直链型双官能度引发剂2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷(DMDEHPH)引发苯乙烯聚合实验与仿真研究

从基于聚合机理的基元反应和物料衡算出发, 考虑聚合过程中的体积收缩和热引发, 详细推导了直链型双官能度引发剂引发苯乙烯聚合的动力学模型, 考虑凝胶、玻璃化和笼蔽效应等对各速率常数和物性参数的影响, 利用基于自由体积理论的扩散控制速率参数和矩方法求解各物种浓度、聚合速率、分子量及多分散度的表达式. 利用模型计算了不同温度和引发剂[2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷(DMDEHPH)]浓度下的转化率、分子量和多分散度, 均与实验结果相符. 模型还可计算各自由基、含过氧键和双端终止聚合物浓度, 结果表明浓度对转化率曲线中均有一峰值, 双自由基浓度比单自由基浓度低几个数量级, 不同聚合物浓度则仅差几倍. 不同引发剂浓度下同物种浓度曲线无交点, 且引发剂浓度越大物种浓度越高; 不同温度下的曲线有交点, 凝胶效应阶段温度越低浓度越大, 凝胶效应之前和之后则温度越低浓度越小.     

引发剂对聚醋酸乙烯酯微乳液聚合的影响

考察了3种引发体系[过硫酸铵一碳酸氢钠(Ⅰ1),偶氮二异丁腈(Ⅰ2),过氧化氢-抗坏血酸(Ⅰ3)]对聚醋酸乙烯酯微乳液聚合的影响.结果表明:Ⅰ2使微乳液聚合体系反应剧烈;Ⅰ3反应较为平稳;Ⅰ1的表现中等.Ⅰ1～Ⅰ3所制得的乳液分子量出现典型的双峰分布.在高分子量部分,Ⅰ3对应的聚合物分子量较高;在低分子量部分,Ⅰ1～ⅠI3差别不大;Ⅰ2对应的乳胶粒径较小,分布也较窄;Ⅰ3次之;Ⅰ1对应的乳胶粒径较大,分布也较宽.     

Effect of Initiator on the Incorporation of Graphite into Polymer Matrix During Suspension Polymerization

Summary: The incorporation of graphite into polystyrene (PS) particles produced by suspension polymerization was studied using a monofunctional and a bifunctional initiator, benzoyl peroxide (BPO) and 2,5-dimethyl-2,5-bis(2-ethyl hexanoyl peroxide) hexane (L256), respectively. The results showed that the polymerization rate was affected by graphite concentration when BPO was used as the initiator while no such effect was observed for L256. Results also showed that the incorporation of graphite in the PS particles was higher when using BPO than when using L256. Molecular weight distribution showed that during the reaction with BPO and graphite oligomers were formed indicating that the free radicals generated by the decomposition of BPO presented a very high reactivity with the functional groups present at the graphite surface while no significant effect was observed for the reaction with L256.     

Cationic Polymerization of Tetrahydrofuran with Fuming Sulfuric Acid Initiator: Effects of Superacid Salts and Aromatic Compounds on Mn and Yield of the Polymer

Bulk polymerization of tetrahydrofuran was studied to find a facile method for the preparation of polytetramethyleneglycol having molecular weight more than 1000 initiated by fuming sulfuric acid as a main component at -5 to 0°C. Superacid salts, being soluble in tetrahydrofuran, showed excellent activity for increasing the molecular weight. The polymerization initiated by fuming sulfuric acid in combination with sodium trifluoromethane sulfonate was examined under several conditions. It was also found that a mixture of fuming sulfuric acid and an aromatic compound such as benzenesulfonic acid, benzene, and xylene, contributed to an increase in the molecular weight of polymer.     

质子捕捉技术在阳离子聚合中的应用

本文介绍了质子捕技术在阳离子聚合中的应用最新研究工作进展。对质子捕捉剂在阳离子聚合反应机理研究中的应用以及质子捕捉剂在活性阳郭聚合引发体系中的作用和功能作了详尽的讨论。     

Effect of the Counterion on the Cationic Polymerization Rate of Ethylene Oxide by Trityl Salts

The cationic polymerization of ethylene oxide by trityl salts (BF₄ ^?, SbCl₆ ^?, AsF₆ ^?, and PF₆ ^? as counterions) in nitrobenzene at different temperatures has been studied. The kinetic analysis was carried out by use of an automatic manometer, and it showed that the polymerization rate constant depends neither on the counterion type nor on the initial initiator concentration. These facts allowed us to conclude that macrocations and macroion pairs have the same reactivity.     

