYNHZTIMNJKVLK-UHFFFAOYSA-N 0.000 description 1
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- 238000007725 thermal activation Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Abstract
The invention discloses a polyfunctional carbazole derivative oxime ester compound shown in the structural general formula I, a preparation method thereof and application of the compound used as a light initiator.
Description
[technical field]
The present invention relates to the light trigger technical field, particularly is some polyfunctional group novel oxime ester compounds, their preparation method, and the Photoepolymerizationinitiater initiater that contains ethylene linkage unsaturated compound system take this compound as effective constituent.
[background technology]
Oxime ester compound at the existing bibliographical information (EuropeanPolymer Journal, 1970,6,933) of the seventies in last century, and business-like product such as Quantacure PDO have occurred as light trigger.Although the light-initiated activity of this compounds is outstanding, do not limited its widespread use owing to thermostability is usually good enough.It should be noted that in this compounds in the past few years again to obtain paying attention to, particularly in containing the unsaturated system of ethylene linkage, form photosensitive composite as photopolymerization initiating activity composition.These photosensitive composites are at light-curable ink, the photosensitive printing version, and recording materials, the fields such as photo-resist are widely used.
The oxime ester compound Recent study is active, and technical paper and patent literature are more, for example: Macromol.Symp.2004,217,77; Patent CN101014569A, CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A, and WO2008138733A1, WO0052530A1, WO2007071497A1, WO2009019173A1, WO2009147031A2, it is A that WO2009147033A1 etc. have described some general structures, B, the oxime ester side chain dimer type compound of C and dependency structure.Business-like oxime ester compound light trigger OXE-1 and OXE-2 have appearred on this basis, the photosensitivity system that these compounds form particularly has sensitive response to 405 or 365 nanometer light, in BM and the RGB making field of giant-screen LCD display important application is arranged.
Patent CN101528694A, CN101528682A, and CN101508744A is A to the said structure general formula respectively, B, the oxime ester compound of C has proposed important improvement, is D thereby disclosed general structure, E, the oxime ester compound of F, wherein structure type D and E find that the suitable replacement of nitro on aromatic nucleus can produce more highly sensitive Photoepolymerizationinitiater initiater, and structure type F has obtained the Photoepolymerizationinitiater initiater of solubility property and thermal stability application preferably by modifying side chain.
But, research and develop the new highly sensitive that has concurrently, the light trigger of excellent solvability and thermostability remains the problem that needs solution.
What be worth paying special attention to is, although the light trigger take general structure A-F compound and related derivatives as representative has disclosed on molecular skeleton a plurality of zones and has carried out the possibility that multiple substituting group changes, but known document and patent are not inquired into any dimerization or poly type polyfunctional group oxime ester compound that makes up from carbazole nitrogen-atoms surveyor's chain, these compounds are novel structures, these compounds are to optimizing the photosensitivity of oxime ester compound, strengthen its solvability and thermostability, improve environment and the healthy friendly of photopolymerization process, particularly reduce volatile organic compounds remnants in postdevelopment bake (Post-development Baking) process, new technology solution route is provided.
[summary of the invention]
The invention provides the class polyfunctional group novel carbazole oxime ester compound of deriving, this class novel compound
Have following general structure I:
In general formula I, the integer of n value 2 to 6, preferred 2,3, and 4; X is NO
2, F, Cl, Br, I, PPh
2, O=PPh
2, SPh, SOPh, or SO
2Ph; R
1And R
2Hydrogen independently of one another, or CN, or CF
3, or CF
2R
3, or CFR
3R
4Or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure, and this alkyl can be for being no more than 8 nitrogen, sulphur, or Sauerstoffatom is interrupted; Or carbonatoms is the aromatic base of 6-36, and this aromatic base can contain 1-6 substituent R independent of each other
5, R
5Can be R
3, OR
3, SR
3, COR
3, Br, F, Cl, I, CN, or NO
2Here R
3And R
4That carbonatoms is the alkyl of 1-16 independently of one another, aromatic base, or azepine, thia, the assorted aromatic base of oxa-; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary epoxy, or polyprotonic acid is derived.
