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     

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.     

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

queous solution polymerization of acrylamide (AAm) was demonstrated by using initiation system consisting of N-methacryloyl-N '-pyrimidinopiperazine (MPMP ) and persulfate (KPS). The polymerization rate equation was obtained to beR_p = K_p[MPMP]^1/2 [KPS]^1/2 [AAm]^1.0The overall activation energy for the polymerization was calculated by Arrhenius quation to be Ea= 5.6 KJ/mol. The redox nature for the polymerization was clarified. A super high molecular weight up to 10⁷ of PAAm was obtained by using this initiation system. From the fluorescent analysis, it was confirmed that MPMP not only acted as a component of the redox system, but also entered into the acrylamide polymer chains.     

含胺基功能性单体的聚合研究——Ⅻ.N-丙烯酰-N′-苯基哌嗪类的合成、光聚合及其作为氧化还原引发体系组分的研究

N-acryloyl-N'-phenylpiperazine (APP) and N-methacryloyl-N'-phenylpiperazine (MPP) were synthesized by the reaction of N-phenylpiperazine with corresponding acryloyl chlorides. The solution of these polymers display the fluorescence phenomenon, but these monomers do not. APP and MPP can be photopolymerized under the UV irradiation. The rate equation of MMA polymerization initiated by APP and BPO is given as RP = [APP]0.5 [BPO]0.5 [MMA] . The redox initiation system would be formed by the. combination of APP and BPO.APP not only initiates the polymerization of MMA ,but also incorporates into the MMA polym-er chains.     

3-甲基丙烯酰胺基-9-乙基咔唑-过硫酸钾氧化还原体系引发丙烯酰胺聚合

合成了可聚合芳香叔胺-3-甲基丙烯酰胺基-9-乙基咔唑,并与过硫酸钾组成氧化还原引发体系引发丙烯酰胺水溶液聚合,测定了聚合反应动力学,得到了超高分子量的聚丙烯酰胺.     

铈离子与4,4′-二乙酰氨基二苯基甲烷体系引发烯类聚合

The polymerization of acrylamide was carried out in H2O-DMF (3:1 v/v) solution using eerie ion (eerie ammonium nitrate, CAN) as initiator. It was found that the presence of 4,4'-diacetaminodiphenylmethane (DAADPM) could promote the polymerization and increase the rate of polymerization. The overall activation energy and rate equation of acrylamide polymerization initiated with eerie ion/DAADPM system were determined respectively. From IR spectrum end-group analysis of polyacrylonitrile (PAN) prepared by solution polymerization of AN using CAN/DAADPM system as initiator,it revealed the presence of DAADPM end-group in the polymer. Accordingly,the initiation step includes the addition of DAADPM radical to monomer and forms the end-group of polymers.     

含胺基功能性单体的聚合研究——ⅩⅦ.N-(4-二甲氨基苯基)马来酰亚胺的聚合及其光化学行为

N-(p-Dimethylaminophenyl)maleimide (DMAPMI) was synthesized and copolymerized with vinyl acetate. The photochemical behavior of DMAPMI and its polymer was studied. It was found that the intensity of monomer was lower than that of its copolymer due to the structural self-quenching effect as we have reported previously. The relationship between Stern-Volmer constant and 'e' value of quenchers was discussed. DMAPMI could act as both of a photosensitizer for vinyl polymerization upon UV irradiation and a component of redox initiation system by combining with BPO to initiate the vinyl thermo-polymerization.     

含胺基功能性单体的聚合研究——Ⅵ.4-N′,N′-二甲氨基苯基N-取代丙烯酰胺的合成及其聚合

<正> 前文报道了含芳香叔胺基丙烯酸酯-甲基丙烯酸4-N,N-二甲氨基苄酯(DMABMA)的合成和聚合。这种在分子中既含有二甲氨基苯基,又含有双键的单体为“可聚合芳香叔胺”,在过氧化二酰如过氧化苯甲酰(BPO),过氧化月桂酰(LPO)引发下,芳香叔胺残基参与氧化还原引发体系,进而双键发生聚合反应。本文报道了二甲氨基苯基取代丙烯酰胺,即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)的合成及聚合。     

含胺基功能性单体的聚合研究——Ⅻ.N-丙烯酰-N′-苯基哌嗪类的合成、光聚合及其作为氧化还原引发体系组分的研究

我们曾报道了含芳香叔胺基功能性单体的合成及其聚合的研究,这些单体都是既参与引发反应又参与聚合的“引发剂单体”。本文报道了一种含有芳香叔胺基的新单体——N-丙烯酰-N′-苯基哌嗪(APP)和N-甲基丙烯酰-N′-苯基哌嗪(MPP)的合成及其光聚合。由于APP或MPP含有芳香叔胺基,它们和过氧化苯甲酰(BPO)配合,     

含β-二酮结构的丙烯酰类单体的聚合研究

含有β 二酮结构的烯类单体,如丙烯酰丙酮,分子中的β 二酮部分存在着酮式 烯醇式的互变异构现象［１～３］,张亦帆等对此进行了详细的研究［４］．ＣＨ２ＣＨＣＯＣＨ２ＣＯＣＨ３ＣＨ２ＣＨＣＯＨＯＣＨＣＣＨ３ＣＨ２ＣＨＣＯＨＯＣＨＣＣＨ３此类单体不同于一般...     

