CN114907502B - 一种可见光引发剂体系及其应用 - Google Patents
一种可见光引发剂体系及其应用 Download PDFInfo
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- CN114907502B CN114907502B CN202210539780.1A CN202210539780A CN114907502B CN 114907502 B CN114907502 B CN 114907502B CN 202210539780 A CN202210539780 A CN 202210539780A CN 114907502 B CN114907502 B CN 114907502B
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- visible light
- initiator system
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- light initiator
- photosensitizer
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Classifications
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- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
本发明公开一种可见光引发剂体系及其应用。该可见光引发剂体系包括光敏剂和助引发剂;所述助引发剂为氨基酸类化合物;其中,所述光敏剂和助引发剂的质量比为1:0.5‑20。该可见光引发剂体系可迅速产生自由基,高效引发单体/低聚物发生聚合/交联,并且展现较好的光漂白特性,有助于深层光固化,有效解决了传统紫外光固化技术固化深度浅、存在安全隐患的问题。此外,该可见光引发剂体系还具有良好的生物安全性,有效克服光引发剂生物毒性大的缺点,因此,在3D打印、生物支架和水凝胶敷料制备等领域具有广阔的应用前景。
Description
技术领域
本发明涉及光功能材料领域。更具体地,涉及一种可见光引发剂体系及其应用。
背景技术
光固化技术,又称光聚合技术,是利用光或电子束为能量,引发流动态材料快速聚合或交联成固态材料的技术,具有绿色、高效、节能、环保等特点。传统的紫外光固化技术已经在涂料、胶黏剂、印刷电路板和3D打印等领域得到广泛的应用,然而该技术也存在一定的固有缺陷,比如产生大量臭氧以及固化深度浅等。此外,紫外光的光子能量较高,会对生物活性组分(细胞、酶以及蛋白质等)具有潜在的损害作用,存在一定生物安全隐患,这也限制了光固化技术在一些新兴领域(例如生物3D打印和生物医学等)的应用。
在光固化反应中,光源的选择是由光引发剂的吸收光谱决定的,光引发剂的吸光效率和活性物种量子产率决定着光固化反应的速率和效率。因此,开发性能优异的可见光引发剂,发展可见光固化能有效解决传统紫外光固化技术存在的问题,拓展光固化技术的应用范围。由于阳离子聚合光引发剂的种类和适用范围远小于自由基聚合光引发剂,在这里仅讨论自由基光引发剂。根据产生自由基的机理不同,光引发剂主要分为裂解型(Type I型)和夺氢型(Type II型)两种类型。由于单个可见光光子所具有的能量通常不能满足光引发剂分子断键所需的能量,常见的可见光引发剂大多是由光敏剂和助引发剂组成的TypeII型光引发剂,如光敏剂/三级胺(CN03105102.2)、光敏剂/六芳基双咪唑(CN107573443)和光敏剂/碘鎓盐、硫鎓盐类化合物(CN107936146A)等。目前,具有较高生物安全性的光敏剂主要有樟脑醌、核黄素和呫吨类化合物等,他们的吸收光谱基本可以覆盖整个可见光区。然而,可供选择的助引发剂大多生物安全性较差,有的还存在着刺激性气味,具有一定毒性。因此,开发与上述光敏剂相匹配且具有较高生物安全性的助引发剂也成为发展可见光引发剂的关键。
发明内容
为解决上述问题,本发明的第一个目的在于提供一种可见光引发剂体系,由光敏剂和助引发剂组成。该可见光引发剂体系的光敏剂和助引发剂选用生物安全性较高的原料,并且可高效利用可见光光源,引发单体/低聚物发生聚合/交联。此外,该可见光引发剂体系还具有较好的光漂白特性,有助于深层光固化。