The invention allows for the derive preparation method of oxime ester compound of above-mentioned polyfunctional group novel carbazole, its general synthesis technique comprises following five steps:
The first step: carbazole parent nucleus functionalization;
Second step: acylations
The 3rd step: connectionization
The 4th step: oximate
The 5th step: esterification
The novel cpd that the present invention proposes has high photosensitivity, can systematically regulate and control its solvability and thermostability via the nitrogen-containing side chains connecting group easily simultaneously, therefore, can be applied to prepare " personalization " high sensitivity light trigger with various kinds of resin system performance compatibility.In addition, they have more polar group and higher molecular weight owing to connecting, thereby can significantly reduce the remnants of volatile organic compounds in the postdevelopment bake process.
[embodiment]
The invention provides a class formation general formula and be the oxime ester compound of deriving of the polyfunctional group novel carbazole shown in (I), this class novel compound has following general structure I:
In general formula I, the integer of n value 2 to 6, preferred 2,3, and 4; X is NO
2, F, Cl, Br, I, PPh
2, O=PPh
2, SPh, SOPh, or SO
2Ph; R
1And R
2Hydrogen independently of one another, or CN, or CF
3, or CF
2R
3, or CFR
3R
4Or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure, and this alkyl can be for being no more than 8 nitrogen, sulphur, or Sauerstoffatom is interrupted; Or carbonatoms is the aromatic base of 6-36, and this aromatic base can contain 1-6 substituent R independent of each other
5, R
5Can be R
3, OR
3, SR
3, COR
3, Br, F, Cl, I, CN, or NO
2Here R
3And R
4That carbonatoms is the alkyl of 1-16 independently of one another, aromatic base, or azepine, thia, the assorted aromatic base of oxa-; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary epoxy, or polyprotonic acid is derived.
When Q derives via polynary haloalkane and when coming, these haloalkanes are preferably as follows alkyl chloride or the bromoalkane of structure:
When Q is when coming from polyol derivative, these alcohol are preferably as follows structure:
When Q derives and when coming, these acrylate are preferably as follows structure from multicomponent methacrylate:
When Q derives and when coming, these carboxylic acids are preferably as follows structure from polycarboxylic acid:
When Q is when coming from polynary oxirane derivative, these oxyethane are preferably as follows structure:
Because the existence of the two keys of C=N may produce cis-trans-isomer, they usually can directly use without separating the oxime ester compound of general structure I in preparation process.
The invention allows for the preparation method of above-claimed cpd, its general synthesis technique comprises following five steps:
The first step: carbazole parent nucleus functionalization
Many carbazole 3-position is that document is known by the carbazole functionalization compound 1 that the X group replaces, be the commercially available prod or can be easily via known technology preparation, for example 3-nitrocarbazole [SupramolecularChemistry, 20 (4), 357-361; 2008], 3-chloro carbazole [Journal of the Chemical SocietySection C:Organic, (16), 2775-7; 1971], 3-bromo carbazole [Synthesis, (10), 1619-1624; 2005], 3-fluoro carbazole [Journal of Organic Chemistry, 73 (13), 5022-5028; 2008], 3-iodo carbazole [Journal of the American Chemical Society, 131 (47), 17452-17463; 2009], 3-cyano group carbazole [Journal ofthe Chemical Society, 500-4; 1942], 3-trifluoromethyl carbazole [Journal of Organic Chemistry, 74 (13), 4720-4726; 2009], 3-benzene sulfuryl carbazole [Tetrahedron, 45 (16), 5059-64; 1989], 3-diphenyl phosphine carbazole [Advanced Synthesis﹠amp; Catalysis, 346 (7), 743-754; 2004].
Second step: acylations
The carbazole compound 1 that X replaces and suitable acyl chlorides R
1C (O) Cl carries out friedel-crafts acylation reaction under Louis's acid type reagent promotes can make intermediate 2, and the Lewis acid that can select comprises AlCl
3, ZnCl
2, FeCl
3, InCl
3, rare earth trifluoromethyl sulfonic acid La (OTf)
3, Sc (OTf)
3, or In (OTf)
3Deng.
The 3rd step: connectionization
Intermediate 2 can with polynary connective element Q via multiple reaction key and.Take the union body Q of divalence as example, the p-methyl benzenesulfonic acid 4 that binary halides 3 or dibasic alcohol are derived and 2 carries out nucleophilic substitution reaction and can make 5 under alkali promotes, the alkali that can select comprises K
2CO
3, CsCO
3, MeONa, EtONa, NaH etc.; The amidation condensation occurs di-carboxylic acid 6 and 2 can make 7; The epoxy ring-opening reaction occurs binary epoxy 8 and 2 can make 9; Michael reaction occurs and can make 11 in binary acrylate 10 and 2 under organic or inorganic alkali promotes.
