多官能团咔唑衍生肟酯类化合物、其制造方法及其光聚合 Polyfunctional carbazole derivative oxime ester compounds, its manufacturing method and a photopolymerization

引发剂 Initiator

【技术领域】 TECHNICAL FIELD

[0001] 本发明涉及光引发剂技术领域，特别涉及是一些多官能团新型肟酯类化合物，它们的制备方法，以及以该化合物为有效成分的含烯键不饱和化合物体系的光聚合引发剂。 [0001] The present invention relates to the technical field photoinitiators, particularly to novel polyfunctional some oxime ester compounds, their preparation, and to the compound as an active ingredient-containing ethylenically unsaturated compound photopolymerizable initiator system.

【背景技术】 BACKGROUND OF THE INVENTION

[0002] 肟酯类化合物作为光引发剂在上世纪七十年代已有文献报道（EuropeanPolymer Journal，1970，6，933)，并出现了商业化的产品如Quantacure PD0。 [0002] oxime ester compounds as photoinitiators in the seventies has been reported (EuropeanPolymer Journal, 1970,6,933), and the emergence of commercial products such as Quantacure PD0. 虽然该类化合物光引发活性突出，但由于热稳定性常常欠佳而限制了其广泛应用。 Although the activity of these compounds photoinitiator prominent, but often poor thermal stability and limit its wider application. 值得注意的是，这类化合物在过去几年里重新得到重视，特别是在含有烯键不饱和体系中作为光聚合引发活性成分而组成感光性组合物。 It is worth noting that these compounds over the past few years to regain attention, especially in containing ethylenically unsaturated photo-polymerization initiator system as the active ingredient and the composition of the photosensitive composition. 这些感光性组合物在光固化油墨，感光性印刷版，记录材料，光致抗蚀剂等领域有广泛的应用。 The photosensitive composition of the light-curable inks, photosensitive printing plates, the recording material, such as a photoresist is widely used in the field.

[0003] 肟酯类化合物近年来研究活跃，科技论文和专利文献报道较多，例如：Macr0m0l. Symp. 2004，217，77 ；专利CN101014569A，CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A,以及W02008138733A1，W00052530A1, W02007071497A1, W02009019173A1, W02009147031A2,W02009147033A1等描述了一些结构通式为A，B，C以及相关结构的肟酯侧链二聚体类型化合物。 [0003] The oxime ester compounds active in recent years, scientific papers and patent literature more, such as:.. Macr0m0l Symp 2004,217,77; patent CN101014569A, CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A, and W02008138733A1, W00052530A1, W02007071497A1, W02009019173A1, W02009147031A2, W02009147033A1 and other structural formula describes some oxime ester side chain dimer type compounds A, B, C and related structures. 在此基础上出现了商业化的肟酯化合物光引发剂0XE-1和0XE-2，这些化合物组成的光敏性体系特别是对405或365纳米光有灵敏的响应，在大屏幕LCD显示器的BM和RGB制作领域有重要应用。 On this basis, the emergence of commercial oxime ester compound Photoinitiator 0XE-1 and 0XE-2, a photosensitive system comprising in particular those compounds of 405 or 365 nm light has a sensitive response, BM in large-screen LCD display and RGB production areas have important applications.

[0004] [0004]

叙X減广人· ^ Less extensive person-Syrian X ^

R1'' 0〜 R/ 0、9. R1 '' 0~ R / 0,9.

Abc Abc

αχΛ? dIh^xr αχΛ? dIh ^ xr

。 . 力r7 R7 force

[0005]专利 CN101528694A，CN101528682A,以及CN101508744A 分别对上述结构通式为A， B，C的肟酯化合物提出了重要改进，从而披露了结构通式为D，E，F的肟酯化合物，其中结构类型D和E发现硝基在芳香环上的适当取代可以产生更高灵敏度的光聚合引发剂，而结构类型F通过修饰侧链得到了溶解性能和热稳定性能更适宜应用的光聚合引发剂。 [0005] Patent CN101528694A, CN101528682A, respectively, as well as the above-described structure CN101508744A oxime ester compound of the formula A, B, C presents significant improvements to the disclosure of the structure of formula D, E, F of the oxime ester compound, wherein the structure Type D and E found in Nitro appropriately substituted on the aromatic ring can produce a higher sensitivity photo-polymerization initiator, and the structure of the side chain of the type of F obtained by modifying the photopolymerization solubility and thermal stability of the application more suitable initiators. [0006] [0006]

