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The rate of copolymerization of vinyl chloride (VC) with sulfur dioxide and the composition of the poly (vinyl chloride sulfone) formed have been measured for comonomer liquid mixtures with XVC = 0.1 to 1.0 and over the temperature range -95 to +46°C. Polymerization was initiated by γ-irradiation (-95 to +46°C) and with the t-butyl hydroperoxide/SO2/methanol redox system (-95 to -18°C). The copolymerization rates and copolymer compositions indicated two distinct temperature regions, with a change in mechanism around 0°C. For radiation initiation below 0°C, the rate versus comonomer composition relationship showed a maximum at an xVC value which increased with increasing temperature. Above 0°C, the rate decreased with increasing temperature and was greatly retarded by SO2. No high molecular weight copolymer or VC homopolymer was formed on irradiation of comonomer mixtures above ~55°C. 相似文献
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CO2基塑料(PPC)是通过CO2与环氧丙烷共聚所得的生物降解高分子,由于PPC的耐紫外老化性能较差,随紫外线的照射不仅PPC的相对分子质量快速下降,且其拉伸强度和断裂伸长率等力学性能也迅速降低,而农用地膜长期处于紫外线照射的环境中,因此亟待改善PPC的耐紫外老化性能。 本文设计合成了含紫外吸收基团的单体2-羟基-4(2,3-环氧丙氧基)二苯甲酮(HEB),与CO2和环氧丙烷进行三元共聚制备了耐紫外光老化的CO2共聚物(PPCH)。 在保证PPCH相对分子质量不低于5.0×104的前提下,PPCH中HEB单元的摩尔分数最高可达0.32%,相应地其玻璃化转变温度(Tg)和起始热分解温度(Td-5%)分别为26.7和216.9 ℃,拉伸强度达到30.97 MPa。 普通PPC经过240 h的紫外辐照后,其数均相对分子质量下降了67.8%,相应地其拉伸强度和断裂伸长率分别下降了10.1%和40.1%。 即使PPCH中的HEB摩尔分数仅为0.06%,经过240 h辐照后其数均相对分子质量仅下降了6.2%,相应地其拉伸强度和断裂伸长率也仅分别下降了1.7%和13.3%,证明PPCH具有较强的耐紫外老化性能,原因在于其主链含有HEB单元,对紫外光具有较好的吸收性能。 PPCH的紫外吸收性能随HEB单元在聚合物中含量的增加而增强,因此随着共聚物中引入的HEB单元含量增加,PPCH的相对分子质量和力学性能的保持率均得到了大幅度提高。 另一方面,对PPCH共聚物与相同二羟基二苯甲酮(BP)含量的PPC/BP共混物进行120 h的50 ℃热水萃取实验,PPCH显示出稳定的紫外光吸收性能,而PPC/BP共混物的紫外吸收性能随热水萃取时间的增长而快速下降,表明三元共聚反应能够有效解决普通共混物面临的小分子紫外吸收剂的外迁移问题。 相似文献
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Chunliang Li Dr. Rafaël J. Sablong Prof. Dr. Cor E. Koning 《Angewandte Chemie (International ed. in English)》2016,55(38):11572-11576
The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2) catalyzed by a zinc β‐diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain. Moreover, polycarbonates bearing pendent cyclic carbonates can be quantitatively prepared by CO2 insertion catalyzed by lithium bromide. 相似文献
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铝卟啉是一类土壤环境友好的金属卟啉,尽管早在1978年Inoue就已经发现它可以催化CO2和环氧丙烷的共聚反应,但是该催化体系一直面临催化活性低、聚合物相对分子质量低等难题。 本文通过改变铝卟啉催化剂配体中苯环上取代基的种类和位置,制备出中心金属电子环境差异化的铝卟啉,并以双三苯基膦氯化铵(PPNCl)为助催化剂,探讨其对CO2与环氧丙烷的共聚反应的催化行为。 结果表明,当铝卟啉中苯环上2,4位同时被Cl-取代后,在90 ℃和3 MPa压力下,转化频率(TOF)达到2672 h-1。 当利用离去能力较强的对甲苯磺酸基团(OTs-)作为铝卟啉的轴向配体,可以合成出数均相对分子质量达1.84×105的脂肪族聚碳酸酯。 相似文献
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以超临界二氧化碳为介质, 进行丙烯酸与苯乙烯共聚反应, 合成出具有疏水链段结构的改性丙烯酸聚合物. 研究了压力和投料比对聚合反应的影响. 用红外光谱、紫外光谱和核磁共振谱分析其结构及组成. 采用粘度计测定其水溶液粘度随pH值的变化. 研究结果表明, 该聚合物水溶液具有明显的疏水缔合作用. 相似文献
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ABSTRACT Previously unknown substituted chelate phenolatoaluminum chloride, (25,27-dimethoxy-p-tert-butylcalix[4]arene-26,28-diolato) aluminum chloride, was derived from the reaction of diethyl-aluminum chloride and 25,27-dimethoxy-26,28-dihydroxy-p-tert-butylcalix[4]arene at reactants 1:1 mole ratio. It was applied successfully for the polymerization of propylene oxide and cyclohexene oxide, and their copolymerization with carbon dioxide, leading to respective oligomers and co-oligomers. The catalyst structure and the structure of the obtained low-molecular-weight polymers and copolymers were studied using NMR spectroscopy. Poly(propylene oxide) obtained in the presence of the studied catalyst appeared to contain isotactic diads predominantly, whereas the obtained poly(cyclohexene oxide) did not exhibit any significantly prevailing sequences of either isotactic nor syndiotactic diads. The polymerization mechanism has been proposed and discussed in view of the obtained results. 相似文献