The 4th step: oximate
Senior intermediate 5,7,9,11 after the Q connectionization and oxammonium hydrochloride condensation in intensive polar solvent can make oxime compound 12, the preferred DMF of reaction solvent, methane amide, dioxane, ethanol, methyl alcohol, ethylene glycol, or the suitable proportion mixture of these solvents and water.
The 5th step: esterification
The oxime compound 12 that the upper step makes and acyl chlorides R
2Esterification occurs and namely makes final product oxime ester 13 (being the general formula I target compound) in C (O) Cl under alkali promotes, employed alkali can be organic bases or mineral alkali, preferred triethylamine, pyridine, propylene oxide, or K
2CO
3
Execution order that it should be noted that these steps can be done suitable adjustment according to the particular case of institute's synthetic compound.For example, for 3-nitro 6-ethanoyl-carbazole synthetic, because nitro is the group of the deactivated aromatics stronger than ethanoyl, for obtaining preferably yield, should first carry out acylation reaction at the carbazole ring, carry out again nitration reaction, thereby obtain target product.
The preferred embodiment of the oxime ester compound that represents as above-mentioned general formula I can list following compound structure:
The new compound that the present invention proposes can be used as unsaturated allyl compound or contains the light trigger of light polymerization of the mixture of unsaturated allyl compound.Below be the specific examples that is used as light trigger:
Embodiment: (1E, 1 ' E)-1-(9-(2-(3-((E)-1-(acetyl oxygen imines) ethyl)-6-nitro-9H-carbazole-9-yl) ethyl)-6-nitro-9H-carbazole-3-yl) ethyl ketone-oxygen-ethyl oxime
The first step: 3,9-diacetyl group carbazole and 3-ethanoyl carbazole synthetic:
Get the dithiocarbonic anhydride that 55.2 gram carbazoles place 1 liter of drying, add 88.0 gram aluminum trichloride (anhydrous)s, under powerful mechanical stirring, 62.2 gram Acetyl Chloride 98Min.s are added in batches.Finishing reaction system refluxed 6 hours; pour in frozen water and the dilute hydrochloric acid, isolate organic phase, water is used the equal-volume ethyl acetate extraction 2 times again; merge organic phase; wash 2 times, dried over mgso, solvent is spin-dried for; resistates obtains 44.8 grams at a funnel that is filled with silica gel with the methylene dichloride wash-out; the product 3 of 54% yield, 9-diacetyl group carbazole, grey chlorine look solid.
Proton nmr spectra
1H MR (CDCl
3, ppm unit):
8.87(s，1H)，8.18(d，1H，J＝8.4Hz)，8.04-8.00(m，3H)，7.58-7.52(t，1H)，7.45-7.40(m，1H)，2.92(s，3H)，2.76(s，3H)；
Synthesizing of 3-ethanoyl carbazole: it can rapid conversion be 3-ethanoyl carbazole namely that 3,9-diacetyl group carbazole is hydrolyzed in the dilute sulphuric acid of 2N, colourless blocks of solid, fusing point 226-228 ℃.
Second step: 3-ethanoyl-6-nitrocarbazole synthetic:
Get 62.8 gram 3-ethanoyl carbazoles and place 1 liter acetic acid, under powerful mechanical stirring, with the urea nitrate [HNO of equivalent
3O=C (NH
2)
2] slowly add, mixed solution continues to stir, and with tlc tracking monitor reaction process, after the reaction in about 4 hours, reaction solution pours in the large water gaging, separates out a large amount of precipitations, filter, washing, drying, thick product recrystallization in acetic acid obtains sterling.
1H?NMR(d
6-DMSO，ppm)：12.27(br，1H)，10.08(dd，2H)，9.13(s，1H)，8.81-8.20(m，1H)，7.66-7.46(m，1H)，7.44-7.26(m，1H)，2.77(s，3H)。
High resolution mass spectrum HRMS (M+H): C
14H
11N
2O
3, theoretical value 255.0770, measured value 255.0775.
