CN112029016B - 一种脂溶性柱（杯）芳烃作为光引发剂的应用 - Google Patents
一种脂溶性柱（杯）芳烃作为光引发剂的应用 Download PDFInfo
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- 230000003000 nontoxic effect Effects 0.000 claims abstract description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
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- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- -1 heterocyclic aryl Chemical group 0.000 claims description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 5
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Abstract
本发明涉及光引发剂技术领域，提供了一种脂溶性柱（杯）芳烃作为光聚合引发剂的方法。公开的脂溶性柱（杯）芳烃结构如下图1所示，具有亚甲基桥连苯单元形成的大环结构，是一种新型的脂溶性光引发剂。在光辐射条件下，柱（杯）芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。与传统商业光引发剂相比，本发明提供的光引发剂本身安全无毒，不需要任何其他助剂，光辐照断裂后形成直链寡聚物，并在引发光聚合反应后被固定到聚合物中，无小分子碎片生成，可以极大的降低光引发剂的迁移，从而避免光聚合固化产物的毒性、气味等问题。
Description
技术领域：
本发明属于光聚合和光固化领域，具体涉及一种脂溶性柱（杯）芳烃作为光引发剂的应用。
背景技术：
光聚合在印刷油墨、涂层、牙疗、光刻、激光成像等领域发挥着重要作用，受到越来越多的关注。作为影响光聚合效率的关键因素，人们在光引发剂的研究和开发方面投入了大量的精力。目前已开发出多种I型裂解和II型夺氢自由基光聚合引发剂。其中I型光引发剂在光辐照下，裂解成两个自由基片段，引发光聚合。II型光引发剂需要供氢化合物作为助引发剂，产生自由基引发聚合反应。但I型和II型引发剂面临着如毒性、气味强、光解后有害物质的浸出等问题，限制了其进一步的应用，特别是在食品包装或生物医学方面的应用。
针对这些问题，本发明提出利用柱（杯）芳烃作为光引发剂的方法。在光辐射条件下，柱（杯）芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。与传统商业光引发剂相比，柱（杯）芳烃本身安全无毒，不需要其他助剂，在光辐照断裂后形成双自由基直链寡聚物，并在引发光聚合后被固定到聚合物中，无小分子碎片生成，可以极大的降低光引发剂的迁移，从而避免光聚合固化产物的毒性、气味等问题。另外制备成本低，容易进行工业化生产，具有很强的市场化潜力。
发明内容
本发明目的在于探索新型脂溶性柱（杯）芳烃类在光引发剂领域内应用，该引发剂具有较低的迁移率，可避免光聚合固化产物的毒性、气味等问题，在光引发剂领域有潜在的应用价值。
一种脂溶性柱（杯）芳烃类光引发剂，其特征在于具有亚甲基桥连苯单元形成的大环结构，并且具有脂溶性。具有通式I所示结构：
通式I中：R1，R2，R3可以是羟基、烷氧基、烷基、芳香基、杂环芳香基、烯基、炔基，以及含有卤素取代基、带氧取代基、带氮取代基、带硫取代基的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基。其中n=2-10。*为与芳香环的键合点。
在光辐射条件下，柱（杯）芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。柱（杯）芳烃安全无毒，迁移率低，从而避免光聚合固化产物的毒性、气味等问题。
本发明涉及的脂溶性柱（杯）芳烃按照已发表的的文献合成：
Tomoki Ogoshi, Suguru Kanai, Shuhei Fujinami, Tada-aki Yamagishi, andYoshiaki Nakamoto， para-Bridged Symmetrical Pillar[5]arenes: Their Lewis AcidCatalyzed Synthesis and Host–Guest Property. J. Am. Chem. Soc. 2008, 130,5022-5023.
Xiao-Bo Hu, Zhenxia Chen, Lei Chen, Ling Zhang, Jun-Li Hou and Zhan-Ting Li, Pillar[n]arenes (n = 8–10) with two cavities: synthesis, structuresand complexing properties. Chem. Commun., 2012, 48, 10999-11001.
