氯化石蜡—52光引发生产工艺条件的开发研究

在建立一套光引发制备氯化石蜡的小试实验装置及过程分析测试方法的基础上，运用正交设计实验方法。系统考察了各工艺条件如光强，光引发时间，氯气流量，反应温度对氯代反应的影响，确定了一较佳的工艺操作参数。为今后开发相应的连续化万吨级生产装置的反应技术提供了依据。     

光对环己烷氯化制备氯代环己烷的影响

首先筛选了光做为环己烷氯化的引发剂,然后建立连续化反应装置,并着重考察了光对环己烷氯化的影响,最后确定最优工艺条件:用蓝色荧光做光源,光照区域占反应器70%,光照强度0.88～1.00 cd条件下,单程转化率为20.45%,选择性为94.49%。     

氯化石蜡—70制备工艺研究

本文主要论述石蜡的光氯化技术,重点讨论光氯化反应的光引发功能及各因素对光氯化反应的影响。本工艺以固体石蜡(C_22～C_26),液氯(含氯:99.5％)为主要原料,经预氯化、深氯化、精制干燥、粉碎等工艺过程制取氯蜡—70,取得了一套优惠的工艺条件。本工艺的特点是反应时间短、产品质量稳定,能耗及原料消耗低。     

国内专利精选

<正>激光引发的循环流化床生产氯化聚氯乙烯的装置及方法:CN107115829A∥程易(北京清诚华宇科技有限公司),公开日期:2017-09-01公开了一种激光引发的循环流化床生产氯化聚氯乙烯的装置及方法。该发明装置包括1个提升管或下行床反应区和1个湍动流化床反应区,以及2个反应区之间的连接装置。提升管或下行床反应区设有紫外激光光源,利用紫外激光活化氯气,引发氯化反应;湍动流化床反应区设有温度控     

气固相法氯化聚氯乙烯的研究进展

介绍了氯化聚氯乙烯(CPVC)的生产工艺和国内外的生产现状,重点阐述了气固相法合成氯化聚氯乙烯的热引发氯化、光引发氯化和等离子体引发氯化工艺的研究。     

气固相法生产氯化聚氯乙烯树脂的研究进展

着重介绍了气固相法制备氯化聚氯乙烯（CPVC）树脂的研究进展,对该法制备CPVC的生产工艺、反应机理以及反应动力学进行了阐述,其中生产工艺主要包括热引发氯化、光引发氯化和等离子体引发氯化等。     

环己烷氯化合成氯代环己烷的研究

由环己烷出发，经光引发氯化制氯代环己烷，对该方法的各工艺条件（反应器，反应温度和光源等）对反应的选择性及转化率的影响进行了考察，确定了生产氯代环己烷的工艺条件。     

氯化苄的合成研究

以甲苯为原料进行氯化合成了氯化苄，并对反应温度、引发剂、光照条件进行了讨论，确定了甲苯在引发剂存在下氯化合成氯化苄的工艺路线。     

2-氯-5-三氯甲基吡啶的定向合成与结构测定

利用3-甲基吡啶为原料，通过光氯化反应合成并分离出了2-氯-5-三氯甲基吡啶。探讨了光氯化反应的机理，通过正交实验对其工艺进行优化，得到了合成产物的最佳工艺条件：温度为180℃，时间为10h，原料与溶剂体积比为1：3，产物产率可达到53．1％。同时用IR、^1HNMR、^13CNMR、MS、UV—Vis等光谱手段确定了产品的结构。     

环己烷氯代合成氯代环己烷的研究

由环己烷出发，经光引发氯化制氯代环己烷。对该方法的各工艺条件（反应器、反应温度和光源等）对反应的选择性及转化率的影响进行了考察，确定了生产氯代环己烷的工艺条件。     

The dyes possessing diazine residue as effective photoinitiators of free radicals polymerization

Summary The series of the dyes possessing diazine residue have been investigated as visible-light absorbing photoinitiators of free radical polymerization. The rates of photoinitiation depend on the structure of the dye. Mechanism of the photoinitiation involves the electron transfer process between the dye and the electron donor (co-initiator). The dyes possessing diazine residue in the presence of a suitable electron donor are very effective photoinitiators. This can be attributed to the high quantum yield of their triplet state formation and high rate constant of electron transfer reaction between the dye and electron donor.     

氯化(2-羟基-3-(4-苯甲酰基苯氧基)-N,N,N-三甲基-1-丙铵)的合成及性质

以4-羟基二苯甲酮和环氧氯丙烷为原料，通过两步法合成了水溶性光引发剂氯化(2-羟基-3-(4-苯甲酰基苯氧基)-N，N，N-三甲基-1-丙铵)。结构用红外光谱得到证实，测定了该光引发剂的水溶性和光引发性能。     

Photografting of methacrylic acid onto HDPE initiated by acetaldehyde in aqueous solutions