[0007] 但是，研发新的兼具高灵敏度，优异溶解性和热稳定性的光引发剂仍然是需要解决的问题。 [0007] However, the development of new combination of high sensitivity, excellent solubility and heat stability photoinitiator still need to be resolved.

[0008] 值得特别注意的是，虽然以结构通式AF化合物及相关衍生物为代表的光引发剂披露了在分子骨架上多个区域进行多种取代基变化的可能性，但已知的文献和专利没有探讨任何自咔唑氮原子测链构建的二聚或多聚型多官能团肟酯类化合物，这些化合物是新型的结构，这些化合物对优化肟酯类化合物的感光灵敏度，增强其溶解性和热稳定性，提高光聚合过程的环境和健康友好性，特别是减少在显影后烘烤（Post-development Baking)过程中挥发性有机化合物残余，提供了新的技术解决途径。 [0008] Of particular note is that, although the structural formula AF compounds and related derivatives represented photoinitiators disclosed the possibility of changes in a variety of substituents on the molecular skeleton in several regions, but the known literature and the patent does not discuss any dimeric or multi-functional oxime ester compounds from carbazole nitrogen atom chain constructs measured, and these compounds are novel structure, these compounds to optimize the sensitivity of the photosensitive oxime ester compounds enhance solubility and thermal stability, improve the environment and health-friendly light polymerization process, in particular to reduce baking after development (Post-development Baking) during the residual volatile organic compounds, provides a new technical solution.

【发明内容】 SUMMARY OF THE INVENTION

[0009] 本发明提供一类多官能团新型咔唑衍生肟酯类化合物，这类新的化合物 [0009] The present invention provides a novel class of multifunctional carbazole derivative oxime ester compounds, such new compounds

[0010] 具有以下的结构通式I: [0010] having the general structural formula I:

[0011] [0011]

[0012] 在通式I中，η取值2至6的整数，优选2，3，和4 ;Χ是NO2, F，Cl，Br，I，PPh2，0 = PPh2, SPh, SOPh,或SO2Ph ；礼和R2彼此独立地是氢，或CN，或CF3,或CF2R3,或CFR3R4 ；或碳原子数为1-24的支链或直链，含有或不含有环系结构的烷基，该烷基可以为不超过8个的氮， 硫，或氧原子间断；或碳原子数为6-36的芳香基，该芳香基可以含有1-6个彼此独立的取代基R5, R5可以是R3, OR3, SR3, COR3, Br，F, Cl, I, CN,或NO2 ；这里R3和R4彼此独立地是碳原子数为1-16的烷基，芳香基，或氮杂，硫杂，氧杂的杂芳香基；Q是一个η价联结基团，它可以经由多元卤代烷，多元醇，多元环氧，或多元酸衍生而来。 [0012] In formula I, η an integer ranging from 2-6, preferably 2, 3, and 4; Χ is NO2, F, Cl, Br, I, PPh2,0 = PPh2, SPh, SOPh, or SO2Ph ; propriety and R2 are each independently hydrogen or CN, or CF3, or CF2R3, or CFR3R4; or 1 to 24 carbon atoms, branched or straight chain alkyl group with or without a ring system structure, the alkyl group may be no more than eight of nitrogen, sulfur, or oxygen atoms interrupted; carbon atoms or an aromatic group 6-36, and the aromatic group may contain 1-6 substituents independently of one another R5, R5 can be R3, OR3, SR3, COR3, Br, F, Cl, I, CN, or NO2; where R3 and R4 are each independently a number of 1 to 16 carbon atoms, an alkyl group, an aromatic group, or aza, thia, oxa hetero aryl; Q is a divalent linking group η, it may be via multivariate Halon, polyol, epoxy, or polyacid derived.

