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纸质出版日期:2009-4-20,
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宋家乐, 陈立新, 王亚洲, 王汝敏. 超支化烯丙基聚硅氮烷-巯基化合物体系紫外光固化研究[J]. 高分子学报, 2009,(4):338-344.
SONG Jiale, CHEN Lixin, WANG Yazhou, WANG Rumin. UV-CURING OF HYPERBRANCHED POLYSILAZANES-THIOL COMPOUND SYSTEM[J]. Acta Polymerica Sinica, 2009,(4):338-344.
宋家乐, 陈立新, 王亚洲, 王汝敏. 超支化烯丙基聚硅氮烷-巯基化合物体系紫外光固化研究[J]. 高分子学报, 2009,(4):338-344. DOI: 10.3724/SP.J.1105.2009.00338.
SONG Jiale, CHEN Lixin, WANG Yazhou, WANG Rumin. UV-CURING OF HYPERBRANCHED POLYSILAZANES-THIOL COMPOUND SYSTEM[J]. Acta Polymerica Sinica, 2009,(4):338-344. DOI: 10.3724/SP.J.1105.2009.00338.
采用等温差示光量热扫描技术(DPC)研究了超支化烯丙基聚硅氮烷-巯基化合物体系的紫外光固化.对比了超支化聚合物-巯基化合物体系、二官能烯丙基硅氮烷-巯基化合物体系和超支化自聚体系的紫外光固化特性
结果表明超支化-巯基化合物体系可在引发剂浓度低(0.1 wt%)、辐照强度低(5 mW/cm2)的情况下迅速发生光固化反应; 与超支化自聚反应相比固化速率高、双键转化率高; 而与低官能-巯基化合物体系相比
由于超支化分子结构的独特性
导致固化速率快
双键转化率偏低. 对引发剂浓度、辐照强度和反应温度对固化行为的影响表明
在引发剂浓度不超过0.5 wt%和辐照强度不大于30.50 mW/cm2时
反应速率分别与引发剂浓度和辐照强度的1/2次方成线性关系. 运用带扩散因子的自催化固化动力学模型研究了不同温度下的固化行为
计算出特定条件下的光固化动力学参数
表观总反应级数约为8.76
表观活化能为13.97 kJ/mol.
A hyperbranched polysilazanes(HBP) with multifunctionality of allyl end groups was prepared by polymerization reaction via hydrosilylation of AB2 type monomer(N-diallyamine) dimethlsilane
which was synthesized by aminolysis of Me2HSiCl.The molecular structure of HBP was characterized and determined by FT-IR
1H-NMR spectra analysis and GPC.Further more
the photo-initiated curing kinetics of HBP with thiol compound was studied by differential photoscanning calorimetry (DPC) technology.The comparing analysis among HBP
HBP-thiol compound and low-functionality monomer of B2M -thiol compound indicated that thiol functional group reacts with allyl functional group quickly under lower amount of photoinitiator (0.1 wt%) and lower light intensity (about 5 mW/cm2) in ambient condition.The curing rate and ultimate conversion of allyl group in HBP-thiol compound is higher than that in HBP
however
the ultimate conversion of allyl group in HBP-thiol compound is lower than that in B2M- thiol compound due to the unique hyperbranched structure and high multifunctionality.The effects of photoinitiator concentration [A]
UV light intensity (I0) and reaction temperature on the UV curing rate and the final allyl bond conversion of HBP-thiol compound system were also investigated by DPC.The results indicate that the effects of photoinitiator concentration ([A])
UV light intensity (I0) and temperature on kinetics of HBP-thiol compound reveal that the curing rate (Rp) is directly proportion to square root of [A] and I0
respectively
which is found to fit with theoretical predictions very well at [A] no more than 050 wt% and I0 lower than 19.40 mW/cm2 Kinetics parameters were determined for HBP-thiol compound according to an autocatalytic model with a diffusion coefficient attached.The total apparent reaction exponent and apparent activation energy are 8.76 and 13.49 kJ/mol
respectively.
超支化聚硅氮烷巯基化合物烯丙基紫外光固化动力学
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