Observation of magnetic field effect on polymer yield in photoinduced dispersion polymerization of styrene

Photoinduced dispersion polymerization of styrene in the presence of dibenzyl ketone as a photoinitiator, with or without magnetic field, has been followed with time. The experiments were carried out at low degrees of conversion of monomer. Since the conditions of the polymerization reaction (viscosity of the medium, reagents concentration, etc.) were approximately unchanged, the results were explained on the basis of a simplified model of dispersion polymerization. The normal growth of the polymerization rates with temperature was registered, and the activation energy of the polymerization was estimated to be about 12 kJ/mol in the temperature range from 20 to 60 °C. The magnetic field effect was best seen at low temperature. The maximum yield of the polymerization product increases by 20% when the magnetic field of 1000 G was applied at the temperature of 20 °C.     

One‐component photoinitiator based on benzophenone and sesamol

A new benzodioxole derivative, 4‐(1,3‐benzodioxol‐5‐yloxy) benzophenone (BPBDO), based on benzophenone and sesamol was precisely synthesized, and it can be used as a 1‐component type II photoinitiator. Elementary analysis, atmospheric pressure chemical ionization mass spectrometry, ¹H nuclear magnetic resonance, and ¹³C nuclear magnetic resonance studies revealed that the molecular structure of BPBDO consisted of both benzophenone (BP) and benzodioxole (BDO) structures. The laser flash photolysis experiments and electron spin resonance test indicated that the process of radicals generated from BPBDO after irradiation was similar to 3 processes of ethyl 4‐dimethylaminobenzoate and BP. The kinetics of photopolymerization of the photoinitiator was also studied by real‐time infrared spectroscopy. The oxygen content, light intensity, and viscosity of the monomer affected the decomposition (R_d) and polymerization rate, and the final double bond conversion was also studied. All the results suggest that BPBDO is a 1‐component photoinitiator that is an efficient photoinitiator for free radical polymerization. In contrast to typical dual‐component photoinitiators, eg, BP/ethyl 4‐dimethylaminobenzoate or BP/BDO, BPBDO does not require an additional amine coinitiator for the initiation and is applicable in nonamine resin systems.     

Synthesis of gradient polymer by using polysiloxane‐based photoinitiator

This paper reported a polysiloxane‐based photoinitiator (184‐AC‐Si), which was synthesized basing on traditional photoinitiator 1‐hydroxy‐cyclohexyl phenyl ketene (184) and polysiloxane. Its structure was confirmed by Hydrogen‐1 nuclear magnetic resonance (¹H NMR), real‐time infrared spectroscopy and gel permeation chromatography (GPC). Ultraviolet (UV) absorption spectra of 184‐AC‐Si showed a red‐shifted maximum absorption compared with 184. The kinetics of photopolymerization was studied by real‐time infrared spectroscopy. More importantly, because of the polysiloxane‐based photoinitiator had good ability to float up, which could be proved by X‐ray photoelectron spectroscopy, mapping energy dispersive spectroscopy, UV absorption, and GPC measurements, a convenient and simple method for preparing gradient polymer initiated by 184‐AC‐Si was successfully developed. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H-NMR, ¹⁹F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.     

Photo-responsive liquid crystalline elastomer with reduced chemically modified graphene oxide

Photo-responsive liquid crystalline elastomer (LCE) with reduced chemically modified graphene oxide (RMGO) was fabricated and studied. Mesogenic groups modified graphene oxide (MGO) was prepared, reduced and characterised, then the obtained RMGO was mixed with an acrylate monomer containing a side-on mesogen, a crosslinker and a photoinitiator. After being oriented with magnetic field, well-defined LCE micropillar as photo-responsive actuators were fabricated from the mixture by the method combining soft lithography and photo-polymerisation/photo-crosslinking. The LCE micropillars showed reversible thermo-mechanical deformation during the nematic-to-isotropic transition temperature. Upon irradiating with red light (650 nm), photo-mechanical responses of the RMGO-containing LCE was demonstrated. This micron-sized LCE actuators can be used for remote photo-responsive devices.     