The 3rd step: 1,1 '-(9,9 '-(butane-Isosorbide-5-Nitrae-two base) two (6-nitro-9H-carbazole-9,3-two bases)) diethyl ketone synthetic:
Under nitrogen protection; get 13.9 gram 3-ethanoyl-6-nitrocarbazoles and place the DMF of 160 milliliters of dryings; add 2.7 gram sodium hydrides (60% mineral oil dispersion) in batches; stirring reaction half an hour; drip 5.8 grams 1; the solution of 4-dibromobutane in 15 milliliters of dry DMF, the mixture stirring reaction spends the night.Reaction solution is poured in 600 ml waters, with 400 milliliters of ethyl acetate extractions 3 times, merge organic phase, respectively wash 1 time with saturated aqueous common salt and water, dried over mgso, solvent is spin-dried for, and resistates obtains 7.8 take ethyl acetate/hexane as eluent wash-out purifying and restrains dimerization products, 51% yield on silica gel column chromatography.
High resolution mass spectrum HRMS (M+H): C
32H
27N
4O
6, theoretical value 563.1931, measured value 563.1936.
The 4th step: under nitrogen protection; get the above-mentioned dimer 1 of 7.4 grams; 1 '-(9; 9 '-(butane-1; 4-two bases) two (6-nitros-9H-carbazole-9; 3-two bases)) diethyl ketone placed 40 milliliters of dimethyl formamides, adds the 4 dust molecular sieves that 2.8 gram oxammonium hydrochlorides and 2.0 restrain in advance thermal activation, 80 ℃ of stirring reactions 3 hours; pour in 200 ml waters after being cooled to room temperature; with equal-volume ethyl acetate extraction 3 times, merge organic phase, respectively wash 1 time with saturated aqueous common salt and water; dried over mgso; solvent is spin-dried for, residual solid directly and 3.3 gram diacetyl oxides is mixed in 60 milliliters of butylacetates, 90 ℃ of stirring reactions 2 hours.Reaction system is cooled to room temperature, and to neutral, the same usefulness 200 ml waters dilute with 5% dilute sodium hydroxide aqueous solution regulation system, and ethyl acetate extraction separates the thick product Crystallization Separation in ethyl acetate that obtains and obtains 5.5 gram pure compounds, 62% yield.
1H NMR (d
6-DMSO, ppm unit): 9.04 (d, 2H), 8.50 (d, 2H), 8.38 (dd, 2H), 8.10 (dd, 2H), 7.52 (d, 2H), 7.42 (d, 2H), 4.46 (t, 4H), (2.52 s, 6H), 2.36 (t, 6H), 1.61 (t, 4H).
High resolution mass spectrum HRMS (M+H): C
36H
33N
6O
8, theoretical value 677.2360, measured value 677.2363.
C/H ultimate analysis: C
36H
32N
6O
8:
Theoretical value: C 63.90%, H 4.77%; Measured value: C 63.94%, H 4.85%.
Light sensitivity and the test of remaining smell:
Sensitivity test sample making: with 20 weight percents (together lower) methacrylic acid, 15 parts of methacrylic acid hydroxyl ethyl esters, 10 parts of methyl methacrylates, and 55 parts of butyl methacrylate and 300 parts of ethyl cellosolves mixing, add 1 part of AIBN 70 degrees centigrade of reactions 5 hours, obtain the multipolymer of aforesaid propylene acid system.Next step is got 65 parts of these acrylic copolymers and 5 parts of dipentaerythritol acrylates and 30 parts of acetone and mixes.Under the gold-tinted protection; the light trigger that adds 2 parts in this mixture; stirring and dissolving; get a little this sample application on aluminium sheet; slowly dry desolventizing in 40 minutes at 65 degrees centigrade; cover cellulose acetate film; 21 GTG standard test egative films of different optical density(OD) are set; use metal halide lamp at the Time Exposure (40 second and 80 second) of 60 centimeters with locking; thereafter develop with 1% yellow soda ash alkali lye, the high gray number that keeps because of polymerizing curable after observation is developed is judged the photosensitivity of initiator system.
Remaining smell evaluation: the sample panel after will developing places airtight vial, and this vial of baking is 1 minute in 100 degrees centigrade of baking ovens, and 7 people estimate respectively the smell rank independently, and the standard of assessment is as follows with figure denote:
0 grade: do not have smell;
1 grade: very slight smell;
2 grades: slight smell;
3 grades: obvious smell;
4 grades: strong smell;
5 grades: very strong smell.
The result that 5 bifunctional initiators that synthesize by embodiment provide is as follows:
Claims (6)
1. structure is the polyfunctional carbazole derivative oxime ester compound of general formula (I),
In general formula I, the integer of n value 2 to 6; X is NO
2R
1And R
2Be hydrogen independently of one another, or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary oxyethane, multicomponent methacrylate or polycarboxylic acid are derived;
Described polynary haloalkane is selected from alkyl chloride or the bromoalkane of following structure:
Described polyvalent alcohol is selected from following structure:
Described polynary oxyethane is selected from following structure:
Described polycarboxylic acid is selected from following structure:
Described multicomponent methacrylate is selected from following structure:
2. structure as claimed in claim 1 is the polyfunctional carbazole derivative oxime ester compound of general formula (I), and wherein: the n value is preferred 2,3, or 4.
