N－甲基丙烯酰－N＇－嘧啶哌嗪与过硫酸钾引发体系引发的丙烯酰胺聚合

Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪与过硫酸钾引发体系引发的丙烯酰胺聚合高青雨，张福莲，杨更须，张举贤（河南大学化学化工系，开封，４７５００１）李福绵（北京大学化学系，北京，１０００８７１）关键词Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪，可聚合芳香叔胺，氧化还原引发...     

N，N－二甲基对甲苯胺引发N－对甲苯基马来酰亚胺光聚合的引发机理

Ｎ，Ｎ－二甲基对甲苯胺引发Ｎ－对甲苯基马来酰亚胺光聚合的引发机理叶克强，董建华，丘坤元，冯新德（北京大学化学系，北京，１００８７１）关键词光引发聚合机理，电荷转移复合物，激基复合物，荧光淬灭，Ｎ，Ｎ－二甲基对甲苯胺，Ｎ－对甲苯基马来酰亚胺Ｎ，Ｎ－二甲...     

N－（N＇，N＇－二甲氨基甲基）丙烯酰胺－过硫酸钾引发丙烯酰胺聚合的研究

Ｎ－（Ｎ＇，Ｎ＇－二甲氨基甲基）丙烯酰胺－过硫酸钾引发丙烯酰胺聚合的研究潘松汉，唐康泰，王贞，王真智中国科学院广州化学研究所，广州，５１０６５０关键词Ｎ－（Ｎ＇，Ｎ＇－二甲氨基甲基）丙烯酰胺、反应动力学、氧化还原体系、相对分子质量及分布为了制备高质量...     

N－（N＇，N＇－二甲氨基甲基）丙烯酰胺－过硫酸钾引发丙烯酰胺聚合的研究

The kinetic of polymerization of aeqlamide (AM ) inihated by the combination of N - (N,'N L dimethylaminomethyl ) acrylamide (DMAAM ) with potassiumpersulfate was stUdied. The rate equation was given as:R_p= K_p[DMAAM]^0.5[K₂S₂O₈]^0.5 [AM]The overall aCtivation energy was determined to be 27.86 KJ/mol. DMAAMwas shown not only joined the ndox initiahon but also incorporated intO thepolymer chains, so that the high molecular weight 107 of polyaCrylamide was obtained but the distribution of molecular weight was broad. The effect of additives on molecular weight and its distribution has been studied.     

Crystal Structure of N－（N－Phenylthiazotone）imino－O－ethyl－N－isopropylaminothiophosphate

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＮ－（Ｎ－Ｐｈｅｎｙｌｔｈｉａｚｏｔｏｎｅ）ｉｍｉｎｏ－Ｏ－ｅｔｈｙｌ－Ｎ－ｉｓｏｐｒｏｐｙｌａｍｉｎｏｔｈｉｏｐｈｏｓｐｈａｔｅ￥ＹａｎｇＨｕａ－Ｚｈｅｎｇ；ＬｉｕＨｕａ－Ｙｉｎ；ＷｕＹｅ（Ｉｎｓｔｉｔｕｔｅｏｆ...     

大分子引发－转移－终止剂

Polystyrene and polyacrylamide prepared by BDC (benzyl diethldithiocarbamate )could be ed as macromolecular iniferter and they initated styrene or acrylamidepolymerization further. The results shoWed that chain enlargement reaction inhomogeneous systems had the character of living radical polymerization and theprodusts still contained iniferter functional groups. Polystyrene macromoleculariniferter can initiate acrylamide polymerizahon in dioxane and thepolystyrene-- block-- polyanylamide copolymers were obtained. Blocking efficiency and polymerization activity were high.     

大分子引发－转移－终止剂

大分子引发－转移－终止剂杨文君，李俊柏，沈家骢（青岛化工学院橡塑工程研究所，青岛，２６６０４２）（吉林大学化学系，长春，１３００２３）关键词聚苯乙烯，聚丙烯酰胺，嵌段共聚，扩链反应，引发－转移－终止剂含有二乙基二硫代氨基甲酸基的有机硫化物或大分子，在...     

Syntheses and Characterization of Metal Complexes of L－Lysine－N，N，N＇，N＇－tetraacetic Acid and L－Lysine－N，N，N＇，N＇－tetramethylenepho sphonic Acid

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＭｅｔａｌＣｏｍｐｌｅｘｅｓＯｆＬ－Ｌｙｓｉｎｅ－Ｎ,Ｎ,Ｎ＇,Ｎ＇－ｔｅｔｒａａｃｅｔｉｃＡｃｉｄａｎｄＬ－Ｌｙｓｉｎｅ－Ｎ,Ｎ,Ｎ＇,Ｎ＇－ｔｅｔｒａｍｅｔｈｙｌｅｎｅｐｈＯｓｐｈｏｎｉ...     