The influence of temperature and photoinitiator concentration on photoinitiated polymerization of diacrylate monomer

The behavior of p-methoxybenzoyldiphenylphosphine oxide, previously synthesized, as a photoinitiator for the polymerization of diacrylate monomer, in the presence of 3% (w/w) tertiary amine (triethyl amine) as synergist additive, was studied. The influence of temperature in the range 30–90°C at 3% (w/w) photoinitiator concentration and the influence of the photoinitiator concentration in the range 0.5–3.5% (w/w) at 30°C was investigated by differential scanning photocalorimetry (photo-DSC). In all experiments the photopolymerization was performed at constant light intensity (3 mW cm⁻²). The maximum conversion was obtained at temperature of 90°C at 3% (w/w) photoinitiator concentration and 3% (w/w) triethyl amine. The optimal concentration of photoinitiator to obtain maximum conversion was 3% (w/w), at 30°C. No thermal polymerization occurred at higher temperature.     

含巯基MTQ树脂的合成及对丙烯酸酯体系光固化性能的影响

以六甲基二硅氧烷、γ-巯丙基三乙氧基硅烷（KH-580）和正硅酸乙酯为原料,在酸性条件下通过水解共聚反应合成了含巯基MTQ树脂（SH-MTQ）。通过傅里叶红外光谱、核磁共振氢谱（¹HNMR）、凝胶渗透色谱和热重,对所合成的树脂进行了表征和分析。以1-羟基环己基苯基甲酮（184）为光引发剂,考察了含巯基MTQ树脂对三丙二醇二丙烯酸酯（TPGDA）光固化过程和材料性能的影响,发现含巯基MTQ树脂的加入使得TPGDA的光固化速率和双键转化率有所提高,并且固化膜硬度、热稳定性、透过率和接触角等材料性能也有所提高。     

Highly efficient alginate-based macromolecular photoinitiator for crosslinking and toughening gelatin hydrogels

Constructing gelatin hydrogels through photopolymerization is getting increasingly attractive due to their excellent biocompatibility and unparalleled flexibility in fabricating complex structures. In this study, an alginate-based macromolecular photoinitiator (Alg-2959) is synthesized by grafting Irgacure2959, a widely used hydrophilic small molecular photoinitiator, onto the framework of alginate. The characterization of Alg-2959 is carried out by ¹H nuclear magnetic resonance (¹HNMR), Fourier infrared spectroscopic (FTIR), Thermogravimetric analysis (TGA), and UV–Vis absorption spectrum. It is shown that Alg-2959 can induce the polymerization of acrylate monomer poly(ethylene glycol) diacrylate (PEGDA400) and glycidyl methacrylate modified gelatin (Gel-GM) with similar initiation efficiency as Irgacure2959. Compared with the pure hydrogels prepared using Irgacure2959, the hybrid hydrogels containing Alg-2959 can be further crosslinked by Ca²⁺ to form the double-network hydrogels, which exhibit enhanced toughness and elasticity. In addition, due to the introduction of alginate, the migration stability of Alg-2959 in the hydrogel networks is significantly improved compared with Irgacure2959. These results indicate the great potential of Alg-2959 in preparing biocompatible and resilient photopolymers.     

季戊四醇四苯甲酰甲酸酯的合成及光引发性能

大分子光引发剂可以解决小分子光引发剂残留碎片带来的毒性对其在食品和医用材料领域应用的限制,为此,本文以苯甲酰甲酸(BF)和季戊四醇(PET)为原料,通过酰氯法在季戊四醇主链上引入了4个苯甲酰甲酸酯基团,制备了多官能度的季戊四醇四苯甲酰甲酸酯(PTF)大分子光引发剂。 PTF在225 ℃时失重15%,热稳定性优于2-羟基-2-甲基-1-苯基-1-丙酮(1173)光引发剂,与1173光引发剂相比,用PTF作光引发剂所制备的光固化涂料,在起始分解温度以及失去相同比例质量所需温度均提高了100 ℃以上。 PTF引发三羟甲基丙烷三丙烯酸酯(TMPTA)聚合时最大反应速率为0.037 s^-1,最终双键转化率为39.5%,PTF光引发活性大于1173光引发剂。 在同等实验条件下,PTF的相对小分子残留量仅为1173光引发剂的5%。     

Polymeric Photoinitiator Containing In‐Chain Thioxanthone and Coinitiator Amines

Summary: A polymeric photoinitiator (PTXP) containing in‐chain thioxanthone (TX) and coinitiator amines was synthesized by step‐growth polymerization, as well as low‐molecular‐weight model compounds. Photopolymerizations of methyl methacrylate (MMA) initiated by these photoinitiator systems were studied. Compared with corresponding low‐molecular‐weight model compounds, PTXP has a similar UV‐vis spectrum with a red‐shifted maximum absorption, and weaker fluorescence emission, and can photoinitiate the polymerization of MMA more effectively.