3. the carbazole claimed in claim 1 preparation method of oxime ester compound that derives, it comprises following five steps:
The first step: carbazole parent nucleus functionalization;
Second step: acylations
The 3rd step: connectionization
The 4th step: oximate
The 5th step: esterification
Wherein, X is NO
2R
1And R
2Be hydrogen independently of one another, or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary oxyethane, multicomponent methacrylate or polycarboxylic acid are derived;
Described polynary haloalkane is selected from alkyl chloride or the bromoalkane of following structure:
Described polyvalent alcohol is selected from following structure:
Described polynary oxyethane is selected from following structure:
Described polycarboxylic acid is selected from following structure:
Described multicomponent methacrylate is selected from following structure:
4. the carbazole claimed in claim 3 preparation method of oxime ester compound that derives, wherein: for 3-nitro 6-ethanoyl-carbazole synthetic, carry out acylation reaction at the carbazole ring first, carry out again nitration reaction.
5. the carbazole of general structure (I) is derived oxime ester compound as the purposes of light trigger,
In general formula I, the integer of n value 2 to 6; X is NO
2R
1And R
2Be hydrogen independently of one another, or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary oxyethane, multicomponent methacrylate or polycarboxylic acid are derived;
Described polynary haloalkane is selected from alkyl chloride or the bromoalkane of following structure:
Described polyvalent alcohol is selected from following structure:
Described polynary oxyethane is selected from following structure:
Described polycarboxylic acid is selected from following structure:
Described multicomponent methacrylate is selected from following structure:
6. purposes as claimed in claim 5, wherein: the n value is preferred 2,3, or 4.
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| WO2013007159A1 (en) * | 2011-07-11 | 2013-01-17 | Chen Ting | N-dual heteronuclear carbazolyl oxime ester compound |
| CN102603720A (en) * | 2012-02-29 | 2012-07-25 | 华南师范大学 | 9-ethyl carbazole chalcone derivative containing coumarin skeleton and synthetic method thereof |
| CN103044581B (en) * | 2012-04-05 | 2014-10-29 | 常州强力电子新材料股份有限公司 | Macromolecular photoinitiator as well as preparation method and application thereof |
| CN105218429A (en) * | 2012-05-09 | 2016-01-06 | 巴斯夫欧洲公司 | Oxime ester photoinitiators |
| EP3044208B1 (en) | 2013-09-10 | 2021-12-22 | Basf Se | Oxime ester photoinitiators |
| CN108484480B (en) * | 2018-04-04 | 2021-02-02 | 三峡大学 | Diphenyl methyl ketoxime acetate containing dicarbazole as photoinitiator, preparation method and application thereof |
| CN112111028A (en) * | 2019-06-21 | 2020-12-22 | 江苏英力科技发展有限公司 | Photoinitiator composition containing acylcarbazole derivative and carbazolyl oxime ester and application of photoinitiator composition in photocuring composition |
| WO2024004426A1 (en) * | 2022-06-27 | 2024-01-04 | 富士フイルム株式会社 | Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator |
| CN115124453A (en) * | 2022-07-13 | 2022-09-30 | 深圳市芯研材料科技有限公司 | Nitrocarbazole oxime ester photoinitiator for improving solubility by group modification and preparation method thereof |
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Denomination of invention: Polyfunctional carbazole derived oxime ester compounds, preparation method and photopolymerization initiator thereof Effective date of registration: 20201102 Granted publication date: 20130529 Pledgee: Industrial and Commercial Bank of China Limited Shenzhen gaoxinyuan sub branch Pledgor: Shenzhen Youwei Technology Holding Co.,Ltd. Registration number: Y2020980007427 |
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Application publication date: 20110112 Assignee: Hubei Youyi New Material Technology Co.,Ltd. Assignor: Shenzhen Youwei Technology Holding Co.,Ltd. Contract record no.: X2024980003537 Denomination of invention: Multifunctional carbazole derived oxime ester compounds, their manufacturing methods, and their photopolymerization initiators Granted publication date: 20130529 License type: Exclusive License Record date: 20240328 |
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