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光敏剂存在下3,4-聚异戊二烯的光交联反应 总被引:1,自引:0,他引:1
本文研究了在敏化剂二苯甲酮存在下3,4-聚异戊二烯的光交联反应。发现在80W高压汞灯辐照下,二苯甲酮敏化的3,4-聚异戊二烯能够发生光交联反应,其凝胶含量、交联密度与光照时间、3,4-聚异戊二烯的分子量以及二苯甲酮的用量有关。用FTIR和C13NMR证实了该交联反应以外双键的2+2加成为主。 相似文献
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三、聚二烯的結构与性能 1,4-聚异戊二烯的结构与物理机械性貭已經熟知,顺-1,4-聚合物相当于天然橡胶,反-1,4-聚合物相当于古塔布胶(杜仲胶)。3,4-聚异戊二烯已经制出,性能研究未见发表。 相似文献
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结晶3,4-聚异戊二烯的合成 总被引:6,自引:0,他引:6
<正> 非结晶的3,4-聚异戊二烯的合成已有一些报道,本文则采用合铁的三元催化体系:三乙酰基丙酮铁-含氮给电子试剂-三异丁基铝,可使异成二烯聚合得到高3,4-链节含量,高分子量以及高熔点的结晶聚合物。 1.试剂及聚合反应 异戊二烯为聚合级产品,用前经常压蒸馏除去阻聚剂后,用活性氧化铝浸泡48小时 相似文献
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Fe(acac)_3-Phen-AlEt_3 催化体系可使异戊二烯聚合成以 3,4-链节为主具有一定结晶性能的聚异戊二烯。本文对该聚合物的~(13)C-NMR 谱进行了全分析,研究了序列分布、微观结构。结果表明不同方法求得的微观结构含量很好地一致,说明对~(13)C-NMR 谱峰归属的正确性。并指出顺-1,4/3,4-序列中存在着头-头,尾-尾的连接方式,3,4-嵌段链节不足够长及存在反节可能是结晶度不太高的主要原因。 相似文献
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本文对二苯甲酮敏化前后3,4-聚异戊二烯-2,6-双(4′-叠氮苄叉)环己酮体系的光交联反应进行了研究。证明了该体系的光交联反应以双氮烯和被二苯甲酮活化的大分子的外双键加成为主。 相似文献
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在紫外光作用下,二苯甲酮、蒽醌和安息香能通过夺氢反应使异戊二烯在四氟乙烯-丙烯共聚物中接枝,接枝反应按三重态自由基引发机理进行,接枝率随光照时间的增长而增加,但不会超过40%。和异戊二烯的自由基聚合反应不一样,接枝物中聚异戊二烯接枝链的微结构以3,4-和1,2-聚合为主,而前者以1,4-聚合为主。Ce+4及Fe+2-H2O2等氧化还原体系对该接枝反应不产生作用.极性溶剂四氢呋喃的加入,对接枝链微结构的影响很小。 相似文献
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It has been presumed in studies of the orientation of low-density polyethylene and its time dependence that the degree of crystallinity remained constant with elongation and did not vary with time following elongation. This paper represents a test of this hypothesis by several methods. The change in crystallinity accompanying stretching has been followed by a modification of an x-ray method for uniaxial orientation proposed by Ruland in which diffraction peaks are resolved into crystalline and amorphous components and their respective areas are determined by two-dimensional integration over both the Bragg angle and the azimuthal angle of diffraction. The weight-fraction crystallinity is then determined from the ratio of the weighted crystalline area to the total area. There appears to be no significant variation in crystallinity up to 50% sample elongation for both slowly and rapidly stretched samples at room temperature. The dynamic crystallinity change accompanying small amplitude vibration has also been determined by the dynamic x-ray diffraction technique and found to be negligible over a wide range of frequency. The degree of crystallinity has also been evaluated from the absolute infrared absorbance of crystallinity-sensitive bands and has also been found to be independent of elongation at room temperature up to 80% elongation. Changes have also been observed by this method during relaxation at constant length following rapid extension and have also been found to be negligible. These results also indicate negligible changes in rotational isomer population. Consequently, we conclude that changes observed during relaxation and vibration arise from orientational changes rather than changes in the degree of crystallinity. 相似文献
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Copolymerization of butadiene and isoprene catalyzed by the catalyst system V(acac)_3-Al(i-Bu)_2Cl-Al_2Et_3Cl_3 has been studied. Composition, microstructure, crystallinity and melting point of the copolymer obtained were determined by PGC, IR, X-ray diffraction and DSC methods respectively. The results revealed that the product was a copolymer and not a blend. The butadiene units presented in the copolymer were of trans-1,4-configuration, while the isoprene units were of both trans-1,4-and 3,4-forms. The melting point and crystallinity of the copolymer decrcascd with increase of molar ratio of isoprene to hutadiene. 相似文献
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The dynamic mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends have been evaluated with special reference to the effect of blend ratio. It has been found that increasing the proportion of LLDPE in the blends decreases the Tg values and increases the storage modulus (E′) and loss modulus (E′′) due to increase in crystallinity. A gradual increase in the values of tanδmax is observed for the blends with increase in EPDM-g-VOS concentration, which indicates that no phase inversion occurs. But however the higher increase in tanδmax after 50 wt.% of EPDM-g-VOS composition is due to small change in crystallinity and is ascertained by SEM micrographs. Mechanical properties such as tensile strength, Young’s modulus and hardness increase with increases in LLDPE concentration in the blends and with dicumyl peroxide (DCP) concentration whereas the values of elongation at break are decreased with increase in LLDPE and DCP concentration. 相似文献
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Influence of multiple processing on selected properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) 下载免费PDF全文
Krzysztof Moraczewski 《先进技术聚合物》2016,27(6):733-739