含胺基功能性单体的聚合研究——ⅫⅠ.丙烯腈在N-丙烯酰-N′-苯基哌嗪及其聚合物作为增感剂下的光聚合

The photopolymerization of AN by using N-acryloyl-N'-phenylpiperazine (APP) and N-methacryloyl-N'-phenylpiperazine (MPP) as sensitizers under UV irradiation has been investigated. The corresponding polymerization kinetic equations are as follows:Rp [APP]^0.81[AN]^0.61 R_p [MPP]^0.48[AN]^0.77 R_p [P(APP)]^0.53[AN]^0.78 From the fluorescent analysis, it was confirmed that APP, MPP and P(APP) not only initiated the polymerization of AN but also entered into the chains of AN polymer. The photopolymerization mechanism for exciplex formation of AN with above sensitizers was proposed.     

含胺基功能性单体的聚合研究——ⅫⅠ.丙烯腈在N-丙烯酰-N′-苯基哌嗪及其聚合物作为增感剂下的光聚合

关于含有芳香叔胺基的烯类单体,我们曾报道过N,N-二甲氨基苯乙烯,N-(4—N′,N′-二甲氨基苯基代丙烯酰胺(DMAPAA),N-(4-N′,N′-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),甲基丙烯酸-4-N,N-二甲氨基苄脂(DMABMA),8-丙烯     

含胺基功能性单体的聚合研究——Ⅱ.甲基丙烯酸N,N-二甲氨基乙酯在过氧化月桂酰引发下的聚合

研究了甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)在过氧化月桂酰(LPO)引发下的聚合动力学。求出了在40、50、60和70℃下的表观聚合速率。得到其聚合速度方程式为: Rp-Kp[DMAEMA]~(1.5)[LPO]~(0.5)其表现聚合活化能E_a为9.7 kcal/mol,并提出了含脂肪叔胺基单体参与氧化还原引发体系而引发其自身单体聚合的历程。     

含叔胺基功能性单体的聚合研究——ⅩⅤⅠ.含吗啉基聚丙烯酸酯类及其水凝胶的温度敏感性

我们曾报道过含吗啉基丙烯酰类单体在过氧化物或芳酮存在下的热聚合及光聚合,以及做为氧化-还原引发体系组分引发烯类单体聚合的研究。利用这类单体与过硫酸盐所构成的引发体系可以获得分子量达千万的聚丙烯酰胺。实验中还发现某些含吗啉基的丙烯酸酯类聚合物的水溶液及其水凝胶具有温度敏感性。本文合成了以下四种含吗啉基丙烯酸酯类单体:     

含胺基功能性单体的聚合研究——X.N-(N′-次甲基吗啉)取代丙烯酰胺的合成及其聚合

<正> 聚丙烯酰胺及其N-取代衍生物是一类医用水凝胶,据Ferruti等报道,含有叔胺基的丙烯酸衍生物的聚合物具有抑制路易斯肺癌扩散的作用,我们曾合成了芳香及脂肪叔胺基取代的丙烯酰胺,并对它们的聚合及其作为氧化还原引发体系组分进行了研究,这些叔胺基取代的丙烯酰胺的聚合物,经复钙法测试,证明具有较好的抗凝血性。     

含胺基功能性单体的聚合研究——Ⅲ.甲基丙烯酸4-(N,N-二甲氨基)苄酯在过氧化月桂酰引发下的聚合动力学

<正> 由芳香叔胺如N,N-二甲基对甲苯胺(DMT),N,N-二甲基苯胺(DMA)与过氧化苯甲酰(BPO)所组成的氧化还原体系以引发烯类单体的聚合已有较多报道,这种引发体系在医用高分子的硬组织材料如齿科材料,骨水泥的甲基丙烯酸甲酯(BMA)的低温快速固化上广被应用,构成这种氧化还原体系的低分子胺具有一定的毒性,其用量虽少,     

含胺基功能性单体的聚合研究 Ⅴ.4-N,N-二甲胺基苯乙烯的合成及其作为氧化还原引发体系组分的研究

<正> 前文我们报告了含有芳香叔胺基的丙烯酸酯、甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA)在过氧化二月桂酰(LPO)引发下的聚合动力学。从所得的聚合速度方程式及低的聚合活化能,认为DMABMA与LPO形成氧化还原体系而使DMABMA聚合,在本文第Ⅳ报中报道了DMABMA不仅能引发甲基丙烯酸甲酯的聚合,还参与聚甲基丙烯酸甲酯的链中,因此称这种既能参与引发聚合反应,又参与聚合物链中的引发“引发剂单体(initiatomer)”。这种含有可聚合胺引发体系的优点是,用于丙烯酸酯类医用