X-Ray structural investigation of 1,3,6-trichloro-3,6-dimethylcycloheptanecarbonitrile and 2,5-dimethyl-2,5-dichlorohexane — Products of the reaction of 2,5-dimethyl-1,5-hexadiene with trichloroacetonitrile

Addition of trichloroacetonitrile to 2,5-dimethyl-1,5-hexadiene in the presence of cuprous amine complexes is studied. Single crystal X-ray diffraction unambiguously proves that the main product is a racemic mixture of the cyclic symmetric nitrile: (1r,3R,6S)-and (1r,3S,6R)-1,3,6-trichloro-3,6-dimethylcycloheptanecarbonitrile. Established relative configuration of the product confirms the ring closure mechanism suggested before. Also, a side product 2,5-dimethyl-2,5-dichlorohexane is isolated (the product of hydrochlorination of the starting alkadiene). Low-temperature (190 K) structural examination of this centrosymmetrical molecule indicates that the unit cell comprises one molecule.     

Anionic Polymerization of Chiral Isocyanate and Influence of the Initiator on Changes in the Optical Activity

A chiral polyisocyanate, poly[6‐{1‐[(S)‐(–)‐2‐methylbutyl]oxycarbonylamino}hexyl isocyanate], was synthesized using sodium diphenylmethanide and sodium naphthalenide as unidirectional and bidirectional initiators, respectively, via anionic polymerization in THF at –98°C. NaBPh₄ as a common ion salt was used to produce the polymer in quantitative yield and with narrow molecular‐weight distribution. The polymer showed different optical activity depending on the nature of the initiator.     

聚合条件对N-羧基-L-丙氨酸-环内酸酐开环聚合产物分子量的影响

用光气法制备了N-羧基-L-丙氨酸-环内酸酐(L-Alanine NCA).系统研究了L-Alanine NCA开环聚合反应过程中引发剂、溶剂、温度对聚合物分子量的影响.用硝基苯作溶剂,三乙胺作引发剂,所得聚合物特性粘度[η]=1.18.实验中发现,L-Alanine NCA可以顺利地进行热聚合反应。反应具有速率快,转化率高,分子量大的特点。甲苯溶剂中反应5小时所得聚合物[η]=2.35,高于采用引发剂的聚合体系产物的相应值。     

Homolytic cyclization of 1,3-propanedithiol to 1,2-dithiolane in the presence of 2,5-dimethyl-2,4-hexadiene

2,2-Diethyl-1,3-propanedithiol undergoes cyclization to 4,4-diethyl-1,2-dithiolane upon interaction with 2,5-dimethyl-2,4-hexadiene in benzene in the presence of azodiisolbutyronitrile. The reaction proceeds according to the radical chain mechanism. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2078–2080, October, 1998.     

聚合介质酸度对聚苯胺的结构和性能的影响

不论电化学还是化学聚合,酸度对聚苯胺(PAn)的合成都有很大影响,说明只有在酸性条件下才能合成电活性的聚苯胺,鉴于聚合介质的酸度对聚苯胺的影响尚无详细的报道,本文研究了聚合介质酸度对聚苯胺的结构和性能的影响.     

乙烯基阳离子聚合引发剂的新进展

本文围绕着乙烯基阳离子聚合这一核心，简要地介绍了近年来在阳离子聚合引发剂方面取得的新进展，包括活性阳离子聚合和普通阳离子聚合引发剂两个部分。     

乳化剂对阳离子乳液聚合及乳胶粒性能的影响

以苯乙烯、丙烯酸丁酯为非离子单体,甲基丙烯酰氧乙基三甲基氯化铵（DMC）为阳离子单体,偶氮二异丁基脒盐酸盐（AIBA）为引发剂,十六烷基三甲基氯化铵（CTAC）和乙撑基双（十六烷基二甲基氯化铵）（G16—2—16）为乳化剂,采用半连续种子乳液聚合法进行阳离子乳液聚合。探讨了乳化剂的分子结构和用量对反应速率、单体转化率以及乳胶粒粒径、Zeta电位等的影响。结果表明：乳化剂的用量越大,反应速率越大,单体转化率越高,而乳胶粒粒径越小;使用G16—2—16作乳化剂时,单体转化率较高,乳胶粒粒径较大,Zeta电位较高。     

Effect of Solvent Polarity on Excited-State Double Proton Transfer Process of 1, 5-Dihydroxyanthraquinone

The excited-state double proton transfer (ESDPT) properties of 1, 5-dihydroxyanthraquinone (1, 5-DHAQ) in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method. The steady-state fluorescence spectra in toluene, tetrahydrofuran (THF) and acetonitrile (ACN) solvents presented that the solvent polarity has an effect on the position of the ESDPT fluorescence emission peak for the 1, 5-DHAQ system. Transient absorption spectra show that the increasing polarity of the solvent accelerates the rate of excited state dynamics. Calculated potential energy curves analysis further verified the experimental results. The ESDPT barrier decreases gradually with the increase of solvent polarity from toluene, THF to ACN solvent. It is convinced that the increase of solvent polarity can promote the occurrence of the ESDPT dynamic processes for the 1, 5-DHAQ system. This work clarifies the mechanism of the influence of solvent polarity on the ESDPT process of 1, 5-DHAQ, which provides novel ideas for design and synthesis of new hydroxyanthraquinone derivatives.     