[0013] 本发明还提出了上述多官能团新型咔唑衍生肟酯类化合物的制备方法，其通用的合成工艺包括下述五个步骤： [0013] The present invention also provides a method for preparing the polyfunctional novel carbazole derivative oxime ester compounds, the general synthesis process comprises the following five steps:

[0014] 第一步：咔唑母核官能团化； [0014] The first step: carbazole nucleus functionalization;

[0015 [0015

[0022] 第五步：酯化 [0022] The fifth step: esterification

[0023] [0023]

[0024] 本发明提出的新型化合物具有高的感光灵敏度，同时可以方便地经由含氮侧链联结基团对其溶解性和热稳定性进行系统地调控，因此，可以应用于制备与多种树脂体系性能兼容的“个性化”高感度光引发剂。 [0024] The novel compounds of the present invention provides a high photosensitivity, while the system can easily regulate their solubility and thermal stability of a nitrogen-containing side chain via a linking group, and therefore, can be applied with a variety of resins prepared System performance is compatible with "personalized" high sensitivity photoinitiator. 此外，他们由于联结而具有较多的极性基团和较高的分子量，因而可以显著降低显影后烘烤过程中挥发性有机化合物的残余。 In addition, they have since the links and more polar groups and higher molecular weight, which can significantly reduce post-development baking process residual volatile organic compounds.

【具体实施方式】 [DETAILED DESCRIPTION]

[0025] 本发明提供了一类结构通式为（I)所示的多官能团新型咔唑衍生肟酯类化合物， 这类新的化合物具有以下的结构通式I ： [0025] The present invention provides a class structure of the formula (I), multifunctional novel carbazole derivative oxime ester compounds, such new compounds having the general structural formula I:

[0026] [0026]

丫、V Ah, V

N——Q (I) N - Q (I)

P P

_ X _ X

η η

[0027] 在通式I中，η取值2至6的整数，优选2，3，和4 ;Χ是NO2, F，Cl，Br，I，PPh2，0 = PPh2, SPh, SOPh,或SO2Ph ；礼和R2彼此独立地是氢，或CN，或CF3,或CF2R3,或CFR3R4 ；或碳原子数为1-24的支链或直链，含有或不含有环系结构的烷基，该烷基可以为不超过8个的氮， 硫，或氧原子间断；或碳原子数为6-36的芳香基，该芳香基可以含有1-6个彼此独立的取代基R5, R5可以是R3, OR3, SR3, COR3, Br，F, Cl, I, CN,或NO2 ；这里R3和R4彼此独立地是碳原子数为1-16的烷基，芳香基，或氮杂，硫杂，氧杂的杂芳香基；Q是一个η价联结基团，它可以经由多元卤代烷，多元醇，多元环氧，或多元酸衍生而来。 [0027] In formula I, η an integer ranging from 2-6, preferably 2, 3, and 4; Χ is NO2, F, Cl, Br, I, PPh2,0 = PPh2, SPh, SOPh, or SO2Ph ; propriety and R2 are each independently hydrogen or CN, or CF3, or CF2R3, or CFR3R4; or 1 to 24 carbon atoms, branched or straight chain alkyl group with or without a ring system structure, the alkyl group may be no more than eight of nitrogen, sulfur, or oxygen atoms interrupted; carbon atoms or an aromatic group 6-36, and the aromatic group may contain 1-6 substituents independently of one another R5, R5 can be R3, OR3, SR3, COR3, Br, F, Cl, I, CN, or NO2; where R3 and R4 are each independently a number of 1 to 16 carbon atoms, an alkyl group, an aromatic group, or aza, thia, oxa hetero aryl; Q is a divalent linking group η, it may be via multivariate Halon, polyol, epoxy, or polyacid derived.