The effect of multiple (up to 10 times) injection molding of processed poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3,4HB)) on its phase transition temperatures, degree of crystallinity, degradation temperature, mass flow rate, mechanical properties, dynamic mechanical properties, and Charpy's impact strength is presented. The studies have shown that the multiple injection lowers the degree of crystallinity and the thermal stability of P(3,4HB). The mass flow rate values increased with increasing the injection number. It was found that the multiple injections had no substantial effect on the tensile strength up to 10 injection cycles and the tensile strength at break, tensile strain at tensile strength, and tensile strain at break up to 6 injection cycles. The maximum value of storage modulus at 30 °C and impact strength were recorded for sample after 4 cycles of injection, while the values of storage modulus at 120 °C increased with increase of the injection cycles. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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The effect of crystallinity of polylactide (PLA) on the structure and properties of tough PLA blends with PEG-b-PPG-b-PEG block copolymers was studied. PLA was melt blended with a set of the copolymers with varying ratio of the hydrophilic (PEG) and hydrophobic (PPG) blocks. Although the blend phase structure depended on the copolymer molar mass and PEG content, as well as on the copolymer concentration in the blend, crystallinity also played an important role, increasing the copolymer content in the amorphous phase and enhancing phase separation. The influence of crystallinity on the thermal and mechanical properties of the blends depended on the copolymer used and its content. The blends, with PLA crystallinity of 25 ÷ 34 wt%, exhibited relatively high glass transition temperature ranging from 45 to 52 °C, and melting beginning above 120 °C. Although with a few exceptions crystallinity worsened the drawability and toughness, these properties were improved with respect to neat crystalline PLA in the case of partially miscible blends, in which fine liquid inclusions of the modifier were dispersed in PLA rich matrix. About 20-fold increase of the elongation at break and about 4-fold increase of the tensile impact strength were reached at a small content (10 wt%) of the modifier. Moreover, crystallinity decreased oxygen and water vapor transmission rates through neat PLA and the blend, and the barrier property for oxygen of the latter was better than that of neat polymer. 相似文献
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Nanocrystallites, acting as physical cross-links in Nafion membranes, play a crucial role in building blocks for improving mechanical durability and stopping fuel crossover. However, Nafion membranes suffer from low crystallinity due to the irregular pendent side chains, which hinder self-aggregation of the poly(tetrafluoroethylene) (PTFE) backbones. For the first time, a molecular gelator was introduced in the membrane casting process to enhance the rate of self-assembly of PTFE backbones so as to increase the membrane's crystallinity as well as proton conductivity without sacrificing the purity of Nafion. The molecular gelator used was 3,4-dimethylbenzaldehyde (DMBA). Addition of 0.5 wt % DMBA led to a 42% increase in crystallinity, a 32% increase in yield strength, a 22% increase in tensile modulus and an 18% increase in proton conductivity at 60 °C and 90% relative humidity. Additionally, the membrane electrode assembly (MEA) prepared from the membranes cast from the solution containing 0.5 wt % DMBA also showed an increase of 17% in maximum power density in comparison to the MEA prepared from pure Nafion membrane in a single cell polarization test without any external humidification. Transmission electron microscopy (TEM) and molecular dynamics simulation were used to elucidate the structural changes in Nafion membrane due to the introduction of DMBA. It was observed that the presence of DMBA gives wider crystalline regions under TEM. The molecular dynamics simulation at 500 K shows that the PTFE backbones become elongated in the presence of DMBA due to the enhanced mobility. This is consistent with the observed increase in crystallinity in the membrane as it means reduced entropic change upon crystallization. 相似文献
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Flamigni L Ventura B Tasior M Becherer T Langhals H Gryko DT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(1):169-183
The bichromophoric systems C2-PI, C3-PI, and C3-PPI consisting of corrole and perylene bisimide units and representing one of the rare cases of elaborate structures based on corrole, have been synthesized. Corroles C2 and C3 are, respectively, meso-substituted corroles with 2,6-dichlorophenyl and pentafluorophenyl substituents at the 5 and 15 positions. The three dyads were prepared by divergent strategy with the corrole-forming reaction as the last step of the sequence. C2-PI and C3-PI differ in the nature of the corroles, whereas C3-PI differs from C3-PPI in the presence of a further phenyl unit in the linker between photoactive units. The dyads display spectroscopic properties which are the superposition of the component spectra, indicating a very weak electronic coupling. Excitation of the corrole unit leads to charge separation with a rate which decreases from 2.4 x 10(10), to 5.0 x 10(9), and to 4.9 x 10(7) s(-1) for C2-PI, C3-PI, and C3-PPI, respectively, where the reaction is characterized by a delta G degrees >0. Excitation of the perylene bisimide unit is followed by competing reactions of: 1) energy transfer to the corrole unit, which subsequently deactivates to the charge-separated state and; 2) electron transfer to directly form the charge-separated state. The ratio of electron-to-energy-transfer rates is 9:1 and 1:1 for C3-PI and C3-PPI, respectively. The yield of charge separation is essentially 100 % for C2-PI and C3-PI, and approximately 50 % (excitation of peryleneimide) or 15 % (excitation of the corrole) for C3-PPI. The lifetime of the charge-separated state, observed for the first time in corrole-based structures, is 540 ps for C2-PI, 2.5 ns for C3-PI, and 24 ns for C3-PPI, respectively. This is in agreement with an inverted behavior, according to Marcus theory. 相似文献