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二氧化碳是一种廉价、低毒、资源丰富的可用于有机合成的理想原料。由二氧化碳和环氧化合物共聚合成的脂肪族聚碳酸酯具有生物可降解性。自1969年井上祥平等发现二氧化碳和环氧化合物通过共聚反应合成脂肪族聚碳酸酯以来,利用二氧化碳制备高分子材料一直备受人们注目。该过程的关键是寻找具有高选择性的高效催化剂,三十余年来通过各国科学家的不懈努力已取得了不少成果,本文对其研究的最新进展进行了综述。 相似文献
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Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide 下载免费PDF全文
Yuan‐Zhao Hua Liu‐Jie Lu Pei‐Jin Huang Dong‐Hui Wei Prof. Ming‐Sheng Tang Prof. Dr. Min‐Can Wang Prof. Dr. Jun‐Biao Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12394-12398
A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO2 under very mild conditions (1 atm CO2, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high Mn value of 28 600 and a relatively narrow polydispersity (Mw/Mn ratio) of 1.43 were also achieved. 相似文献
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探讨了有机金属催化剂的组成及其对二氧化碳同环氧丙烷交替共聚产物结构的影响,发现二乙基锌—助剂体系的催化活性按如次顺序递降:二乙基锌—连苯三酚>二乙基锌—间苯二酚>二乙基锌—对苯二胺>二乙基锌—亚乙基脲。若用三异丁基铝代替二乙基锌同连苯三酚构成催化剂,则失去对二氧化碳同环氧丙烷交替共聚反应的活性同时,著者发现二乙基锌—二元芳胺催化体系与二乙基锌—二元酚催化体系的催化活性规律完全不同。 相似文献
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The ring-opening alternating copolymerization processes of epoxides with small-molecule monomers, such as carbon dioxide(CO2), carbonyl sulfide(COS) and cyclic anhydrides, are powerful strategies for preparing polymeric materials with degradable carbonate/ester/thiocarbonate main-chain backbone units. The catalysts selected for copolymerization processes play crucial roles in determining their reaction rates and productivities, as well as the selectivity, regio-and stereochemistry, co... 相似文献
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Summary: In-line Fourier Transform – near infrared (FT-NIR) spectroscopy is a very elegant method to follow conversion as well as phase behaviour throughout a reaction. It was applied to two examples of homogeneous phase syntheses of fluorinated copolymers in supercritical carbon dioxide (scCO2). The conventional free radical copolymerization of vinylidene fluoride (VDF) and hexafluoropropene (HFP) on the one hand side, and the Activators Generated by Electron Transfer (AGET) Atom Transfer Radical Polymerization (ATRP) of F-decene (1H-1H, 2H perfluoro-1-decene) and tBA (tert-butyl acrylate) on the other hand side were studied. Poly(VDF-co-HFP) were synthesized at 75 and 100 °C at pressures above 800 bar to remain in solution, even at high VDF contents. The reactivity ratios, r, were determined from a small number of experiments using the entire conversion vs. time data from in-line FT-NIR measurements. The estimated values are rVDF = 4.3 and rHFP = 0.1. In the case of poly(F-decene-co-tBA), a fluorinated macroligand was introduced for AGET ATRP. Molecular weights between 10000 and 40000 g/mol and polydispersities between 1.1 and 2.1 were obtained while remaining in homogeneous phase. Reactivity ratios were determined as rF-decene = 0.02 and rtBA = 9.1. 相似文献
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Polymer-supported zinc catalysts were prepared by the reaction of di-ethylzinc with polymers containing carboxyl groups. The catalysts were employed in the alternating copolymerization of carbon dioxide and propylene oxide to give poly(propylene carbonate) of high molecular weight. Copolymers of styrene and acrylic acid were shown to be better catalyst supports than poly(acrylic acid) and some other polymers. Maximum activity was achieved when the molar ratio of Zn/COOH was around unity. The yield and molecular weight of the polycarbonate rose with increasing reaction time. Higher reaction rates but lower molecular weights of the product were observed at elevated reaction temperatures 相似文献