本发明的第二个目的在于提供一种如上所述的可见光引发剂体系在光固化技术领域中的应用。
本发明的第三个目的在于提供一种包含上述可见光引发剂体系的光固化材料。
本发明的第四个目的在于提供一种制备如上光固化材料的方法。
为达到上述第一个目的,本发明采用下述技术方案:
本发明公开一种可见光引发剂体系,包括光敏剂和助引发剂;所述助引发剂为氨基酸类化合物;
其中,所述光敏剂和助引发剂的质量比为1:0.5-20;示例性地,所述光敏剂和助引发剂的质量比可以为1:0.5、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:16、1:17、1:18、1:19、1:20等等。
本发明中的可见光引发剂体系,在可见光照射下,光敏剂吸收光子能量后发生电子跃迁至激发单线态,然后经系间窜跃至激发三线态。处于激发三线态的光敏剂分子具有较高的反应活性,能与氨基酸类助引发剂发生能量传递、电子转移或质子转移产生自由基,引发单体/低聚物发生聚合/交联,解决了现有技术中光引发剂需要采用紫外光带来的安全问题。此外,选用的光敏剂和助引发剂均为生物安全性较高的化合物,避免生物安全性问题的同时,还赋予了其较好的光漂白特性,有助于深层光固化,有效克服了传统紫外光固化技术固化深度浅的问题。
进一步,所述助引发剂选用的是生物安全性较高、水溶性较好的氨基酸类化合物,包括但不限于N-苯基甘氨酸、L-精氨酸、蛋氨酸、半胱氨酸、脯氨酸或组氨酸中的一种或多种。
进一步,所述光敏剂选用的为本领域常见的生物安全性较高的光敏染料,包括但不限于樟脑醌、核黄素、曙红Y、伊红Y、孟加拉玫瑰红、赤藓红B或姜黄素中的一种或多种。
在一个具体实施方式中,所述可见光引发剂体系中,当光敏剂为伊红Y,助引发剂为L-精氨酸,或者,光敏剂为曙红Y,助引发剂为N-苯基甘氨酸进行组合时,光引发效率提高明显。
为达到上述第二个目的,本发明公开该可见光引发剂体系可应用于包括3D打印、生物支架和水凝胶敷料制备在内的光固化技术领域。该可见光引发剂体系具有优异的引发活性和生物安全性,具有良好的应用前景。
为达到上述第三个目的,本发明采用下述技术方案:
本发明公开一种包含有如上所述可见光引发剂体系的光固化材料,按重量份数计,包括以下组分:
低聚物0-80份;
单体5-90份;
可见光引发剂体系0.1-10份;
溶剂5-90份。
进一步,所述可见光引发剂体系的重量份为0.2-5份。
进一步,所述低聚物包括但不限于环氧丙烯酸酯、聚醚丙烯酸酯、聚酯丙烯酸酯或聚氨酯丙烯酸酯中的一种或多种。
进一步,所述单体包括但不限于丙烯酸酯类单体、丙烯酰胺类单体、乙烯基醚类单体、N-乙烯基吡咯烷酮或丙烯酸中的一种或多种;优选地,所述单体包括但不限于乙烯基/(甲基)丙烯酰基改性的合成高分子材料(聚乙烯醇、聚乳酸、聚己内酯、聚乙二醇等)和天然高分子材料(明胶、壳聚糖、硫酸软骨素、海藻酸钠、淀粉、纤维素、木质素、蚕丝蛋白、透明质酸)等。
进一步,所述溶剂选自去离子水、磷酸盐缓冲溶液(PBS)、细胞培养基、乙醇、乙酸乙酯等。
所述光固化材料还可以包括0-20份的其他助剂,所述其他助剂包括颜料、填料、消泡剂、抗氧化剂、或者他们的任意比例混合物。
为达到上述第四个目的,本发明采用下述技术方案:
本发明公开一种制备如上所述的光固化材料的制备方法,包括如下步骤:
将光固化材料的各原料混合均匀后,置于辐照光源下进行光固化成型。
进一步,所述辐照光源为激光器或LED;优选地,所述辐照光源的波长为385-750nm,光照强度为0.5-1000mW/cm2,光照时间为0.5-10min。
本发明的有益效果如下:
本发明公开一种可见光引发剂体系及其应用。在本发明中选用了生物安全性较高的光敏剂和氨基酸类助引发剂,可有效解决TypeⅡ型光引发剂体系生物安全性差以及具有刺激性气味和毒性的问题,符合当今绿色化学的发展理念。并且该可见光引发剂体系中光敏剂分子具有较高的反应活性,能与氨基酸类助引发剂发生能量传递、电子转移或质子转移产生自由基,引发单体/低聚物发生聚合/交联。此外,该可见光引发剂体系具有较好的光漂白特性,有助于深层光固化,有效克服了传统紫外光固化技术固化深度浅的问题。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出实施例1中的顺磁共振谱图。