Acetaldehyde could act as a very effective photoinitiator for water‐borne photografting. The photografting of methacrylic acid (MAA) onto polyethylene initiated by acetaldehyde in aqueous solutions was reported. Acetaldehyde had higher photoinitiation efficiency than acetone and formaldehyde. The extent of grafting varied with the acetaldehyde content in the solution and it showed the maximum when the content of acetaldehyde was about 10 w/w %. The extent of grafting firstly increased with the increase of monomer concentration till 2 mol/L and then kept constant or slightly decreased. ATR‐FTIR characterizations of the grafted samples proved the successful grafting of MAA onto PE, and the calculated carbonyl indexes were in accord with the results obtained by the gravimetric method. The water absorbency of the grafted samples increased almost linearly with the extent of grafting. The difference in the photoinitiation efficiencies of acetaldehyde, acetone and formaldehyde was discussed through their differences in the n‐π* transitions in water and the photoinitiation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electron transfer processes in photoinitiating systems composed of hemicyanine sec-butyltriphenylborate ion pairs

Summary Borate hemicyanine salts, namely sec-butyltriphenyl styrylbenzoxazole borates are shown to be effective photoinitiators for the polymerization of vinyl monomers. Mechanism of the photoinitiation involves sec-butyl radicals formed from the heterolytic cleavage of carbon-boron bond that follows the electron transfer process. The capability of the salts to act as initiators for the polymerization of multifunctional monomer is documented.     

二苯酮-可聚合胺引发1，6-己二醇二丙烯酸酯的光聚合研究

以UV-Vis分光光度计法和Photo-DSC法分别研究了合成的3种可聚合胺类助引发剂DMPDA、EGDPM、EGMPM与二苯甲酮（BP）组成的引发体系的光化学初级过程及引发1，6-已二醇二丙烯酸酯（HDDA）的紫外光聚合动力学．考察了助引发剂胺的含量对BP的光化学初级过程和对引发HDDA光聚合动力学的影响，以及光强和温度对聚合动力学的影响．结果表明，随着胺含量的增加，BP的光化学初级反应速率增加，从而使体系的聚合反应速率增加．随着温度和光强的增加，单体最终转化率、最大反应速率增大，达到最大反应速率所需的时间减小．     

Spatial and temporal evolution of the photoinitiation rate for thick polymer systems illuminated by polychromatic light: selection of efficient photoinitiators for LED or mercury lamps

BACKGROUND: Four common free radical photoinitiators were evaluated for use in thick photopolymerizations illuminated with a medium‐pressure 200 W mercury–xenon arc lamp and a high‐intensity 400 nm light‐emitting diode (LED) lamp. For each photoinitiator/lamp combination, the spatial and temporal evolution of the photoinitiation rate profile was analyzed by solving the set of differential equations that govern the light intensity gradient and initiator concentration gradient for polychromatic illumination. RESULTS: The simulation results revealed that two of the four photoinitiators evaluated were ineffective for photoinitiating thick polymer systems. The photoinitiator bis(2,4,6‐trimethylbenzoyl)‐phenylphosphine oxide, in combination with the 400 nm LED lamp, was shown to be the most efficient photoinitiator/light source combination for photoinitiation of thick systems. CONCLUSION: The results show that some photoinitiators commonly used for photopolymerization of thin coatings are ineffective for curing thick systems. LED light sources provide advantages over traditional mercury lamps, and may have tremendous potential in the effective photoinitiation of thick polymer systems. Copyright © 2008 Society of Chemical Industry     

Photopolymerization of acrylonitrile in concentrated aqueous zinc halide solutions

Crosslinked polyacrylonitrile (PAN) was obtained with a high yield from the photoinduced polymerization of acrylonitrile (AN) in concentrated aqueous zinc chloride solution. It was found that the presence of zinc chloride results in the promotion of the radical generation in the photoinitiation process as well as an increase in the rate of propagation. Any attempt to isolate the polymer from the reaction mixture was not successful due to the insolubility of the polymer to any conventional solvents to polyacrylonitrile (PAN); therefore, the reaction mixtures, consisting of PAN, zinc chloride, and water—which are referred to as the polymer hybrid system—was used without further purification. The effect of other zinc halides on the polymerization such as zinc bromide and zinc iodide was also investigated in connection with the photoinitiation mechanism, which reveals that the complex (Zn⁺⁺(AN)_x(OH⁻)_yCl) is the species that is responsible for the photoinitiation. It was found that the transparent, stretchable polymer hybrid systems are electric conductive and turn to black upon heating to 160°C due to the conversion of the nitrile group of PAN to tetrahydronaphthyridine rings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2588–2594, 2000     

The influence of the photophysics of 2-substituted thioxanthones on their activity as photoinitiators

The polymerization of methyl methacrylate photoinitiated by thioxanthones (TXs) substituted in the position 2 of the chromophore ring in the presence of 2-(N,N-diethylamino)ethanol has been investigated. The photoinitiation efficiency of these systems is highly dependent on the structure of the 2-substituent. At high amine concentrations, compounds with electron-withdrawing substituents appear as more efficient photoinitiators. The photophysics of the ketones was studied in the polymerization medium. These data show that the singlet excited state of TXs is deactivated by the amine with a rate constant near the diffusional control limit. The triplet rate constants for quenching by the amine and the monomer are highly dependent on the ketone structure. Compounds with electron-withdrawing substituents in the position 2 are more reactive. These studies allow to simulate the dependence of the photoinitiation efficiency with the amine concentration and indicate that the active radicals are produced by the interaction of the ketone triplet with the amine.