高官能度聚氨酯丙烯酸酯的设计制备及光固化性能
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摘要
为了提高树脂的光固化活性,以不同官能度的苯酐聚酯多元醇(PAPP)为核,异佛尔酮二异氰酸酯(IPDI)和季戊四醇三丙烯酸酯(PET3A)为支设计制备了一系列高官能度聚氨酯丙烯酸酯。将其与活性稀释剂、光引发剂复配,通过紫外光(UV)固化,得到树脂浇铸体。用红外光谱、UV固化机、万能材料试验机、动态力学热分析仪及同步热分析等对光固化树脂及其浇铸体的结构、活性、力学及热学性能等进行测试分析。结果表明,合成了预期结构的聚氨酯丙烯酸酯,当其碳碳双键官能度从6增加到12时,树脂湿膜(100μm)光固化时间从21 s下降至18 s;树脂浇铸体弯曲与拉伸性能呈上升趋势,冲击韧性则有所降低; Tg从135℃上升到147℃,耐热性能变好。
To improve the photosensitivity of the resin,a series of multifunctional polyurethane acrylate(PUA) were synthesized by using phthalic anhydride based polyester polyol(PAPP) as core and isophorone diisocyanate(IPDI),pentaerythritol triarylate(PET3 A) as branch. The preparation of the UV-cured PUA resin casting was divided into two steps. The first step was mixing active diluent,photoinitiator and the resin in a specific proportion,and the second step was UV illumination. The molecular structures of resultant PUA,the photosensitivity of the PUA resins,the mechanical properties and thermal properties of the UV-cured resin castings were investigated by FT-IR,UV solidifying machine,universal material testing machine,dynamic thermomechanical analysis(DMA) and simultaneous thermal analysis(STA). The results show that,the structure of PUA is identified,and with increase of the functionality from 6 to 12,the curing time of wet film(100 μm) decreases from 21 s to 18 s,which indicates the photosensitivity of the resin gets larger,and the bending properties,tensile properties of the UV-cured PUA become better,while the impact strength decreases,and thermal stability gets better,where Tgincreases from 135 ℃ to 147 ℃.
To improve the photosensitivity of the resin,a series of multifunctional polyurethane acrylate(PUA) were synthesized by using phthalic anhydride based polyester polyol(PAPP) as core and isophorone diisocyanate(IPDI),pentaerythritol triarylate(PET3 A) as branch. The preparation of the UV-cured PUA resin casting was divided into two steps. The first step was mixing active diluent,photoinitiator and the resin in a specific proportion,and the second step was UV illumination. The molecular structures of resultant PUA,the photosensitivity of the PUA resins,the mechanical properties and thermal properties of the UV-cured resin castings were investigated by FT-IR,UV solidifying machine,universal material testing machine,dynamic thermomechanical analysis(DMA) and simultaneous thermal analysis(STA). The results show that,the structure of PUA is identified,and with increase of the functionality from 6 to 12,the curing time of wet film(100 μm) decreases from 21 s to 18 s,which indicates the photosensitivity of the resin gets larger,and the bending properties,tensile properties of the UV-cured PUA become better,while the impact strength decreases,and thermal stability gets better,where Tgincreases from 135 ℃ to 147 ℃.
引文
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[3] Pitchaimari G,Vijayakumar C T. Studies on thermal degradation kinetics of thermal and UV cured N-(4-hydroxy phenyl)maleimide derivatives[J]. Thermochim. Acta,2014,575:70-80.
[4] Chattopadhyay D K,Panda S S,Raju K V S N. Thermal and mechanical properties of epoxy acrylate-methacrylates UV cured coatings[J]. Prog. Org. Coat.,2005,54:10-19.
[5]徐朝华,陈婵,孙宁,等.双键可控紫外光固化超支化聚氨酯丙烯酸酯的制备与表征[J].高等学校化学学报,2016,37(6):1224-1228.Xu Z H,Chen C,Sun N,et al. Preparation and characterization of UV curable hyperbranched polyurethane acrylate with adjustable double bond[J]. Chemical Journal of Chinese Universities,2016,37(6):1224-1228.
[6] Lu J H,Youngblood J P. Adhesive bonding of carbon fiber reinforced composite using UV-curing epoxy resin[J]. Composites Part B,2015,82:221-225.
[7] Li G,Hedlund S,Pang S S,et al. Repair of damaged RC columns using fast curing FRP composites[J]. Composites Part B,2003,34:261-271.
[8]汪雷敏,潘铁英,史新梅,等. IPDI的NMR数据解析[J].波谱学杂志,2005,22(1):79-84.Wang L M,Pan T Y,Shi X M,et al. Characterization of isophrone diisocyanate(IPDI)by NMR spectroscopy[J]. Chinese Journal of Magnetic Resonance,2005,22(1):79-84.
[9] Hailu K,Guthausen G,Becker W,et al. In-situ characterization of the cure reaction of HTPB and IPDI by simultaneous NMR and IR measurements[J]. Polym. Test.,2010,29:513-519.
[10]刘博,李勇,肖军,等.双酚A型环氧树脂紫外光固化工艺及其力学性能[J].航空学报,2014,35(5):1424-1432.Liu B,Li Y,Xiao J,et al. UV-curing process and mechanical properties of bisphenol a epoxy resin[J]. Acta Aeronautica ET Astronautica Sinica. 2014,35(5):1424-1432.
[11] Studer K,Decker C,Beck E,et al. Overcoming oxygen inhibition in UV-curing of acrylate coatings by carbon dioxide inerting,Part I[J]. Prog. Org. Coat.,2003,48:92-100.
[12] Erickson K L. Thermal decomposition mechanisms common to polyurethane,epoxy,poly(diallyl phthalate),polycarbonate and poly(phenylene sulfide)[J]. J. Therm. Anal. Calorim.,2007,89:427-440.