The structure of PTXP, the photoinitiator synthesized here.     

Influence of sample thickness on ultra-violet initiated polymerisation

The extent of photoinitiated polymerisation of butyl acrylate has been determined using a range of sample thicknesses. For each of the sample thicknesses a range of photoinitiator (benzoin) concentrations were used. It was found that the extent of polymerisation was greatest when the sample thickness was least. For each sample thickness there is a maximum in the graph of extent of polymerisation versus photoinitiator concentration. The optimum concentration of photoinitiator, for maximum extent of polymerisation, increases as the path length increases. As the photoinitiator concentration becomes greater the extent of polymerisation becomes less susceptible to changes in the sample thickness.     

大分子量二苯甲酮光引发剂的合成及动力学研究

以4-羟基二苯甲酮(HBP)、甲苯-2,4-二异氰酸酯(TDI)、4,4′-二羟基二苯甲酮(DHBP)为原料,通过两步反应,合成了一种大分子量二苯甲酮光引发剂:HBP-TDI-DHBP-TDI-HBP(HTDTH).通过实时红外研究了HTDTH的光聚合动力学.结果表明,HTDTH是一种有效的光引发剂.采用HTDTH/胺光引发体系引发二缩三丙二醇二丙烯酸酯(TPGDA)聚合时,随着胺和引发剂浓度的增大,反应速率(R_p)和单体最终转化率(P)同时增大.     

2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑复合光引发体系的光聚合动力学研究

本文研究了对2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑(BMOIM)复合光引发体系引发聚合动力学过程.采用紫外光谱仪对引发剂、供氢体、增感剂在紫外区的吸收谱图进行了表征.利用实时红外光谱仪对复合光引发体系引发聚合动力学过程进行实时监测,考察了不同光强、引发剂浓度以及不同官能度单体对反应速率及最终双键转化率的影响.结果表明,在引发剂浓度为0.6%(质量分数)时,20s内双键转换率达到96%,随着引发剂浓度的提高,聚合速率增大.聚合速率以及最终双键转化率随着光强增大而增大;双官能团单体的最终双键转化率比三官能团单体的最终双键转化率要高.     

Fabrication and characterization of UV‐crosslinkable thermoresponsive composite fibers with magnetic properties

Crosslinking magnetic thermoresponsive composite (MTC) fiber mats were fabricated by electrospinning process and followed by UV curing. Thermoresponsive poly‐(N‐isopropylacrylamide) (PNIPAAm) and magnetic Fe₃O₄ were firstly synthesized by redox‐initiated polymerization and co‐precipitation, respectively. A crosslinking agent (dipentaerythritol hexylacrylate) and photoinitiator for providing crosslinking ability were then mixed with PNIPAAm and Fe₃O₄ in ethanol as the electrospinning solution. After electrospinning and subsequent UV irradiation, the MTC fiber mats were thus obtained. Thermoresponsivity of the MTC fibers was measured by both DSC and swelling test. MTC fiber mat exhibited better water‐absorption capability and thermoresponsivity than corresponding film. Morphological analysis was observed by SEM and TEM, and the magnetic property was measured by SQUID. The thermoresponsive magnetic behavior of MTC fiber mat in water was observed under various temperatures and magnetic fields. Vitamin B₁₂ used as a model drug was loaded in the MTC fiber mats and the drug‐release behavior was then studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2152–2162     

Auto‐Initiating Performance of Styrene on Surface Photografting Polymerization

Investigating the surface photografting polymerization of styrene (St), it was found that in the absence of photoinitiator and at high temperatures, a remarkable amount of St‐grafted polymer is formed. The initiation performance of St was further confirmed by surface photografting polymerization of acrylic acid, where St was used as the photoinitiator. This finding is useful to investigate the reaction mechanism of aromatic compounds under UV radiation and develop photoinitiator‐free polymerization systems.     