附图说明：
图1为脂溶性柱（杯）芳烃的化学结构通式。
图2为两端带有乙氧基的柱[6]芳烃(P6OC2H5)作为光引发剂的示意图和不同单体的化学结构式。
图3是P6OC2H5作为光引发剂引发不同单体的光聚合动力学曲线。
图4是光引发剂TPO、1173、 P6OC2H5的迁移率。
下面结合实施例对本发明提供的方案进行详细的说明。但是不能把它们理解为对本发明保护范围的限定。
实施例1
优选的，如图2，我们选择两端带有乙氧基的柱[6]芳烃(P6OC2H5)作为引发剂，选择带有一个双键的HEA，带有两个双键的PEGDA，带有三个双键的TMPTA作为单体。称取10 mgP6OC2H5, 分别溶于1 g HEA、TPGDA、TMPTA单体中，配置质量分数为1%的引发剂-单体混合体系。然后在20 mW/cm2汞灯辐照下，用实时红外测定其光聚合动力学曲线。
实验结果如图3所示，在光辐照下，HEA、TPGDA、TMPTA三种单体的双键发生快速的转化，且最终的转化率较高。说明P6OC2H5作为光引发剂，可以高效的引发HEA、TPGDA、TMPTA三种单体的光聚合。其中TMPTA由于粘度较大，双键转化率略有下降，属于正常情况。
取10.68 mg P6OC2H5，溶于1 mL PEG200DA单体中，用汞灯辐照固化成为0.1 mm厚度薄膜。取0.1 g 薄膜浸泡在10 mL乙腈中，2 h、4 h、8 h、10 h测定乙腈溶液的紫外吸收，从而计算其迁移率。对于商用引发剂TPO和1173，采用同样的步骤测定迁移率。
实验结果如图4所示，与商用的引发剂TPO和1173相比，P6OC2H5作为光引发剂具有更低的迁移率。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (2)
1.一种脂溶性柱芳烃类光引发剂在光聚合领域的应用，其特征在于所述脂溶性柱芳烃具有亚甲基桥连苯单元形成的大环结构，并且具有脂溶性， 具有通式I所示结构：
通式I
通式I中：R1，R2，R3是羟基、烷氧基、烷基、芳香基、杂环芳香基、烯基、炔基，以及含有卤素取代基、带氧取代基、带氮取代基、带硫取代基的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基，其中n=2-10，*为与芳香环的键合点。
2.根据权利要求1所述的应用，其特征在于，在光辐照下，所述脂溶性柱芳烃类光引发剂引发单体光聚合反应，并且柱芳烃安全无毒，迁移率低，从而避免光聚合固化产物的毒性、气味问题。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0334955A (ja) * | 1989-06-30 | 1991-02-14 | Ricoh Co Ltd | カリックスアレーン誘導体 |
| CN101337865A (zh) * | 2008-08-11 | 2009-01-07 | 同济大学 | 一种制备含羟基杯[4]芳烃衍生物的方法 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0334955A (ja) * | 1989-06-30 | 1991-02-14 | Ricoh Co Ltd | カリックスアレーン誘導体 |
| CN101337865A (zh) * | 2008-08-11 | 2009-01-07 | 同济大学 | 一种制备含羟基杯[4]芳烃衍生物的方法 |
Non-Patent Citations (2)
| Title |
|---|
| para-Bridged Symmetrical Pillar[5]arenes: Their Lewis Acid Catalyzed Synthesis and Host–Guest Property;Tomoki Ogosh et al.,;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 》;20080416;第130卷(第15期);第5022–5023页 * |
| Pillar[n]arenes (n = 8–10) with two cavities: synthesis, structures and complexing properties;Xiao-Bo Hu et al.,;《CHEMICAL COMMUNICATIONS》;20120924;第48卷;第10999-11001页 * |
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