[0028] 当Q经由多元卤代烷衍生而来时，这些卤代烷优选如下结构的氯代烷或溴代烷： [0028] When Q is derived via multivariate alkyl halides, such as Halon preferably chlorinated or brominated alkyl having a structure:

[0029] [0029]

[0030] 当Q是从多元醇衍生而来时，这些醇优选如下结构： [0030] When Q is derived from polyols, such alcohols preferably the following structure:

[0031] [0031]

[0032] 当Q是从多元丙烯酸酯衍生而来时，这些丙烯酸酯优选如下结构： [0032] When Q is derived from the multivariate acrylate, these acrylates preferably the following structure:

[0033] [0033]

[0034] 当Q是从多元羧酸衍生而来时，这些羧酸优选如下结构： [0034] When Q is derived from polycarboxylic acids, these acids preferably the following structure:

[0035] [0035]

[0036] 当Q是从多元环氧乙烷衍生而来时，这些环氧乙烷优选如下结构： [0036] When Q is derived from ethylene oxide polyol, such as ethylene oxide preferred structure:

[0037 [0037

[0038] 结构通式I的肟酯化合物在制备过程中由于C = N双键的存在可能产生顺反异构体，他们常常不经分离可以直接使用。 [0038] oxime ester compounds of the formula I in the preparation process due to the presence of N = C double bond of cis and trans isomers may occur, they often can be used directly without isolation.

[0039] 本发明还提出了上述化合物的制备方法，其通用的合成工艺包括下述的五个步骤： [0039] The present invention also provides a method for preparing the compounds, their general synthesis process comprises the following five steps:

[0040] 第一步：咔唑母核官能团化 [0040] The first step: carbazole nucleus functionalized

[0041] 许多咔唑3-位被X基团取代的咔唑官能团化化合物1是文献已知的，是市售产品或可以方便地经由已知技术制备，例如3-硝基咔唑[SupramoIecularChemistry，20(4)，357-361 ;2008]，3-氯代咔唑[Journal of the Chemical SocietySection C ： Organic, (16)，2775-7 ;1971]，3-溴代咔唑[Synthesis, (10)，1619-1624 ;2005]，3-氟代咔唑[Journal of Organic Chemistry，73 (13)，5022-5028 ;2008]，3-碘代咔唑[Journal of the American Chemical Society，131(47)，17452-17463 ;2009]，3-氰基咔唑[Journal ofthe Chemical Society, 500-4 ; 1942]，3-三氟甲基咔唑[Journal of Organic Chemistry, 74 (13), 4720-4726 ；2009], 3-苯砜基咔唑[Tetrahedron，45 (16)，5059-64 ； 1989]，3-二苯膦基咔唑[Advanced Synthesis&Catalysis, 346 (7), 743-754 ；2004] „ [0041] Many carbazol-3-position is substituted X groups carbazole functionalized compound is known in the literature, it is commercially available or can be readily prepared via known techniques, for example, 3-nitro-carbazole [SupramoIecularChemistry , 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-carbazole [Journal ofthe Chemical Society, 500-4; 1942], 3- trifluoromethyl-carbazole [Journal of Organic Chemistry, 74 (13), 4720- 4726; 2009], 3-phenyl sulfone carbazole [Tetrahedron, 45 (16), 5059-64; 1989], 3- diphenylphosphino carbazole [Advanced Synthesis & Catalysis, 346 (7), 743-754; 2004] "

[0043] 第二步：酰基化 [0043] The second step: acylated

[0044] X取代的咔唑化合物1和适当的酰氯R1C(O)Cl在路易斯酸型试剂促进下进行傅_克酰基化反应即可制得中间体2，可以选用的路易斯酸包括AlCl3, ZnCl2, FeCl3, InCl3, 稀土三氟甲基磺酸盐La (OTf) 3，Sc (OTf) 3，或In (OTf) 3等。 [0044] X-substituted carbazole compound and the appropriate acid chloride R1C (O) Cl were Fu _ acylation reaction in a Lewis acid-type agent promotes intermediate 2 can be prepared, you can use the Lewis acids include AlCl3, ZnCl2 , FeCl3, InCl3, rare earth triflate La (OTf) 3, Sc (OTf) 3, or In (OTf) 3 and the like.

