吡咯烷基-N-甲酸,丙烯酸乙二醇酯的合成及其光聚合动力学的研究

合成了不含氢键的低粘度的吡咯烷基-N-甲酸-丙烯酸乙二醇酯(PLW),并采用实时红外光谱法检测了光强和光引发剂浓度对光聚合动力学的影响。随着光强的增加光聚合的最终转化率基本不变,但是光聚合速率有明显的增加,并且达到最大聚合速率的时间也缩短。随着光引发剂浓度的增加,最终转化率和最大聚合速率都有了显著的增加。所合成单体的转化率在30 s内能达到90%以上。     

DPPH引发丙烯酸酯单体光聚合动力学研究

采用傅立叶红外光谱仪、核磁共振仪对阳离子光引发剂4-(苯硫基)苯基二苯基硫鎓六氟磷酸盐(DPPH)结构进行了表征,紫外光谱分析表明该引发剂在302nm处有最大紫外吸收。通过实时红外(RT-IR)对DPPH引发丙烯酸酯单体光聚合动力学过程进行了研究,考查了引发剂浓度、光强及不同官能度单体对双键转化率及聚合速率的影响。随引发剂浓度增加,最大转化速率先增大后减小,而光强增加,最大转化速率增加。单体官能度越高,双键转化率与最大转化速率越低,达最大转化速率的时间越长。     

丙烯酰胺在聚乙二醇水溶液中可逆加成-断裂链转移聚合

结合双水相聚合和可逆加成-断裂链转移(RAFT)聚合,提出在聚乙二醇(PEG)水溶液中进行丙烯酰胺(AM)的RAFT双水相聚合,考察反应条件对聚合反应速率和产物分子量及分布的影响。结果表明:高引发剂浓度、单体浓度和聚合温度可以提高初始聚合速率和最终转化率,PEG和RAFT试剂浓度的增加会导致聚合速率减慢和最终转化率降低;峰值聚合速率随引发剂浓度、单体浓度和聚合温度的增加而增大,同时峰值聚合速率对应的时间提前;RAFT试剂浓度增加会推迟峰值聚合速率对应的时间,但可制得分子量分布较窄的产物;PEG浓度的增加会导致产物的分子量分布变宽。     

吡咯烷基-N-甲酸-丙烯酸乙二醇酯光聚合动力学的研究

采用实时红外技术对所合成的活性稀释剂吡咯烷基-N-甲酸-丙烯酸乙二醇酯的聚合动力学进行了测试.研究了光强、引发剂浓度及引发剂种类对其光聚合的影响.结果表明光强越强、引发剂浓度越大,聚合速率越高,但是反应的最终双键转化率基本不变,均能达到100%左右.引发剂种类对其光聚合的最终双键转化率的影响不是特别明显,但对聚合速率有一定的影响.     

MMA—St高转化率共聚动力学

在60～90℃范围内,以AIBN、BPO为引发剂进行甲基丙烯酸甲酯(MMA)～苯乙烯(St)本体共聚,研究了高转化率下聚合温度、引发剂浓度及单体配比对共聚速度的影响。结果表明,聚合温度升高、引发剂浓度增大及单体配比中MMA含量增加,均使MMA～St共聚速率增大。但当聚合反应进行到转化率达70%左右时,聚合速率开始显著降低?当转化率达到90%以上时,聚合反应几乎停止。推导并关联了高转化率下共聚动力学模型,在转化率70%以下,模型计算值与实验结果符合很好,该模型为MMA～St共聚生产控制提供了理论依据。     

乙酸乙烯酯无乳化剂乳液聚合的影响因素探讨

采用乙酸乙烯酯(VAc)在水中以过硫酸钾(KPS)和亚硫酸氢钠氧化还原体系作为引发剂进行无乳化剂乳液聚合,探讨了引发剂浓度、聚合温度、单体浓度和搅拌速度对聚合速率及转化率的影响。结果表明:当VAc质量分数为30%,KPS:VAc摩尔比为1:2 000,聚合温度10℃,反应时间10 h,搅拌速度80 r/min,时聚合产物聚乙酸乙烯的聚合度达到10 848;当VAc质量分数为35%时,聚合转化率可达到96%,聚合速率与引发剂浓度的0.944次方成正比;当搅拌速度达到200 r/min以上时,搅拌速度对聚合速率以及转化率影的响可以忽略。     

