自由基型超支化大分子光引发剂的合成及表征
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摘要
UV固化是辐射固化技术的一种,是快速发展的“绿色”新技术,广泛应用于光固化涂料、光刻胶、光固化油墨、电子封装材料等领域。光引发剂在UV固化中占据十分重要的地位,是决定体系固化速度和固化程度的重要因素。大分子光引发剂具有挥发度低、抗迁移能力强、环境兼容性好、树脂相容性好、功能多样性等优点,近年来倍受关注。但是,目前许多大分子光引发剂仍会产生小分子迁移,其引发剂活性也有待提高。
超支化聚合物具有独特的球状结构,应用于涂料中具有粘度低、固化速度快和成膜性好等优点。因此,近年来国内外关于用超支化聚合物的研究异常活跃。本文将光引发剂与超支化低聚物结合起来,对超支化聚(酰-胺酯)端基进行改性,成功制备了两种光活性良好的自由基型超支化大分子光引发剂。
通过TMP和AB_2型单体DKBA进行酯化反应合成第二代超支化聚合物HBP-2,利用FT-IR、DSC对其结构及热性能进行分析,所合成的聚合物HBP-2具有溶解性好、粘度低、热稳定性好等特点。
将TDI改性后的1173通过端基改性引入到超支化聚合物HBP-2上,成功制备了裂解型超支化大分子光引发剂HBP-2-TDI-1173,利用FT-IR对其结构进行表征,通过紫外光谱和荧光光谱对其光性能进行研究。相对于小分子光引发剂1173,HBP-2-TDI-1173具有紫外光谱最大吸收红移、荧光发射略强、引发NVP光聚合转化率略低等特点。
将TDI改性后的4-BP和DMEA通过端基改性引入到超支化聚合物HBP-2上,成功制备了提氢型超支化大分子光引发剂HBP-2-TDI-DMEA-4-BP,利用FT-IR对其结构进行表征,利用紫外光谱和荧光光谱对其光性能进行研究。相对于小分子引发剂体系4-BP/DMEA,HBP-2-TDI-DMEA-4-BP具有相似的紫外吸收、荧光发射较弱、引发NVP光聚合转化率较高等特点。
UV curing as a kind of radiation curing technology is the rapid development of "green" new technology, widely used in photocurable coatings,photoresist, photocurable ink, electronic packaging materials, and other fields. Photoinitiators ccupy a very important position in the UV curing,which is the most important factor to determine the extent and speed of curing system. Polymeric photoinitiators have been the subject of increasing increast with the advantages of low vlatility,strong ability against migration,good compatibility with environment andresins and diversity in function in recent years. However, at present, many polymeric photoinitiators still result small molecular migration and the initiator activity has yet to be enhanced.
Hyperbranched polymers have been the subject of increasing increast at home and abroad in recent years with its advantages of unique spherical structure, low viscosity of coating, curing speed and good film. In this paper, hyperbranched polymer was combined with photoinitiator by modifying the hyperbranched poly(amide-ester) to synthesis two kinds of hyperbranched polymeric potoinitiators.
The second generation hyperbranched polymer HBP-2 has been synthesized by the monomer of TMP and DKBA .Using FT-IR and DSC to Characterize the HBP-2 of the structure and thermal sability .The HBP-2 has good solubility, low viscosity and good thermal stability.
Hyperbranched polymer HBP-2 was introduced to the compound of 1173 which modified by TDI to synthesis the hyperbranched polymeric photoinitiator HBP-2-TDI-1173. Chemical titration and FT-IR analyses have confirmed the structures of HBP-2-TDI-1173. HBP-2-TDI-1173 has low viscosity and good solubility . UV-vis and fluorescence spectras have been used to study their optical properties. The UV-vis spectra of the polymeric photoinitiator exhibits the maximal absorption red shift. Fluorescence emission spectra of the polymeric photoinitiator is strongger .The conversion rate of NVP photopolymerization is slightly lower.
Hyperbranched polymer HBP-2 was introduced to the compounds of 4-BP and DMEA which modified by TDI to synthesis the hyperbranched polymeric photoinitiator HBP-2-TDI-DMEA-4-BP. Chemical titration and FT-IR analyses have been used to confirm the structures of HBP-2-TDI-DMEA-4-BP. HBP-2-TDI-DMEA-4-BP has low viscosity and good solubility .UV-vis and fluorescence spectra shave been used to study their optical properties. The UV-vis spectra of the polymeric photoinitiator exhibits the same absorption. Fluorescence emission spectra of the polymeric photoinitiator is munch weaker. The conversion rate of NVP photopolymerization is slightly strogger.