图2示出实施例2-4中树脂的双键转化率(DBC)随光照时间的变化曲线。
图3示出实施例5-7中树脂的双键转化率(DBC)随光照时间的变化曲线。
图4示出实施例8中树脂在532nm激光器照射不同时间的实物图。
图5示出实施例9中树脂在532nm激光器照射不同时间以及固化后样品的实物图;
其中,a为照射1min的效果图,b为照射5min的效果图,c为固化后的实物图。
图6示出实施例10中的光固化材料采用DLP 3D打印的实物图。
图7示出实施例11中可见光引发剂在制备可注射式原位固化小鼠皮肤创面敷料中的应用。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
采用0.01份的核黄素和0.01份的N-苯基甘氨酸组成的可见光引发剂体系,加入100份的去离子水中制备光引发剂溶液,并取100μL置于顺磁测试毛细管中,然后加入20μL5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)的水溶液(0.2molL-1)并混合均匀,通N2半小时充分除气并密封。测试时,激发光源为450nmLED(50mWcm-2),光照时间约5min,其顺磁共振谱图如图1所示。从图中可以看出,在可见光照射下,该引发剂体系能迅速产生活性自由基。
实施例2
采用0.02份的伊红Y和0.2份的组氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.78份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,监测碳碳双键吸收峰的变化情况,设置辐照光源(525nm LED)的光强约50mW cm-2,树脂的光聚合动力学曲线如图2所示。
实施例3
采用0.02份的伊红Y和0.2份的甘氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.78份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,监测碳碳双键吸收峰的变化情况,设置辐照光源(525nm LED)的光强约50mW cm-2,树脂的光聚合动力学曲线如图2所示。
实施例4
采用0.02份的伊红Y和0.2份的L-精氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.78份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,监测碳碳双键吸收峰的变化情况,设置辐照光源(525nm LED)的光强约50mW cm-2,树脂的光聚合动力学曲线如图2所示。
对比实施例2-4的光聚合动力学曲线,可以看出,各树脂的DBC都随光照时间的增长而增加,其中伊红Y/L-精氨酸的引发效率明显优于伊红Y/组氨酸和伊红Y/甘氨酸的组合。
实施例5
采用0.01份的曙红Y和0.1份的L-精氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.89份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,辐照光源为白光LED(100mW/cm2),树脂的光聚合动力学曲线如图3所示。
实施例6
采用0.01份的曙红Y和0.1份的甘氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.89份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,辐照光源为白光LED(100mW/cm2),树脂的光聚合动力学曲线如图3所示。
实施例7
采用0.01份的曙红Y和0.1份的N-苯基甘氨酸组成的可见光引发剂体系,加入5份的去离子水中充分溶解,然后将上述光引发剂溶液加入94.89份的聚乙二醇二丙烯酸酯(PEGDA 400)中混合均匀,将上述树脂注入含硅胶片(厚0.3mm)的玻璃模具中并进行实时红外测试,辐照光源为白光LED(100mW/cm2),树脂的光聚合动力学曲线如图3所示。