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．     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

甲基丙烯酸甲酯的光引发聚合研究

本文探讨了光引发剂的种类与浓度、光照强度、光聚合组合物体系粘度及光聚合体系氛围对甲基丙烯酸甲酯(MMA)光引发聚合硬化时间、产率、重均分子量及分子量分布的影响。结果表明,体系初始粘度或引发剂含量的增加均有利于加快光聚合速度以及提高产率,产物具有良好的实用价值。PMMA的重均分子量Mw随着光引发剂浓度的增加而降低,但对紫外(UV)光强不敏感。     

橡胶接枝苯乙烯本体共聚合全程聚合动力学

研究了橡胶含量、引发方式和橡胶种类对橡胶接枝苯乙烯本体共聚合动力学的影响.研究发现,橡胶链活性中心浓度较低,橡胶对引发剂自由基的笼蔽效应和对自由基的包埋是化学引发时低顺式聚丁二烯橡胶加入后聚合速率下降的主要原因;随着橡胶中苯乙烯结构单元含量的增加,橡胶的加入对接枝聚合速率的影响逐渐降低;当橡胶的黏度较高时,橡胶加入后体系的凝胶效应将导致聚合速率的增加;与热引发聚合相比,化学引发时接枝聚苯乙烯和包埋聚苯乙烯的含量较高,故其速率的下降更明显,且在相转变点出现转折点.     

Electron‐beam curing of bismaleimide‐reactive diluent resins

Electron‐beam (E‐beam) curing of 4,4′‐bismaleimidodiphenylmethane (BMPM)/BMI‐1,3‐tolyl/o,o′‐diallylbisphenol A (DABPA)–based bismaleimide (BMI) systems and their mixing with various reactive diluents, such as N‐vinylpyrrolidone (NVP) and styrene, were investigated to elucidate how temperature, electron‐beam dosage, and diluent concentration affect the cure extent. The effect of free‐radical initiator on the cure reactions was also studied. It was found that low‐intensity E‐beam exposures cannot cause the polymerization of BMI. High‐intensity E‐beam exposures give high reaction conversion attributed to a high temperature increase, which induced thermal curing. It was shown that the dilution and activation of NVP in BMI cause a more complete BMI cure reaction under E‐beam radiation. BMI/NVP can be initiated easily by low‐intensity E‐beam without thermal curing. FTIR studies indicate that about 70% of the reaction is complete for BMI/NVP with 200 kGy dosage exposure at 10 kGy per pass. The sample temperature only reaches about 75°C. The free‐radical initiator, dicumyl peroxide, can accelerate the reaction rate at the beginning of E‐beam exposure, but does not affect the final reaction conversion. The increase of the concentration of NVP in the BMI/NVP systems increases the reactive conversions almost linearly. © 2004 Wiley Periodicals Inc. J Appl Polym Sci 94: 2407‐2416, 2004     

可见光固化树脂的固化性能的研究

研究了在532nm激光条件下，环氧丙烯酸树脂的光固化过程。实验表明：光引发剂质量分数为4％时，临界曝光量Ec最小；随着叔胺质量分数的和有机色素质量分数的增加，临界曝光量逐渐增加；激光能量越大，临界曝光量越小，激光能量大于400mW时，激光能量增加对临界曝光量几乎无影响。     

Equation of consumption rate of free-radical vinyl polymerization. II

The vinyl polymerization reaction is a two-molecule reaction. However, it is more convenient to use a specially defined rate constant than to use the general constant, because a new radical is formed instantaneously in the same radical compound when one monomer combines with an existing radical in a living polymer or an initiator radical. This special rate constant is named the propagation constant and is proportional to the concentration of monomer when the polymer is formed from a unit mole concentration of the initiator radical. The specific propagation constant is related to the concentration of monomers which react in unit time and unit concentration of monomer and radical. Arnett's experiments are discussed in terms of the equation formulated. The value of Δ[M]/([M]₀·t) is found not to be a reaction rate but a value of ln [M]₀/[M] when [M]₀ – [M] is very small. Autoacceleration of the polymerization is found with high concentrations of monomer which yield an increase in the velocity of propagation and also at low concentrations of initiator, which cause prolongation of the propagation stage. When the concentration of initiator is high, this phenomenon does not take place until enough initiator is consumed and the necessary low initiator level is reached. The time required is called the induction period. The larger the polymer molecule is, the higher the viscosity becomes.     