2,2′,5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4′,5′-二苯基-1,1′-二咪唑复合引发体系光聚合动力学性能研究

利用实时红外对由光引发剂2,2′,5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4′,5′-二苯基-1,1′-二咪唑(WJ-HABI)、增感剂4,4—二(N,N′—二甲基氨基)苯甲酮(EMK)及供氢体N-苯基甘氨酸(NPG)组成的复合引发体系进行光聚合动力学研究.探讨了复合引发体系的浓度、不同配比、紫外光的强度及...     

Cyclopentadienyl(iron)arene-bis-(p-N,N-dimethylaminobenzylidene)-cyclopentanone Photoinitiated Polymerization of Methyl Methacrylate and Styrene

Abstract

Polymerization of methyl methacrylate and styrene can be effectively photoinitiated by a binary photoinitiator system consisting of cyclopentadienyl(iron)arene hexafluorophosphonate salt and bis(p-N, N-dimethylaminobenzylidene)cyclopentanone in the spectral range of 400–500 nm. The amine-type radical formed from the exciplex of the binary photoinitiator system is probably responsible for the radical polymerization of vinyl monomers. A probable mechanism of initiation of polymerization is discussed.     

Novel,highly efficient polymeric benzophenone photoinitiator containing coinitiator moieties for photopolymerization

A novel polymeric photoinitiator P(MPBP‐co‐DMAEMA), bearing side‐chain benzophenone (BP) and coinitiator amine, was synthesized through free radical copolymerization of a polymerizable photoinitiator, 4‐[(4‐maleimido)phenoxy]benzophenone (MPBP), and a polymerizable coinitiator amine, N, N‐dimethylaminoethyl methacrylate (DMAEMA). In order to find out the influences of coinitiator amine on photopolymerization, a polymeric coinitiator amine, P(DMAEMA), was also synthesized for comparison. FT‐IR, ¹H NMR, and GPC analyses confirm the structures of polymers. The UV‐Vis spectra of polymeric photoinitiator P(MPBP‐co‐DMAEMA) and polymerizable photoinitiator MPBP are similar, and both exhibit high red‐shifted maximal absorption as compared with BP. The photopolymerization of 1,6‐hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA), initiated by MPBP/DMAEMA, MPBP/P(DMAEMA), and P(MPBP‐co‐DMAEMA) systems, was studied by photo‐DSC. The results indicate that P(MPBP‐co‐DMAEMA) is most efficient for the polymerization of both HDDA and TMPTA, and MPBP/P(DMAEMA) is the least efficient of the three photoinitiating systems. Copyright © 2009 John Wiley & Sons, Ltd.     

三官能度甲基丙烯酰氧基单体的合成与性能研究

用甲基丙烯酰氯分别与二乙醇胺和三乙醇胺反应合成了两种三官能度甲基丙烯酰氧基单体.以实时红外光谱(RT-IR)法研究了两种单体的光聚合动力学性质,考察了不同单体、不同引发剂和引发剂浓度、不同光强对聚合性能的影响,并采用动态力学分析仪(DMA)测试了光固化后材料的力学性能.结果表明,随着引发剂浓度的增大,单体转化率、最大反应速率都增大,随着光强的增大,单体转化率、最大反应速率都降低.与二苯甲酮(BP)相比,2-羟基-2-甲基-1-苯基丙酮(1173)对两种单体具有较好的引发效果.两种单体加入三缩四乙二醇双甲基丙烯酸酯(SR209)中后,对体系光固化后的产物力学性能有不同影响.     

Well‐controlled RAFT polymerization initiated by recyclable surface‐modified Nb(OH)5 nanoparticles under visible light irradiation

A recyclable solid‐state photoinitiator based on the surface modified niobium hydroxide is prepared and successfully introduces into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed by gel permeation chromatography analysis that well‐defined polymers with controlled molecular weight and narrow polydispersity index can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to external stimulus and when light is removed from the system polymerization stops almost immediately. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. At last, the mechanism for the light initiated polymerization is proposed to illuminate how the initiation and chain propagation proceed. This facile, green and visible light initiation methodology could attract more and more applications in polymer science with the depletion of fossil energy. A recyclable solid‐state photoinitiator based on the surface modified niobium hydroxide was prepared and successfully introduced into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed that well‐defined polymers with controlled molecular weight and narrow polydispersity index (PDI) can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to light initiation. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2715–2724