CN113372259A - 可溶性手性非对映异构体肟酯化合物及其混合物 - Google Patents
可溶性手性非对映异构体肟酯化合物及其混合物 Download PDFInfo
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Classifications
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- G—PHYSICS
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- 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
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- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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Abstract
本发明涉及光固化功能新材料化学品领域,首次披露了一类手性非对映异构体性(diastereomers)肟酯化合物及其混合物,通过在其分子结构中引入多重手性中心(chiral centers)干扰其分子间识别作用,从而有效抑制其芳环母核之间的π‑π堆积(π‑πstacking)结晶效应,解决了其应用溶解度瓶颈难题。所述化合物是重要的含烯键(C=C)不饱和型可辐射聚合体系光敏引发剂。
Description
【技术领域】
本发明涉及光固化功能新材料化学品领域,首次披露了一类手性非对映异构体性(diastereomers)肟酯化合物及其混合物,通过在其分子结构中引入多重手性中心(chiralcenters)干扰其分子间识别作用,从而有效抑制其芳环母核之间的π-π堆积(π-πstacking)结晶效应,解决了其应用溶解度瓶颈难题。所述化合物是重要的含烯键(C=C)不饱和型可辐射聚合体系光敏引发剂。
【背景技术】
某些肟酯(oxime ester)类结构的化合物是已知的含烯键不饱和型可辐射聚合体系高效光敏引发剂。其光吸收特性宽泛,从紫外短波一直延续到350-420纳米的长波波段,使得其在传统以高压汞灯为代表的紫外光源,以及以节能环保型发光二极管(LED)光源,的辐照下均展现优良的光聚合引发能力,在光固化PCB油墨,特种涂料,印刷包装油墨,胶粘剂,复合材料,光导纤维,以及TFT-LCD液晶显示等领域均拥有广泛的应用。商业化产品例如巴斯夫公司的Irgacure OXE-01和OXE-02。代表性的文献披露例如CN101014569,WO2009147033,CN101528694,CN102250115,WO2008078678等。
随着光刻技术的深入发展,对于肟酯产品的性能要求越来越高,突出地体现在溶解度和i/g/h线波长感光灵敏度两个关键指标上。由于平板显示制程等相关工业应用场合通常只固定使用拥有特定技术参数的溶剂体系,特征的例如丙二醇甲醚醋酸酯(PGMEA)或环己酮,为了确保油墨配方产品的低温贮存稳定性,这转而要求肟酯光引发剂化合物必须针对这样的固定溶剂体系展现优异的溶解性能(通常的标准是室温下溶解度必须达到重量百分比8%或以上)。
以咔唑芳杂环为骨架的肟酯化合物拥有突出的i/g/h线感光灵敏度,在应用测试中一个突出的瓶颈问题是,该类化合物在丙二醇甲醚醋酸酯或环己酮体系中难以溶解,或者,在初期加热和/或剪切式搅拌促进溶解后,在后续低温贮存过程(3-6个月)中又逐渐出现沉淀析出质量事故现象。从分子结构分析,咔唑芳杂环是典型的平面的π-电子大共轭(conjugation)体系,其分子间极易发生所谓π-π堆积(π-π stacking)结晶效应,从而诱发单体分子在低温贮存过程中发生分子间的逐渐相互识别继而堆积析出沉淀。
从分子设计理念上,如果能有效地通过结构调控,系统性地“掺杂”干扰和抑制咔唑基肟酯芳杂环大π共轭体系之间的分子识别和π-π堆积结晶效应,则有可能突破性解决上述难题。