[0046] 第三步：联结化 [0046] The third step: the coupling of the

[0047] 中间体2可以和多元联结单元Q经由多种反应键和。 [0047] Intermediate 2 and multivariate coupling unit Q can be via a variety of reactions and bond. 以二价的联结体Q为例，二元卤代物3或者二元醇衍生的对甲基苯磺酸4与2在碱促进下进行亲核取代反应可以制得5，可以选用的碱包括K2CO3, CsCO3, MeONa, EtONa, NaH等；二元羧酸6与2发生酰胺化缩合可以制得7 ；二元环氧8与2发生环氧开环反应可以制得9 ；二元丙烯酸酯10和2在有机或无机碱促进下发生迈克尔加成反应可以制得11。 Divalent coupling body Q, for example, binary halides 3 or glycol derivative of methyl p-4 and 2 in the base-promoted nucleophilic substitution reaction can be prepared 5, you can use bases include K2CO3 , CsCO3, MeONa, EtONa, NaH and the like; dicarboxylic acids 6 and 2 amidation condensation can be obtained by 7; 8 and 2 two yuan ethylene epoxide ring-opening reaction occurs can be obtained 9; 10 and two yuan acrylate 2 Michael addition reaction of an organic or inorganic base can be prepared to promote 11.

[0048] [0048]

[0042] [0042]

[0045] [0045]

[0049] 第四步：肟化 [0049] Step Four: Oximation

[0050] Q联结化后的高级中间体5，7，9，11和盐酸羟胺在强极性溶剂中缩合可制得肟化合物12，反应溶剂优选N，N-二甲基甲酰胺，甲酰胺，二氧六环，乙醇，甲醇，乙二醇，或这些溶剂与水的适当比例混合物。 [0050] Q coupling of advanced intermediates after 5,7,9,11 and hydroxylamine hydrochloride can be prepared by condensation in a polar solvent, an oxime compound 12, the reaction solvent is preferably N, N- dimethylformamide, formamide , an appropriate proportion dioxane, ethanol, methanol, ethylene glycol, or a mixture of these solvents with water.

[0051] [0051]

[0052] 第五步：酯化 [0052] The fifth step: esterification

[0053] 上步制得的肟化合物12和酰氯R2C(O)Cl在碱促进下发生酯化反应即制得最终产物肟酯13(即通式I目标化合物），所使用的碱可以是有机碱或无机碱，优选三乙胺，吡啶， 环氧丙烷，或κ2ω3。 [0053] a step 12 obtained oxime compound and chloride R2C (O) Cl occurs at a base to promote the esterification reaction to obtain the final product i.e. oxime ester 13 (i.e., the target compound of formula I), the base used may be organic or inorganic bases, preferably triethylamine, pyridine, propylene oxide, or κ2ω3.

[0054] [0054]

[0055] 值得注意的是，这些步骤的执行次序可以根据所合成化合物的具体情况做适当调整。 [0055] It is worth noting that the implementation of the order of these steps can be adjusted according to the specific circumstances of the synthesized compounds. 例如，对于3-硝基6-乙酰基-咔唑的合成而言，由于硝基是比乙酰基更强的钝化芳环的基团，为取得较好的收率，宜先在咔唑环上进行酰基化反应，再进行硝化反应，从而得到目标产物。 For example, 3-nitro-6-acetyl - carbazole, since the nitro group is greater than the acetyl group passivation aromatic ring, to achieve better yields, the carbazole advised acylation reaction carried out on the ring, then the nitration reaction, to thereby obtain the desired product.

[0056] 作为上述通式I表示的肟酯化合物的优选实施例，可以列举出以下的化合物结 [0056] Preferably oxime ester compound represented by the above general formula I embodiments, it may include the following compounds junction

构： Structure:

[0057] [0057]

[0059] 本发明提出的新化合物可用做烯不饱和化合物或含有烯不饱和化合物的混合物的光聚合作用的光引发剂。 Light [0059] The present invention provides novel compounds are useful as ethylenically unsaturated compound or an ethylenically unsaturated compound containing photopolymerization initiator mixture. 以下是用做光引发剂的具体实例： The following are specific examples of photoinitiators used:

