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烯烃高效催化剂及聚合与共聚合的研究 总被引:1,自引:0,他引:1
为中山大学高分子研究所烯烃配位聚合研究室在高效Ziegler-Natta催化剂、茂金属催化剂烯烃聚合与共聚合方面部分研究工作的概述。重点叙述了催化剂的设计、过渡金属配合物配体结构及聚合条件对乙烯、丙烯、1-丁烯、丁二烯、苯乙烯等烯烃单体聚合及共聚合活性以及聚合产物结构和分子量的影响。 相似文献
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电化学方法聚合乙炔报道甚少,且聚合条件较为苛刻,尚无人将Fe催化剂用于该反应。本文主要报道在Fe(NO_3)_3·9H_2O-DMF溶液中,室温下恒以1 mA/cm~2左右的电流,在不锈钢阴极上聚合乙炔成膜,并经表征证实。 相似文献
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芳香醚在光照下能引发丙烯腈聚合。醚的苯环上带正性取代基时,引发活性大。带负性取代基时,引发活性小。从激发态的电荷转移机制讨论了引发机理。 相似文献
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两亲性丙烯酸酯共聚物的聚合研究 总被引:1,自引:0,他引:1
利用过氧化苯甲酰为引发剂探讨了甲基丙烯酸β-羟乙酯和丙烯酸长链烷基酯的自由基共聚合。重点讨论了合成条件如溶剂、沉淀剂、引发剂用量、单体配比、反应时间等对共聚反应的影响以及各种聚合条件对该共聚物的组成、结构和性能的影响。并用IR,GPC,^13CNMR等手段对共聚物进行了表征。 相似文献
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研究了亚硝酸钠引发硝酸溶液中丙烯腈的聚合反应。测得表现聚合速度 Rp=Ae~(-10,800/RT)[AN]~2.2[NaNO_2]~(0.17-1.0)[HNO_3]~(1.0-0.67 丙烯腈-丙烯酸甲酯共聚合反应中竞聚率分别是γ_An=0.96,γ_MA=1.17,表明聚合反应是按自由基机理进行。 根据聚合动力学和红外光谱分析,认为以亚硝酸钠引发硝酸溶液中丙烯腈的聚合反应与电解或金属溶蚀过程中的次级引发相同。 相似文献
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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, 相似文献
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<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 相似文献
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Aliphatic tertiary amino-group N-substituted acrylamides, N-acryl-N′-methylpiperazine (AMP)and N-methacryl-N′-methylpiperazine (MAMP) were synthesized directly from N-methylpiperazinewith corresponding acryloyl chlorides and characterized by elementary analysis of their picrates,~1H-NMR, IR and MS. AMP did not polymerize with benzoyl peroxide (BPO), but could poly-merize with lauroyl peroxide (LPO). The rate equation of the polymerization was given as R_P=K_P [AMP]~(1.5)[LPO]~(0.5) and the overall activation energy of this polymerization system was 10.8Kcal/mol. The redox nature of LPO with the monomer itself was suggested. Even though AMP and MAMP hardly proceed the polymerization initiated with BPO, butunder lower concentration would form redox system with BPO to initiate the polymerization of MMAreadily. The rate equation of the polymerization of MMA initiated with MAMP-BPO systemwas given as R_P=K_P [MMA] [MAMP}~(0.5) [BPO]~(0.5) and the overall activation energy was 10.2Kcal/mol. The analysis of the obtained polymers confirmed that MAMP not only initiated the poly-merization of MMA by combining with BPO, but also took part in the polymer chains impartingthem with better biocompatibility. 相似文献
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<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 相似文献
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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 相似文献
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Fu-Mian Li Shuang-Ji Chen Zi-Chen Li Jian Qiu 《Journal of polymer science. Part A, Polymer chemistry》1996,34(10):1881-1888
Two novel acrylic monomers bearing aromatic tertiary amino groups, i.e., N-acryloyl-N′-phenylpiperazine (APP) and N-methacryloyl-N′-phenylpiperazine (MPP) are synthesized by the reaction of N-phenylpiperazine and the corresponding acryloyl chlorides in the presence of triethylamine. They can be polymerized easily by using AIBN as an initiator or photopolymerized without any sensitizer. The photochemical behavior of APP, MPP, and their polymers are explored by recording the fluorescence spectra in solution. It has been found that the fluorescence intensities of these monomers are dramatically lower than those of their polymers in the same chromophore concentration, and such phenomenon is termed as “structural self-quenching effect” (SSQE). The strong fluorescence of these polymers can be quenched by adding electron-deficient monomers which have no chromophore moieties such as MMA, AN, etc., and their Stern–Volmer constants are determined. It is observed that the higher the electron-deficiencies of the quenchers, the higher the Stern–Volmer constants, which means stronger quenching effect. The SSQE displayed by APP and MPP make them useful as probes to pursue their photopolymerization process. As polymerizable aromatic tertiary amines, APP and MPP themselves or combining with organic peroxides such as BPO can initiate the photopolymerization or thermal polymerization of vinyl monomers such as MMA, AN by free radical nature, and at the same time enter the polymer chain. © 1996 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 34:1881–1888, 1996 相似文献
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N-甲基-N-(2-甲基丙烯酰氧乙基)-对-甲苯胺对甲基丙烯酸甲酯聚合的影响 总被引:2,自引:2,他引:2
<正> 我们曾报道可聚合的芳叔胺N-甲基-N-(2-甲基丙烯酰氧乙基)苯胺(MEMA)与有机过氧化物如过氧化二苯甲酰(BPO)、过氧化二月桂酰(LPO)组成氧化还原引发体系用于甲基丙烯酸甲酯的聚合。虽然文献报道了N-甲基-N-(2-甲基丙烯酰氧乙基)-对-甲苯胺(MEMT)的合成,但没有研究它对甲基丙烯酸甲酯自由基聚合的影响。本文研究了MEMT对BPO或LPO引发MMA聚合的影响,从聚合动力学研究表明BPO/MEMT组成氧化还原引发体系。其引发机理与BPO/MEMA很相似。 相似文献
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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 Rp [MPP]0.48[AN]0.77 Rp [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. 相似文献
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有机过氧化物-芳叔胺体系引发甲基丙烯酸甲酯聚合的研究 总被引:1,自引:2,他引:1
以过氧化二酰(BPO、LPO)或有机过氧化氢物(TBH、CHP)和芳叔胺如DMA或对位具有不同取代基的衍生物组成的引发体系进行MMA聚合,研究过氧化物与胺的结构对聚合的影响。结果表明,过氧化二酰的活性要比有机过氧化氢物大,其顺序为BPO>LPO>CHP>TBH。对于BPO-芳叔胺或LPO-芳叔胺体系,芳叔胺中给电子取代基能提高聚合速度,而吸电子取代基能降低聚合速度。测定了MMA聚合的总活化能E_α,BPO-芳叔胺体系时E_α=36-54kJ/mole,LPO-芳叔胺体系时E_α=56-71kJ/mole;还研究聚合动力学。 相似文献