基于α-羟烷基苯酮（HAPK）可聚合大分子光引发剂的合成及其引发三丙二醇双丙烯酸酯（TPGDA）光聚合动力学的研究

以α-羟烷基苯酮(HAPK)、甲苯-2,4-二异氰酸酯(TDI)、聚乙二醇600(PEG600)和丙烯酸-β-羟乙酯(HEA)为原料,通过3步反应,合成了一种可聚合大分子光引发剂:HAPK-TDI-PEG600-TDI-HEA(HTPTH).用IR对反应过程进行了监测.通过Photo-DSC研究了HTPTH引发三丙二醇双丙烯酸酯(TPG-DA)光聚合动力学,考察了光强、引发剂浓度对TPGDA光聚合动力学的影响.结果表明,随着引发剂浓度和光强的增大,最大反应速率对应的转化率、单体最终转化率、最大反应速率都增大,达到最大反应速率所需的时间减小.     

Synthesis of Triblock Copolymers via Photopolymerization of Styrene and Methyl Methacrylate Using Macrophotoinitiators Possessing Poly(ethylene glycol) Units

Macrophotoinitiators based on poly(ethylene glycol)s bearing benzyl tereftalmono amid moieties were synthesized by the reaction of poly(ethylene glycol) (PEG) terminated with terephtaloyl chloride and benzyl amine. The initiators possessing PEG with different molecular weights were used in the photoinduced radical polymerization of styrene (S) and methyl methacrylate (MMA) to yield poly(styrene-b-ethylene glycol-b-styrene) and poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) triblock copolymers. Characterization of macrophotoinitiators were performed by elemental anlysis, IR and ¹H-NMR spectrum. The elemental analysis results agreed with the theoretical values. The IR and ¹H-NMR spectra showed that the poly(ethylene glycol) units were reacting with the tereftloyl chloride and benzylamine. Characterization of the block copolymers was carried out by spectral measurements, GPC and fractional precipitation methods. The polydispersities of the block copolymers were observed between 1.2–2.32 for poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) and 1.25–1.90 for poly(styrene-b-ethylene glycol-b-styrene) from GPC measurements.     

Synthesis of poly(methyl methacrylate‐g‐glycidyl azide) graft copolymers using N,N‐dithiocarbamate‐mediated iniferters

A glycidyl azide polymer with pendent N, N‐diethyl dithiocarbamate groups (GAP‐DDC) was prepared by the reaction of poly(epichlorohydrin) (PECH) with pendent N, N‐diethyl dithiocarbamate groups (PECH‐DDC) and sodium azide (NaN₃) in dimethylformamide (DMF). It was then used as a macro‐photoinitiator for the graft polymerization of methyl methacrylate (MMA). Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Conversion was determined gravimetrically and first‐order time conversion plot for the polymerization system showed linear increase with the polymerization time indicating that polymerization proceed in controlled fashion. The molecular weight distribution (M_w/M_n) was in the range of 1.4–1.6 during polymerization. The formation of poly(methyl methacrylate‐g‐glycidyl azide) (PMMA‐g‐GAP) graft copolymer was characterized by gel permeation chromatography, FT‐IR spectroscopy, Thermogravimetric analysis, and differential scanning calorimetry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

大分子阳离子光引发剂聚苯乙烯-碘鎓六氟锑酸盐的合成及其感光性能的研究

本文用羟基对甲苯磺酰氧基碘苯与聚苯乙烯进行亲电取代反应,得到大分子阳离子碘鎓盐光引发剂聚苯乙烯碘鎓-六氟锑酸盐(PS-I·SbF_6).用核磁共振仪、傅立叶红外光谱仪、凝胶渗透色谱仪、差示扫描量热仪、紫外分光光度仪对其进行了表征.与小分子碘鎓盐系光引发剂相比,PS-I·SbF_6的紫外最大吸收波长λ_(max)红移,在240—270 nm范围内有较强的吸收;固化成膜后其相对迁移率较小分子光引发剂有显著下降.初步研究了PS-I·SbF_6在环氧体系中的光固化性能,结果表明该体系有较好的光固化和后固化特性.     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dendritic carbosilane‐based macrophotoinitiator: synthesis,characterization, and photoinitiating behavior

A novel radical dendritic macrophotoinitiator, bearing alkyl pheone moieties linked to the surface of the dendrimer, was synthesized via alcoholysis of carbosilane dendrimer and the small‐molecule photoinitiator 2‐hydroxy‐2‐methyl‐1‐(4‐tert‐butyl)phenylpropane‐1‐one. The structure of the dendritic carbosilane‐based macrophotoinitiator (MPI) was characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, ²⁹Si NMR, elemental analysis, size exclusion chromatography/multi‐angle laser light scattering, UV‐visible spectroscopy, and differential photocalorimetry (DPC). UV‐visible analysis indicates that the absorption band of photosensitive moieties shifts towards high wavelength by introducing the carbosilane dendrimer core. The DPC results demonstrate that the initiating efficiency of MPI is effective when using epoxy acrylate (EA) as a model resin. Furthermore, thermogravimetric analysis of cured EA resin indicates that the thermal stability can be improved markedly by the incorporation of MPI in the curing formulation. Copyright © 2007 Society of Chemical Industry     

一种含硅大分子光引发剂的合成及其性能研究

以2-羟基-2-甲基-1-苯基丙酮(HMPP)、异佛尔酮二异氰酸酯(IPDI)、羟基封端聚硅氧烷HOSiOH为原料,通过两步反应,合成了一种含硅大分子光引发剂HMPP-IPDI-HOSiOH-IPDI-HMPP(HISiIH)。用IR对反应过程进行了监测。通过配备有紫外光点光源的差动热分析仪(Photo-DSC)研究了HISiIH引发三丙二醇双丙烯酸酯(TPGDA)光聚合动力学。与小分子光引发剂HMPP复配,解决氧阻聚对光聚合反应的影响。