Crystal and Molecular Structure of N，N－Bis（2－chloroethyl）－N＇－isopropyl－N＂－phenyl Thioureido Phosphoramide

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆＮ,Ｎ－Ｂｉｓ（２－ｃｈｌｏｒｏｅｔｈｙｌ）－Ｎ＇－ｉｓｏｐｒｏｐｙｌ－Ｎ＂－ｐｈｅｎｙｌＴｈｉｏｕｒｅｉｄｏＰｈｏｓｐｈｏｒａｍｉｄｅＣｈｅｎＲｕ－Ｙｕ;ＷａｎｇＨｕｉ－Ｌｉｎ;ＺｈｏｕＪ...     

N，N－二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲酯的光接枝交联聚合反应

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响．结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

含胺基功能性单体的聚合研究 XIV.含二甲氨基丙烯酰类衍生物与过硫酸钾引发体系引发的丙烯酰胺聚合

The polymerization of acrylamide (AAm) initiated by the combination of N-(N', N'-dimethylaminomethylene)methacrylamide (DMAMMA) or N, N,-dimethylaminoethyl methacry-late with potassium persulfate were studied kinetically. The rate equation for the AAm polymerization initiated by the above initiation systems were given asRp- Kp[AAm][K₂S₂O₈]^1/2[DMAMMA]^1/2 Rp=Kp[AAm][K₂S₂O₈]^1/2[DMAEMA]^1/2 respectively. The overall activation energies for the above polymerization were determined to be 8.7 Kcal/mol and 9.2 Kcal/mol respectively. The UV analysis for the PAAm initiated by the above initiation systema showed that the polymerizable amines,DMAMMA and DMAEMA notonly joined the redox initiation but also incorprated into the AAm polymer chains. The super high molecule weight,10⁷of PAAm were obtained by using these initiation systems.     

一种水溶性可聚合敏化剂N－甲基丙烯酰－N＇－嘧啶哌嗪敏化的丙烯酰胺光聚合

The photopolymerization of acrylamide (AAm) was studied by using N-methacrylyl-N'-pyrimidinopip (MPMP) as sensitizer under UV irradiation.The photopolymerition rate of AAm in water with MPMP as sensitizer is proportional to 0.36th power of MPMP comcentration and 0.88th power of AAm concentration. The overall activation energy for the polymerization is determined to be 5.02Kcal/mol. A super-high MW (10⁷) of PAAm are obtained. The MW is decreased with both the increasing of MPMP concentration and the raising of polymerizat-ion temperature,and inereased with the increase of AAm concentration. Fluoresce-nt analysis indicates that MPMP not only initiates the photopolymerization of vinyl monomers,but also enters into the polymer chains.     

Polymerizabilities of Several Polar Vinyl Monomers by Imidazole

Polymerizabilities of several polar vinyl monomers in the presence of imidazole (Im) have been studied in CDC1₃ and CD₃OD by NMR spectra. Acrylic acid formed a bimolecular adduct with Im as the initial adduct, while methacrylic acid was not obtained, On the other hand, methyl acrylate, methyl methacrylate (MMA), acrylamide (AAm), and acrylonitrile formed the initial adduct between Im and monomer, respectively. In these monomers, AAm and MMA gave each polymer in tetrahydrofuranat room temperature. The number-average molecular weight ([Mbar]_n) of AAm polymers was determined to be in the range of 1000 to 1500, and the [Mbar]_n of MMA polymers was found to be in the range of 2500 to 4500, The rate of polymerization R_p was expressed by the equations R_p = k[Im][AAm] and R_p = k[Im] [MMA]², respectively. The activation energy E_R was obtained by Arrheniuss's plots as E_R(AAm) = 9.6 kcal/mol and E_R(MMA) = 3.8 kcal/mol. These polymerization mechanisms are discussed on the basis of these results.     

含胺基功能性单体的聚合研究 XIV.含二甲氨基丙烯酰类衍生物与过硫酸钾引发体系引发的丙烯酰胺聚合

N-(N′,N′-二甲氨基亚甲基)甲基丙烯酰胺、甲基丙烯酸N,N二甲氨基乙酯、可聚合叔胺、氧化还原引发体系、超高分子量聚丙烯酰胺     

Surface Grafting onto Barium Sulfate: Polymerization of Acrylamide Initiated by the System Consisting of Alcoholic Hydroxyl Groups on the Surface and Ceric Ion