超支化聚合物具有独特的球状结构,应用于涂料中具有粘度低、固化速度快和成膜性好等优点。因此,近年来国内外关于用超支化聚合物的研究异常活跃。本文将光引发剂与超支化低聚物结合起来,对超支化聚(酰-胺酯)端基进行改性,成功制备了两种光活性良好的自由基型超支化大分子光引发剂。
通过TMP和AB_2型单体DKBA进行酯化反应合成第二代超支化聚合物HBP-2,利用FT-IR、DSC对其结构及热性能进行分析,所合成的聚合物HBP-2具有溶解性好、粘度低、热稳定性好等特点。
将TDI改性后的1173通过端基改性引入到超支化聚合物HBP-2上,成功制备了裂解型超支化大分子光引发剂HBP-2-TDI-1173,利用FT-IR对其结构进行表征,通过紫外光谱和荧光光谱对其光性能进行研究。相对于小分子光引发剂1173,HBP-2-TDI-1173具有紫外光谱最大吸收红移、荧光发射略强、引发NVP光聚合转化率略低等特点。
将TDI改性后的4-BP和DMEA通过端基改性引入到超支化聚合物HBP-2上,成功制备了提氢型超支化大分子光引发剂HBP-2-TDI-DMEA-4-BP,利用FT-IR对其结构进行表征,利用紫外光谱和荧光光谱对其光性能进行研究。相对于小分子引发剂体系4-BP/DMEA,HBP-2-TDI-DMEA-4-BP具有相似的紫外吸收、荧光发射较弱、引发NVP光聚合转化率较高等特点。
UV curing as a kind of radiation curing technology is the rapid development of "green" new technology, widely used in photocurable coatings,photoresist, photocurable ink, electronic packaging materials, and other fields. Photoinitiators ccupy a very important position in the UV curing,which is the most important factor to determine the extent and speed of curing system. Polymeric photoinitiators have been the subject of increasing increast with the advantages of low vlatility,strong ability against migration,good compatibility with environment andresins and diversity in function in recent years. However, at present, many polymeric photoinitiators still result small molecular migration and the initiator activity has yet to be enhanced.
Hyperbranched polymers have been the subject of increasing increast at home and abroad in recent years with its advantages of unique spherical structure, low viscosity of coating, curing speed and good film. In this paper, hyperbranched polymer was combined with photoinitiator by modifying the hyperbranched poly(amide-ester) to synthesis two kinds of hyperbranched polymeric potoinitiators.
The second generation hyperbranched polymer HBP-2 has been synthesized by the monomer of TMP and DKBA .Using FT-IR and DSC to Characterize the HBP-2 of the structure and thermal sability .The HBP-2 has good solubility, low viscosity and good thermal stability.
Hyperbranched polymer HBP-2 was introduced to the compound of 1173 which modified by TDI to synthesis the hyperbranched polymeric photoinitiator HBP-2-TDI-1173. Chemical titration and FT-IR analyses have confirmed the structures of HBP-2-TDI-1173. HBP-2-TDI-1173 has low viscosity and good solubility . UV-vis and fluorescence spectras have been used to study their optical properties. The UV-vis spectra of the polymeric photoinitiator exhibits the maximal absorption red shift. Fluorescence emission spectra of the polymeric photoinitiator is strongger .The conversion rate of NVP photopolymerization is slightly lower.
Hyperbranched polymer HBP-2 was introduced to the compounds of 4-BP and DMEA which modified by TDI to synthesis the hyperbranched polymeric photoinitiator HBP-2-TDI-DMEA-4-BP. Chemical titration and FT-IR analyses have been used to confirm the structures of HBP-2-TDI-DMEA-4-BP. HBP-2-TDI-DMEA-4-BP has low viscosity and good solubility .UV-vis and fluorescence spectra shave been used to study their optical properties. The UV-vis spectra of the polymeric photoinitiator exhibits the same absorption. Fluorescence emission spectra of the polymeric photoinitiator is munch weaker. The conversion rate of NVP photopolymerization is slightly strogger.
引文
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[11]王生杰等.树状硅基大分子光引发剂的合成与表征[J].高分子学报,2006,(5):707-710
[12]Jun Wei,et al.A Highly Efficient Polyurethane-TypePolymeric Photoinitiator Containing In-chain Benzophenone and Coinitiator Amine forPhotopolymerization of PU Prepolymers.Macromolecular Chemistry and Physics,2006,207:2321-2328
[13]Corrales T,et al.A chemiluminescence study of micron and nanoparticle titanium dioxide:effect on the thermal stability of metallocene polyethylene[J]Photochemistry and Photobiology A:Chemistry,2003,156(1):151-160
[14]梁驻军等.大分子光引发剂研究进展[J].精细与专用化学品,2003,(19):15
[15]黄亮等.大分子光引发剂的研究进展[J].功能高分子学报,2004,17(2):325
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