[0060]实施例：（1Ε，Γ Ε)-1-(9-(2-(3-((Ε)-1-(乙酰氧亚胺）乙基）_6_ 硝基_9Η_ 咔唑-9-基）乙基）-6-硝基-9Η-咔唑-3-基）乙酮-氧-乙基肟 [0060] Example: (1Ε, Γ Ε) -1- (9- (2- (3 - ((Ε) -1- (imine acetoxy) ethyl) _6_ carbazol-9-nitro _9Η_ yl) ethyl) -6-nitro -9Η- carbazol-3-yl) ethanone - oxo - ethyl oxime

[0061] [0061]

[0062] 第一步：3，9-双乙酰基咔唑和3-乙酰基咔唑的合成： [0062] The first step: 3,9-bis-acetyl-3-acetyl-carbazole and carbazole:

[0063] 取55. 2克咔唑置于1升干燥的二硫化碳中，加入88. O克无水三氯化铝，在强力机械搅拌下，将62. 2克乙酰氯分批加入。 [0063] 55.2 g carbazole take into 1 liter of dry carbon disulfide added 88. O g of anhydrous aluminum chloride, with vigorous mechanical stirring, 62.2 g of acetyl chloride was added in portions. 加毕反应体系回流6小时，倒入冰水和稀盐酸中，分离出有机相，水相再用等体积乙酸乙酯萃取2次，合并有机相，水洗2次，硫酸镁干燥，溶剂旋干，残余物在一个装填有硅胶的漏斗上用二氯甲烷洗脱得到44. 8克，54%收率的产物3， 9-双乙酰基咔唑，灰氯色固体。 After complete addition the reaction system was refluxed for 6 hours, poured into ice water and dilute hydrochloric acid, the organic phase was separated, the aqueous phase was extracted with an equal volume of ethyl acetate twice. The combined organic phase was washed twice with water, dried over magnesium sulfate, and the solvent spin dry , packed with a residue with methylene chloride afforded 44.8 g, 54% yield of product 3, 9-bis-acetyl carbazole, chloro gray solid on silica gel funnel.

[0064] 核磁共振氢谱1H MR (CDCl3, ppm单位）： [0064] H NMR 1H MR (CDCl3, ppm units):

[0065] 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)； [0065] 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);

[0066] 3-乙酰基咔唑的合成：3，9-双乙酰基咔唑在2N的稀硫酸中水解即可以快速转化为3-乙酰基咔唑，无色块状固体，熔点226-228°C。 [0066] 3-acetyl-carbazole synthesized: 3,9-bis-acetyl-carbazole in a dilute sulfuric acid hydrolysis of 2N i.e. can rapidly converted to 3-acetyl-carbazole, colorless bulk solid, mp 226-228 ° C.

[0067] 第二步：3-乙酰基-6-硝基咔唑的合成： [0067] Step: 3-acetyl-6-nitro-carbazole synthesized:

[0068] 取62. 8克3-乙酰基咔唑置于1升的乙酸中，在强力机械搅拌下，将等当量的硝酸尿素[HNO3 ·0 = C(NH2)2]缓缓加入，混合液继续搅拌，用薄层色谱法跟踪监测反应进程，约4小时反应后，反应液倾倒入大量水中，析出大量沉淀，过滤，水洗，干燥，粗产品在乙酸中重结晶得到纯品。 [0068] Take 62.8 g 3-acetyl-carbazole placed in 1 liter of acetic acid, under strong mechanical stirring, the equivalent amount of urea nitrate [HNO3 · 0 = C (NH2) 2] was slowly added, mixed was continued stirring, thin layer chromatography to track and monitor progress of the reaction, after about four hours, the reaction solution was poured into a large amount of water to precipitate a lot of precipitation, filtration, washing, drying, the crude product was recrystallized in acetic acid to give the pure product.

[0069] 1H NMR(d6-DMS0, 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)。 [0069] 1H NMR (d6-DMS0, 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).

[0070]高分辨质谱 HRMS (M+H) =C14H11N2O3,理论值255. 0770,实测值255. 0775。 [0070] High Resolution Mass Spectrometry HRMS (M + H) = C14H11N2O3, the theoretical value of 255.0770, found 255.0775.