对比实施例5-7的光聚合动力学曲线,可以看出,曙红Y/N-苯基甘氨酸的光引发效率明显优于曙红Y/L-精氨酸和曙红Y/甘氨酸的组合。
实施例8
采用0.01份的曙红Y和0.2份的组氨酸组成的可见光引发剂体系,加入10份的去离子水中充分溶解,然后将上述光引发剂溶液加入89.79份的聚乙二醇二丙烯酸酯(PEGDA400)中混合均匀,并将其注入聚四氟乙烯模具。利用532nm半导体激光器(10mW/cm2)对其进行光固化处理,光照不同时间后的树脂如图4所示。从图中可以看出,在光照区域,树脂发生了明显的光漂白现象,并且随着光照时间的增加,光漂白区域的面积显著增大。
实施例9
采用0.01份的曙红Y和0.1份的N-苯基甘氨酸组成的可见光引发剂体系,加入10份的去离子水中充分溶解,然后将上述光引发剂溶液加入89.89份的聚乙二醇二丙烯酸酯(PEGDA 400)中混合均匀并将其注入血清瓶(20mL)。利用532nm半导体激光器(10mW/cm2)对其进行光固化处理,光照不同时间后的树脂如图5所示。从图中可以看出,随着光照时间的增长,树脂光漂白的程度、激光在树脂中的渗透深度以及固化后聚合物的体积都增大。
实施例10
可见光引发剂用于商用丙烯酸酯的3D打印:
采用0.01份的曙红Y、0.2份的N-苯基甘氨酸组成的可见光引发剂体系,加入5份的乙醇中充分溶解,然后将上述光引发剂溶液加入94.79份的1,6-己二醇二丙烯酸酯(HDDA)和聚乙二醇二丙烯酸酯(PEGDA 400)的混合溶液(质量比1:1)中,避光条件下搅拌使乙醇挥发。将上述光固化材料置于DLP 3D打印机的液槽中,设置打印机光源(405nmLED)功率密度约60mW/cm2,每层曝光时间1min,打印出的3D结构如图6所示。
实施例11
可见光引发剂用于制备可注射式原位固化小鼠皮肤创面敷料:
采用0.02份的曙红Y、0.2份的N-苯基甘氨酸组成的可见光引发剂体系,加入89.78份的PBS充分溶解。然后将10份的生物大分子单体甲基丙烯酰化明胶(Gel-MA,取代度为90%)加入上述光引发剂溶液,并置于40℃的水浴中使其溶解,取1mL注入小鼠背部全层皮肤缺损创面(6-8周龄,雌性,c57小鼠,直径约1厘米),在白光LED(100mW/cm2,3.0min)照射下完成光固化。实验结果显示,水凝胶敷料具有良好的创面贴附性和保湿效果,小鼠创面覆盖敷料后的实物图如图7所示。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (8)
1.一种可见光引发剂体系,其特征在于,所述可见光引发剂体系由光敏剂和助引发剂组成;
所述可见光引发剂体系使用的辐照光源为白光LED;
其中,所述可见光引发剂体系中,光敏剂为曙红Y,助引发剂为N-苯基甘氨酸;所述光敏剂和助引发剂的质量比为1:0.5-20。
2.一种如权利要求1所述可见光引发剂体系的应用,其特征在于,应用于包括3D打印、生物支架和水凝胶敷料制备在内的光固化技术领域。
3.一种包含有如权利要求1所述可见光引发剂体系的光固化材料,其特征在于,按重量份数计,包括以下组分:
低聚物0-80份;
单体5-90份;
可见光引发剂体系0.1-10份;
溶剂5-90份。
4.根据权利要求3所述的光固化材料,其特征在于,所述可见光引发剂体系的重量份为0.2-5份。
5.根据权利要求3所述的光固化材料,其特征在于,所述低聚物包括环氧丙烯酸酯、聚醚丙烯酸酯、聚酯丙烯酸酯或聚氨酯丙烯酸酯中的一种或多种。
6.根据权利要求3所述的光固化材料,其特征在于,所述单体包括丙烯酸酯类单体、丙烯酰胺类单体、乙烯基醚类单体、N-乙烯基吡咯烷酮或丙烯酸中的一种或多种。
7.一种如权利要求3-6任一所述的光固化材料的制备方法,其特征在于,包括如下步骤:
将光固化材料的各原料混合均匀后,置于辐照光源下进行光固化成型;
所述辐照光源为白光LED。
8.根据权利要求7所述的制备方法,其特征在于,所述辐照光源的波长为385-750 nm,光照强度为0.5-1000 mW/cm2,光照时间为0.5-10 min。
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