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     

Study on spatial–temporal kinetics of photo‐initiated frontal polymerization in stacked reaction cells

The spatial–temporal kinetics for photo‐initiated frontal polymerization(PFP) of isobornyl acrylate with 2,4,6‐trimethylbenzoyldiphenyl phosphine oxide (TPO) as photobleaching initiator was studied experimentally in stacked reaction cells. FTIR and NMR spectroscopy were employed to measure the polymerization conversion, which is dependent on the exposure time, sample depth, light intensity and photo‐initiator concentration. The experimental results are consistent with the theoretical model prediction and show that prolonged irradiation time, higher light intensity and lower photo‐initiator concentration are favorable in enhancing the advance of the polymerization front. The depth‐resolved GPC analysis shows that the average molecular weight of the PFP product dramatically increases with sample depth, while the molecular weight polydispersity reduces steadily with increase in sample depth. Copyright © 2006 Society of Chemical Industry     

聚氨酯丙烯酸酯光固化反应动力学的研究

用光DSC (DPC)考察了三种聚氨酯丙烯酸酯 (PUA)预聚物 ,即传统的、扩链的以及接枝的PUA的光固化动力学行为。讨论了不同的反应条件对三种PUA的光固化动力学的影响。利用DPC数据计算出反应速率与各种影响因素的指数关系。预聚物的引发剂指数均小于 0 5。对于传统的和扩链的PUA ,光强指数稍低于0 5 ,单体浓度指数近似于 1,而对于接枝PUA则分别为 0 5 6～ 0 6 8和 1 2 5。在恒定光强和引发速率条件下反应速率与转化率的关系算出kp/kt1/ 2 ,在非稳态条件下反应速率对时间的关系算出kt/kp,可以求出kp 和kt 值。结果表明 ,体系的凝胶效应使kp 和kt 随转化率增加而大大下降     

有机硅改性丙烯酸酯树脂的合成及其光固化动力学研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(n-BA)、二缩三丙二醇二丙烯酸酯(TPGDA)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)为单体,正十二烷基硫醇(NDM)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,合成了一种可紫外光固化的丙烯酸酯树脂(UV-WZF)。通过FT-IR、DSC、TGA对其结构和性能进行了研究。讨论了KH-570的含量和TPGDA的含量对光固化膜的附着力、光固化速率的影响。结果表明:当硅烷偶联剂KH-570的用量为6%时,涂膜附着力良好;当TPGDA的用量为26%时,固化漆膜的光固化时间最短。采用实时红外光谱原位跟踪监测了该树脂的光固化动力学行为,结果表明:当光引发剂Darocur1173含量为树脂质量的5%时,体系的光固化速率最优,增大光强利于光固化。     

Analytic formulas and numerical simulations for the dynamics of thick and non-uniform polymerization by a UV light

The kinetics of UV light photoinitiated polymerization system (PPS) with non-uniform initiator concentration is theoretically presented. Analytic formulas are derived for the cross linking time (T*), defined by the depletion level of the initiator, which is an exponentially increasing function of the thickness, whereas it is inverse proportional to the UV light intensity. Typical T* (on the surface, at z?=?0) is about 2 min for a UV light intensity of 20 (mW/cm²) and the range of T*(at z?>?0) is about 3 to 5 min, for a polymer thickness of 1.0 cm. Optimal photoinitiation rate is found to be the result of the competing parameter between the UV light intensity and the initiator concentration. The roles of each of the key parameters in PPS are numerically shown including the initiator concentration and its distribution, the UV light intensity and the three absorption coefficients. Our analytic formulas and numerical results provide useful guidance for the parameters selection and optimalization in PPS with the prediction of the cross linking time in various system thickness.