[0071]第三步:1，1，-(9，9，_(丁烷-1，4-二基)双(6_ 硝基_9H_ 咔唑_9，3_ 二基）)二乙酮的合成： [0071] Third Step: 1,1, - (9,9, _ (butane-1,4-diyl) bis (carbazol _9,3_ _9H_ 6_ nitro-diyl)) diethyl ketone Synthesis:

[0072] 在氮气保护下，取13. 9克3-乙酰基-6-硝基咔唑置于160毫升干燥的DMF中，分批加入2. 7克氢化钠（60%矿物油分散物），搅拌反应半小时，滴加5. 8克1，4_ 二溴丁烷在15毫升干燥DMF中的溶液，混合物搅拌反应过夜。 [0072] Under nitrogen, 13.9 g take 3-acetyl-6-nitro-carbazole placed in 160 ml of dry DMF was added portionwise 2.7 g of sodium hydride (60% dispersion in mineral oil) , the reaction mixture was stirred for half an hour, a solution of 5.8 g 1,4_-dibromobutane in 15 ml of dry DMF, the reaction mixture was stirred overnight. 反应液倒入600毫升水中，用400毫升乙酸乙酯萃取3次，合并有机相，用饱和食盐水和水各洗涤1次，硫酸镁干燥，溶剂旋干，残余物在硅胶柱色谱上以乙酸乙酯/己烷为淋洗剂洗脱纯化得到7. 8克二聚化产物，51%收率。 The reaction solution was poured into 600 ml of water and extracted with 400 ml of ethyl acetate three times, the combined organic phase was washed with saturated brine and water, washed one time each, dried over magnesium sulfate, and the solvent spin dry, and the residue was chromatographed on a silica gel column with acetic acid acetate / hexane as the eluent to give 7.8 g eluting dimerization product, 51% yield.

[0073]高分辨质谱 HRMS (M+H) =C32H27N4O6,理论值563. 1931，实测值563. 1936。 [0073] High Resolution Mass Spectrometry HRMS (M + H) = C32H27N4O6, the theoretical value of 563.1931, found 563.1936.

[0074] 第四步：在氮气保护下，取7. 4克上述二聚体1，1' _ (9，9 ' - (丁烷-1，4- 二基）双(6-硝基-9H-咔唑-9，3- 二基））二乙酮置于40毫升二甲基甲酰胺中，加入2. 8克盐酸羟胺和2. 0克预先热活化的4埃分子筛，在80°C搅拌反应3小时，冷却至室温后倒入200毫升水中，用等体积乙酸乙酯萃取3次，合并有机相，用饱和食盐水和水各洗涤1次，硫酸镁干燥，溶剂旋干，残余固体直接和3. 3克乙酸酐混合于60毫升乙酸丁酯中，在90°C搅拌反应2 小时。 [0074] Fourth step: In a nitrogen atmosphere, to take the above-described dimer 7.4 g of 1,1 '_ (9,9' - (1,4-diyl) bis (6-nitro - 9H- carbazole -9,3- diyl)) placed in 40 ml of diethyl ketone dimethyl formamide, was added 2.8 g of hydroxylamine hydrochloride and 2.0 g 4 Å molecular sieves pre-heat activated, at 80 ° C The reaction was stirred for 3 hours, cooled to room temperature, poured into 200 ml of water and extracted with an equal volume of ethyl acetate three times, the combined organic phase was washed with saturated brine and water, washed one time each, dried over magnesium sulfate, and the solvent spin dry residue solid direct and 3.3 g of acetic anhydride were mixed in 60 ml butyl acetate, stirring at 90 ° C for 2 hours. 反应体系冷却至室温，用5%稀氢氧化钠水溶液调节体系至中性，同上用200毫升水稀释，乙酸乙酯萃取分离得到的粗产品在乙酸乙酯中结晶分离得到5. 5克纯化合物，62% 收率。 The reaction system was cooled to room temperature, diluted with 5% aqueous sodium hydroxide to adjust the system neutral, supra was diluted with 200 ml of water, the crude product was extracted with ethyl acetate separated crystallized from ethyl acetate to give 5.5 g of pure isolated compound 62% yield.