Polymerization of Methyl Methacrylate in the Presence of Imidazole Derivatives. Additive Effect of the Initiator Adduct and Copolymerization with Acrylamide

In the anionic polymerization of methyl methacrylate (MMA) induced by imidazole (Im), an Im‐MMA adduct forms as an initiator adduct in methanol at 30°C in an argon atmosphere by the equimolar reaction of Im with the MMA monomer. The additive effect of the adduct on the homopolymerization of MMA in tetrahydrofuran at 30°C was investigated by dilatometry. The existence of the adduct increased the duration of the propagation step without shortening the formation step of the initiator adduct. The H‐D exchange reaction of the adduct was observed in D₂O by ¹H NMR. Proton transfer of the MMA unit in the adduct was not observable until 45 h after initiation. The copolymerizability of MMA with acrylamide (AAm) induced by the Im catalyst in THF at 30°C was also investigated. It was found that the homo‐and copolymerizations proceeded at the same time. On the other hand, in the MMA homopolymerization system, the addition of AAm monomer during the initial propagation step yielded copolymer of MMA and AAm for near equimolar concentration of the charged monomers.     

Polymerization of methyl methacrylate in the presence of 2,5-di-tert-butyl-p-benzoquinone

Polymerization of methyl methacrylate in the presence of 2,5-di-tert-butyl-p-benzoquinone is a combination of two processes: inhibited and controlled radical polymerization. The adduct of chain propagation radicals and p-quinone formed due to the inhibited polymerization is a macroinitiator of controlled radical polymerization. The fraction of the pseudo-living process is determined by the concentration of p-quinone in the starting polymerized composition. Post-polymerization proceeds via the reversible inhibition mechanism.

     

Effect of Cationic Micelle on the Kinetics of Oxidation of Citric Acid by N-Bromophthalimide in Acidic Medium

Kinetics of the oxidation of citric acid (CA) by N-bromophthalimide (NBP) has been studied in the presence of cationic surfactant cetyltrimethylammonium bromide (CTAB) at 35°C. The CMC value is lower than those given in the literature for aqueous solutions of CTAB without added electrolyte. The reaction is strongly catalyzed by cationic micelle, CTAB with a progressive increase in CTAB concentration the reaction rate increased, at higher concentration constancy in the rate constant was observed. The reaction follows first and fractional order kinetics in NBP and citric acid, respectively. The reaction follows inverse fractional order with respect to perchloric acid. The Arrhenius equation is found to be valid for the reaction. A detailed mechanism with the associated reaction kinetics is discussed. The catalytic role of CTAB micelles is discussed in terms of the Menger and Portnoy model.     

The Steric Course of the Cationic Polymerization of Vinyl and Related Monomers. The Counterion Effect

Polymerization with many triphenylmethyl salts was conducted for α-methylstyrene, isobutyl vinyl ether, t-butyl vinyl ether, and spiro[2,4]hepta-4,6-diene (SHD). The variation of polymer structure (the isotactic unit content for the first three monomer systems and the amount of the 1,4-addition structure for SHD) showed fairly simple correlations with the counteranion size. The results can be interpreted in terms of the tightness of the propagating ion pair within the framework of a theory of the cationic propagation which had been proposed. When the counteranion radius was greater than 3.5 Å, the counteranion exerts a parallel influence on the tightness of the growing ion pair without regard to the monomer structure. However, in the case of smaller counterions, the tightness appears to be determined by the relative sizes of counteranion and monomer. The penta-coordinated counteranions gave rise to the polymer structure which would arise from tighter ion pairs than expected from their sizes alone. The polymer structure was also affected by the initiator concentration in these cases. These results are attributed to peculiar characteristics of penta-coordinated anions.     

Mechanistic studies in the reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with 2,5-dimethyl-2,4-hexadiene

Secondary isotope effect measurements of methanol adducts from the reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with 2,5-dimethyl-2,4-hexadiene, support the formation of an aziridinium imide intermediate rather than an open dipolar intermediate in the rate determining step.