【发明内容】
本项申请现已首次意外地发现,一类通式(I)描述的手性非对映异构体性(diastereomers)肟酯化合物,通过在分子结构中特定区域位置引入两个或两个以上的多重手性中心(chiral centers)形成非对映异构体性立体异构体混合物,手性中心的引入干扰了其分子间手性识别(chiral recognition)作用,从而有效抑制其芳环母核之间的π-π堆积(π-π stacking)效应和晶体生长,出乎意料地解决了其溶解度长期瓶颈问题。所示(I)化合物展示了高超的(22%以上)的PGMEA或环己酮溶解度,以及优异的i/g/h线波长曝光感光灵敏度。
其中X是羰基(C=O)或SO2基;
R1是1-24个碳原子(记为C1-C24,下同)的含有0-12个非氢取代基的直链或支链的烷基,或R1是含有0-6个非氢取代基的C6-C24芳基;优选的R1是CH3,Ph,CH3CH2,CF3,CF3CF2,C4F9,C8F17;非氢取代基是指氢原子以外的原子或基团,包括但不限于氧原子,氮原子,硫原子,硅原子,卤素原子,烷基,芳基,杂芳基;
R2和R3分别独立的是含有0-12个非氢取代基的直链或支链的C3-C24烷基,或R2和R3分别独立的是含有0-6个非氢取代基的C6-C24芳基;约束条件是,R2和R3分别独立的各自含有至少一个手性中心,即通式(I)化合物在R2和R3侧链结构区域至少含有2个或2个以上的不同的手性中心;优选的,上述两个独立的手性中心各自距离咔唑芳环母核在2-10个化学键距离,更优选的是2-6个化学键距离;
R4是NO2,CN,或C(O)R5基;这里R5是含有0-6个非氢取代基的C6-C24(杂)芳基。
当X是C=O基时,通式(I)化合物的示例性而非限定性结构是如下结构:
当X是SO2基时,通式(I)化合物的示例性而非限定性结构是如下结构:
作为示例性对比,我们分别制备了化合物1的非手性但全碳等价类似物1A,只含有R2侧链手性而R3为非手性全碳等价类似物1B,只含有R3侧链手性而R2为非手性全碳的支链等价类似物1C,只含有R3侧链手性而R2为非手性全碳的直链等价类似物1D。与1相比,碳数等同的结构类似物1A-1D由于缺乏非对映异构体对分子间手性识别的有效干扰性抑制,从而倾向于发生分子芳环母核之间的π-π堆积(π-π stacking)效应,进而导致晶格不断生长,溶解性急剧下降和最终析出沉淀。
下面结合具体实施例进一步说明本发明要旨。
【具体实施方式】
实施例:
第一步:冰水浴下,取咔唑500克置于2L干燥的DMF中,然后分批加入氢氧化钠240克,之后缓慢滴加溴代异辛烷900克。待滴加完毕后,在0℃下继续搅拌2小时,之后缓慢升温至80℃继续搅拌过夜(TLC跟踪)。反应完毕后,之后降温至0℃,在搅拌下将1L的水和0.5L的乙酸乙酯缓慢加入,室温下静置,分出水层,有机层用饱和氯化钠溶液洗涤3次(每次0.5L),收集母液,旋蒸浓缩收集粗产品。
第二步:冰水浴下,取56克上述化合物溶于200mL的二氯乙烷中,然后缓慢滴加31mL的68%硝酸,滴加完毕后,继续搅拌30分钟(TLC跟踪)。反应完毕后,将100mL的水缓慢倒入反应液中,用半体积二氯乙烷萃取3次,收集母液,旋转蒸发浓缩即得到粗产品,之后将其稀释到100mL的正己烷中,硅胶过滤,最终旋转蒸发得到黄色液体约58克目标化合物。
第三步:冰水浴下,取43克异壬酰氯溶于100mL的二氯乙烷中,然后缓慢加入32克无水AlCl3并继续搅拌30分钟;在另一反应器中,取65克上述化合物溶于300mL干燥的二氯乙烷中,然后将上述酰氯反应液缓慢滴加到其中,并继续搅拌2-3小时(TLC跟踪)。反应完毕后,将反应液缓慢倒入500mL的冰水浴中,二氯乙烷萃取3次,收集母液,然后用饱和碳酸氢钠溶液调制到pH值为6-7,萃取并收集母液,旋转蒸发浓缩得到粗产品,用500mL的正己烷洗涤并抽滤得到黄色固体粉末约84克目标化合物。