[0075] 1H NMR (d6_DMS0，ppm 单位）：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)。 [0075] 1H NMR (d6_DMS0, ppm units):.. 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 ).

[0076]高分辨质谱 HRMS (M+H) =C36H33N6O8,理论值677. 2360，实测值677. 2363。 [0076] High Resolution Mass Spectrometry HRMS (M + H) = C36H33N6O8, the theoretical value of 677.2360, found 677.2363.

[0077] C/H 元素分析=C36H32N6O8 ： [0077] C / H elemental analysis = C36H32N6O8:

[0078]理论值：C 63. 90%, H 4. 77% ；实测值：C 63. 94%, H 4. 85%。 [0078] Theory: C 63. 90%, H 4. 77%; Found: C 63. 94%, H 4. 85%.

[0079] 感光度和残余气味测试： [0079] sensitivity and residual smell test:

21[0080] 感光度试验样品制作：将20重量百分比（下同)甲基丙烯酸，15份甲基丙烯酸羟基乙酯，10份甲基丙烯酸甲酯，以及55份甲基丙烯酸丁酯和300份乙基溶纤剂混合，加入1 份AIBN在70摄氏度反应5小时，得到上述丙烯酸体系的共聚物。 21 [0080] Sensitivity Test Sample production: 20 percentage by weight (hereinafter the same) of methacrylic acid, 15 parts of hydroxyethyl methacrylate, 10 parts of methyl methacrylate, and 55 parts of butyl methacrylate and 300 parts of mixing ethyl cellosolve, 1 part of AIBN was added at 70 ° C the reaction for 5 hours to obtain the acrylic copolymer system. 下一步，取65份此丙烯酸系共聚物和5份二季戊四醇六丙烯酸酯和30份丙酮混合。 Next, taking this mixing 65 parts of acrylic copolymer and 5 parts of dipentaerythritol hexaacrylate and 30 parts of acetone. 在黄光保护下，向此混合物中加入2份的光引发剂，搅拌溶解，取少许此样品涂敷于铝板上，在65摄氏度缓缓烘干40分钟除去溶剂，覆盖醋酸纤维素薄膜，设置不同光密度的21灰阶标准试验底片，使用金属卤灯在60厘米处以锁定的时间曝光（40秒和80秒），其后用碳酸钠碱液显影，观测显影后因聚合固化保留的最高灰阶数判定引发体系的感光灵敏度。 Under yellow light protection, to this mixture was added 2 parts of the photoinitiator, stirred and dissolved, take a little of this sample was applied onto an aluminum plate, dried at 65 ° C 40 minutes the solvent was removed slowly, covering the cellulose acetate film, provided 21 grayscale standard test different optical density of the film, using a metal halide lamp at 60 cm impose lock the exposure time (40 seconds and 80 seconds), followed by sodium carbonate lye developed after observing the development of the highest retention due to polymerization curing ash order determination system caused photosensitivity.

[0081] 残余气味评价：将显影后的样品板置于密闭的玻璃瓶中，在100摄氏度烘箱中烘烤该玻璃瓶1分钟，7个人分别独立地评价气味级别，评估的标准以数字标示如下： [0081] Residual Odor Evaluation: The sample plate after development is placed in a sealed glass bottle, the bottle baked in an oven at 100 ° C for 1 minute, 7 independent individual odor level evaluation standards, respectively, in order to assess the numerals below :

[0082] 0级：没有气味； [0082] 0: no odor;

[0083] 1级：非常轻微的气味； [0083] 1: Very slight odor;

[0084] 2级：轻微的气味； [0084] 2: Slight odor;

[0085] 3级：明显的气味； [0085] 3: obvious odor;

[0086] 4级：强烈的气味； [0086] 4: strong odor;

[0087] 5级：非常强烈的气味。 [0087] 5: very strong smell.

[0088] 按实施例合成的5个双官能团引发剂给出的结果如下： [0088] by five pairs of functional initiators synthesized in the examples given in the results of agent as follows:

[0089] [0089]

22 Twenty two