Abstract

To modify the surface of barium sulfate, the grafting of polymers onto the surface by the polymerization of acrylamide (AAm) initiated by the system consisting of eerie ion and alcoholic hydroxyl groups on the surface was investigated. Barium sulfate modified by 12-hydroxystearate (BaSO₄-HS) was prepared by the reaction of barium chloride with sodium sulfate containing a small amount of sodium 12-hydroxystearate. The presence of 12-hydroxystearate groups on the BaSO₄ surface was confirmed by XPS analysis and infrared spectra. It was found that the graft polymerization of AAm is initiated by the system consisting of eerie ion and BaSO₄-HS to give poly (AAm)-grafted BaSO₄. This indicated that the grafted polymer chains are propagated from surface radicals formed by the redox reaction of eerie ion with 12-hydroxystearate groups on the surface. The polymerization rate (R _p) of AAm initiated by the redox system was given by R _p = k[AAm][Ce(IV)][BaSO₄-HS] where k is constant, [AAm] is AAm concentration, [Ce(IV)] is cerie ion concentration, and [BaSO₄-HS] is BaSO₄-HS concentration. The result suggested that in such an initiating system, the unimolecular termination of growing polymer radicals from the surface of BaSO₄ proceeds preferentially. Furthermore, by grafting of poly(AAm) onto the BaSO₄-HS surface, the wettability of the surface was found to turn from hydrophobic to hydrophilic.     

一种水溶性可聚合敏化剂N－甲基丙烯酰－N＇－嘧啶哌嗪敏化的丙烯酰胺光聚合

一种水溶性可聚合敏化剂Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪敏化的丙烯酰胺光聚合高青雨，杨更须，张福莲，张举贤，李福绵（河南大学化学化工系开封４７５００１）（北京大学化学系北京１００８７１）关键词Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪，丙烯酰胺，水溶性光敏剂，光聚合...     

Kinetics of the Copolymerization of Methyl Vinyl Ketone and Acrylamide Initiated by the Adduct of Methyl Vinyl Ketone and Imidazole

N-(Butyl-3-one)imidazole acts as an initiating adduct which is formed in the anionic polymerization of methyl vinyl ketone (MVK) induced by imidazole (Im) and is directly formed from Im and the MVK monomer. The kinetics of the anionic homopolymerization of MVK and acrylamide (AAm) under argon in the presence of the adduct were investigated in tetrahydrofuran (THF). The rate of polymerization for the MVK system is expressed as R_p = k[Adduct] [MVK], where k = 3.1 × 10^?6 L/(mol·s)in THF at 30°C. The overall activation energy, E_a , was found to be 5.34 kcal/mol. The R_p for the AAm system is expressed as R_p = k[Adduct] [AAm], where k = 6.8 × 10^?6 L/(mol·s) in THF at 30°C, with E_a 7.78 kcal/mol. The mechanism of the polymerization induced by the initiator adduct is discussed on the basis of these results.     

STUDIES ON THE INITIATION MECHANISM OF CERIC ION AND ACETYLACETONE REDOX SYSTEM IN VINYL POLYMERIZATION

The initiation mechanism of acrylamide (AAM)polymerization using ceric ion/acetylacetone system as an initiator has been studied. The redox polymerization was revealed by the low value of overall activation energy of AAm polymerization. The structure of free radicals formed from above-mentioned initiation sytem were detected by radical trapping and ESR spectra techniques and the end groups of polymers obtained were determined by FT-IR spectra analysis method. Based on these results the initiation mechanism is proposed.     

含胺基功能性单体的聚合研究——Ⅶ.N-(4-N′,N′-二甲氨基苯基)代丙烯酰胺作为氧化还原引发体系组分的研究

<正> 我们曾报道过甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),4-N,N-二甲氨基苯乙烯(DMAS)等含芳香叔胺基的烯类衍生物不仅可以作为氧化还原引发体系组分引发烯类单体如甲基丙烯酸甲酯(MMA)的聚合,而且还进入MMA的聚合物链中。在另文中报道了两个芳香叔胺取代的丙烯酰胺:N-(4-N′,N′-二甲氨基苯基)丙烯酰胺(DMAPAA)和N-(4-N′,N′-二甲氨基苯基)甲基丙烯酰胺(DMAPMA)的合成及其聚合的研究,本文研究了这两个丙烯酰胺衍生物与过氧化苯甲酰(BPO)组成的氧化还     

Polymerization of Methacrylamide Initiated by the Persulfate/Thiolactic Acid Redox System

The aqueous polymerization of methacrylamide initiated by the ammonium persulfate/thiolactic acid redox system has been studied at 35 ± 0.2°C. The rate of polymerization is governed by the expression, R_p + K_p [MAA] ^1.33 [TLA]^0.22 [ammonium persulfate]^0.6. The deviations from normal kinetics are discussed. A tentative mechanism of initiation is given. The temperature dependence of the rate of polymerization has been studied over the range 30–55°C. The overall activation energy of polymerization is 10.4 kcal/mole.