第四步:室温下,取465克上述化合物,98克盐酸羟胺和123克乙酸钠置于1200克乙醇和300克水的混合液中,然后在回流下搅拌约24小时(TLC跟踪)。待反应结束后,冷却至室温,加入200mL的水,过滤,得到黄色滤饼,将滤饼放入1.5L的乙醇中进行打浆,抽滤成滤饼,干燥成黄色固体粉末。
第五步:冰水浴下,取47.9克上述化合物置于200mL干燥的DCE中,缓慢滴加14.2mL乙酸酐,待滴加完毕后,继续搅拌2-3小时(TLC跟踪)。反应完毕后,搅拌下加入200mL的去离子水,静置,乙酸乙酯萃取3次,收集母液,旋转蒸发浓缩至液体不滴为止,再加入500mL的无水乙醇,搅拌3小时并析出黄色固体,抽滤,干燥即产品化合物1,收率约84%。
核磁共振波谱数据表征如下:1H-NMR 400MHz(CDCl3):δ=9.12(s),8.47(s),8.41(d),7.94(d),7.58(d),7.43(d),4.28(dd),2.12(br),1.59(s),1.58-1.25(m),1.26(s),0.95(t),0.87(t);13C-NMR 100MHz(CDCl3):δ=144.3,141.3,140.7,134.3,126.9,123.5,122.6,121.7,119.4,117.3,110.3,108.6,48.0,39.4,31.8,30.9,29.6,28.7,24.4,22.9,22.6,14.0,13.9,10.8ppm。
对比实施例(溶解度测试):遵循上述实施例的试验步骤,使用相应的不同的卤代烷和酰氯,依次制备得到目标化合物1A,1B,1C,1D,以及2,3,均为黄色固体粉末。在室温下,以PGMEA为标准溶剂,测定得到化合物的溶解度数据如下:化合物1:大于等于22%;化合物1A:2.6%以下;化合物1B:3.2%以下;化合物1C:3.0%以下;化合物1D:2.8%以下;化合物2:约16.3%;化合物3:约18.0%。这些数据证实,含有2个不同手性中心的非对映异构体混合物1/2/3均取得了优异的溶解性。
对比实施例(贮存稳定性测试):以深圳华星光电技术有限公司提供的彩色滤光片(CF)制程之黑色矩阵(BM)油墨体系为标准配方(PGMEA为稀释性溶剂,不含光引发剂),将上述1A,1B,1C,1D,以及2,3分别作为光引发剂以1%的添加量在高速搅拌下加入,复配油墨在4℃左右贮存105天,用显微镜涂片观察,含有1A,1B,1C,和1D的油墨均发生颗粒析出,而含有1,2,3的油墨均没有析出,展示了优异的贮存稳定性。
需要强调的是,上述实施例仅仅为示例性而非限定性说明,基于本项申请披露,任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨,本专利的保护范围应以相关的权利书记载条目为准。
Claims (3)
1.通式(I)描述的手性非对映异构型肟酯化合物:
其中X是羰基(C=O)或SO2基;R1是1-24个碳原子(记为C1-C24,下同)的含有0-12个非氢取代基的直链或支链的烷基,或R1是含有0-6个非氢取代基的C6-C24芳基;非氢取代基是指氢原子以外的原子或基团,包括但不限于氧原子,氮原子,硫原子,硅原子,卤素原子,烷基,芳基,杂芳基;R2和R3分别独立的是含有0-12个非氢取代基的直链或支链的C3-C24烷基,或R2和R3分别独立的是含有0-6个非氢取代基的C6-C24芳基;约束条件是,R2和R3分别独立的各自含有至少一个手性中心,即通式(I)化合物在R2和R3侧链结构区域至少含有2个或2个以上的不同的手性中心;R4是NO2,CN,或C(O)R5基;这里R5是含有0-6个非氢取代基的C6-C24(杂)芳基。
2.根据权利要求1,优选的R1是CH3,Ph,CH3CH2,CF3,CF3CF2,C4F9,C8F17;优选的,R2和R3侧链结构区域的两个或以上的独立的手性中心各自距离咔唑芳环母核在2-10个化学键距离,更优选的是2-6个化学键距离。
3.权利要求1所述化合物在含烯键(C=C)不饱和型可辐射聚合体系作为光敏引发剂(photo-initiator)和/或光产酸剂(photo-acid)的应用。
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