Cellulose propionate/poly(N-vinyl pyrrolidone-co-vinyl acetate) blends : dependence of the miscibility on propionyl DS and copolymer composition
Cellulose propionate/poly(N-vinyl pyrrolidone-co-vinyl acetate) blends : dependence of the miscibility on propionyl DS and copolymer composition
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丙酸纤维素/聚（N-乙烯基吡咯烷酮-共-乙酸乙烯酯）共混物：混溶性对丙酰 DS 和共聚物组成的依赖性
DOI：
10.1007/s10570-012-9797-y
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发表时间：
2013
期刊：
影响因子：
5.7
通讯作者：
Y. Nishio
中科院分区：
文献类型：
--
作者：
K. Sugimura;S. Katano;Y. Teramoto;Y. Nishio
研究了丙酸纤维素（CP）与n -乙烯基吡罗烷酮（VP）和醋酸乙烯酯（VAc）合成共聚物的共混性，并构建了CP和VP在共聚物组分中取代度（DS）的函数图。差示扫描量热法和傅里叶变换红外测量结果表明，CP/P（VP-co- vac）的配对根据以下因素的有效性平衡形成了一个可混相或不可混相的共混体系：(1)CP的残余羟基与P的VP羰基之间的氢键（VP-co- vac）；(2)丙基侧基对(1)中规定的相互作用的位阻；(3)构成乙烯基共聚物的两个单元之间的分子内斥力；此外，(4)分别涉及丙酰基团和VAc单元的两个片段之间的结构亲和性。诱导组分间相互吸引的因子3是在混相图中出现所谓“混相窗口”的原因，因子4大大扩大了混相区域的整体，相对于基于醋酸纤维素和丁酸酯的相应共混系列的图中的区域更宽。通过动态力学分析和固态13c NMR的t1ρ h定量进一步精细估计，发现氢键型共混物（使用DS < 2.7的CPs）在几纳米尺度上是完全均匀的，而位于窗口区域的聚合物对（使用DS > 2.7的CPs）形成的共混物表现出较大的非均匀性（约5-20 nm）。
Blend miscibility of cellulose propionate (CP) with synthetic copolymers comprisingN-vinyl pyrrolidone (VP) and vinyl acetate (VAc) units was examined, and a data map was constructed as a function of the degree of substitution (DS) of CP and the VP fraction in the copolymer component. Results of differential scanning calorimetry and Fourier transform infrared measurements indicated that the pairing of CP/P(VP-co-VAc) formed a miscible or immiscible blend system according to the balance in effectiveness of the following factors: (1) hydrogen bonding between residual hydroxyls of CP and VP carbonyls of P(VP-co-VAc); (2) steric hindrance of propionyl side-groups to the interaction specified in (1); (3) intramolecular repulsion between the two units constituting the vinyl copolymer; and, additionally, (4) structural affinity between two segmental moieties involving the propionyl group and VAc unit, respectively. The factor 3 inducing intercomponent attraction is responsible for the appearance of a so-called “miscibility window” in the miscibility map, and the factor 4 substantially expands the miscible region whole, wider relative to those in the maps for the corresponding blend series based on cellulose acetate and butyrate. In further refined estimation by dynamic mechanical analysis andT1ρHquantification in solid-state13C NMR, it was found that the miscible blends of hydrogen-bonding type (using CPs of DS < 2.7) were completely homogeneous on a scale within a few nanometers, whereas the polymer pairs situated in the window region (using CPs of DS > 2.7) formed blends exhibiting a somewhat larger size of heterogeneity (ca. 5–20 nm).