Inhomogeneity of hydrolytic polyamide 6 with respect to the average molecular mass

The point of view was advanced that in spinning fibres from polymer melts, the molecular inhomogeneity of the melts is not due to the polydispersity of the polymer but to important differences in the average molecular mass of the individual granules. Using the example of three industrial samples of hydrolytic PA 6, it was shown that the standard deviation of the average molecular mass of the polymer with respect to the individual granules from its mean statistical values is at the level of 10–11% for a practically significant (for up to several percent of granules) deviation of 30–50%. The use of samples of PA 6 with the mass provided by GOST 18245–72, OST 6-06-S9-76, and GOST 11034-82 in determining the viscosity a solution of the polymer in H₂SO₄ allows correctly estimating its average molecular mass but makes it impossible to obtain reliable information relative to the real degree of inhomogeneity of the granulate based on this index. Translated from Khimicheskie Volokna, No. 5, pp. 26–28, September–October, 2008.     

Synthesis of Ultra-high Weight Average Molecular Mass of Poly-L-lactide

High purity in high yield L-lactide was prepared using a new purification method, and poly-L-lactide (PLLA) with ultra-high weight average molecular mass and narrow polydispersity index was synthesized by ring-opening polymerization. The effects of the purification method on the purity and yield of L-lactide were investigated, and the influences of initiator concentration, polymerization temperature and polymerization time on the weight average molecular mass of PLLA were also studied. A synthetic purification method involving a water bath and two times recrystallization could improve the purity of L-lactide to 100%. The yield of L-lactide reached 40.6% and increased 12.1% compared with the recrystallization method. Poly-L-lactide with a weight average molecular mass of about 102.4 × 10⁴ and a polydispersity index of 1.16 was obtained when polymerization was conducted with molar ratio of monomer to initiator ([M]/[I]) of 12000 for 24 h at 140°C.     

提高转化率对乳聚丁苯橡胶性能的影响

以吉林石化公司有机合成厂的乳聚丁苯橡胶(SBR)生产配方为标准配方,研究了聚合反应时间对转化率的影响,分析了提高转化率对SBR的生胶门尼黏度、结合苯乙烯含量、凝胶含量、相对分子质量及其分布、胶乳黏度等基本性能的影响。结果表明,在标准配方条件下,延长聚合反应时间,转化率可以达到70%。转化率为70%时所得SBR与转化率为62%时所得SBR相比,前者的生胶凝胶含量和胶乳黏度均增大了1倍,数均相对分子质量、重均相对分子质量和Z均相对分子质量均高于后者,相对分子质量分布变宽,且前者的生胶结合苯乙烯含量能够达到产品标准,而生胶门尼黏度和在50 m in时的300%定伸应力偏高于产品优级品要求。     

蒲公英总黄酮在聚乙二醇-硫酸铵双水相体系中的分配与提取

蒲公英中内含的黄酮类物质具有较高药用价值,用双水相萃取法提取植物中有效成分是新型提取高附加值生物质的有效方法。本文考察了PEG/(NH4)2SO4双水相体系萃取分离蒲公英总黄酮时聚乙二醇相对分子质量、PEG质量分数、(NH4)2SO4质量分数、温度、pH值5个因素对分配行为的影响,并通过正交实验优化了工艺条件。结果表明最佳双水相提取工艺条件为：(NH4)2SO4质量分数18%,PEG1000质量分数23%,pH值5.34,提取温度25℃,NaCl盐的存在与否对萃取影响很小,蒲公英中总黄酮的提取率可达5.47%。因此,使用双水相法提取蒲公英总黄酮是该类提取技术中一种更加绿色环保和高效的方法。     

PET/PEG共聚酯连续熔融终缩聚过程两相稳态模型分析

针对高性能共聚酯PET/PEG缩聚过程,建立了圆盘反应器中连续熔融聚合两相稳态模型,模拟分析了缩聚反应温度、压力、停留时间以及传质系数对气相组成、共聚酯数均分子量、端羧基浓度以及副产物二甘醇和水浓度的影响。结果表明：挥发组分主要在反应器的前半部分产生,在z > 0.4后气相挥发总量已经很小;乙二醇占气相组成的比例极高,约为90%,而二甘醇的含量极低,只为0.5%左右;随反应器温度、真空度、停留时间、传质系数的增加,共聚酯产物的分子量增大,当传质系数大于0.1 s^-1后,反应器出口的共聚酯分子量几乎不再变化,此时已不受传质控制,最终产物的分子量约26000。     

一种新型聚醚离子液体电解质的制备和表征

以端羟基聚环氧氯丙烷(PECH)、N-甲基咪唑(NMIM)为原料,制备了一种新型的含端羟基的聚醚离子液体(NMIM-g-PECH)。考察了反应温度、反应配比、反应时间、接枝PECH的数均相对分子质量对反应接枝率的影响;用红外光谱和核磁共振氢谱对聚醚离子液体进行了结构表征;对聚醚离子液体的溶解性、电化学稳定性和离子导电性进行了分析。结果表明合成聚醚离子液体的较优工艺条件为:反应时间10h,反应温度40℃,n(PECH中氯甲基):n(NMIM)=1.0:1.8,PECH的数均相对分子质量为1000,此条件下反应接枝率可达82.3%;所得聚醚离子液体具有良好溶解性、电化学稳定性、离子电导性能,质量分数为5%的这种聚醚离子液体甲醇溶液室温电导率可达2.40×10-3S/cm。     

薄膜级EVA树脂的结构与性能

研究了两种薄膜级乙烯-乙酸乙烯共聚物(EVA)GN1和GN2的结构与性能,并在农膜生产厂进行了薄膜加工试验。结果表明:GN1和GN2均具有较高的相对分子质量,重均分子量分别比进口树脂高18%,15%;相对分子质量分布相对较宽,力学性能好,加工性能、耐老化性能优良;与功能母粒及其他树脂的相容性较好,综合性能与同类进口树脂相当。用GN2加工薄膜的过程中,温度对薄膜性能影响较小;随吹胀比增大,薄膜的横向拉伸断裂应力提高,纵向拉伸断裂应力降低。     

Emulsion polymerization of isoprene. Estimation of the branching exponent with the help of a mathematical model

This work investigates a batch and unseeded emulsion polymerization of isoprene at 10°C with n‐dodecylmercaptan as chain transfer agent (CTA). The obtained polyisoprene (PI) was analyzed by size exclusion chromatography (SEC) with on‐line viscometry. A global polymerization model was adjusted to the measurements of conversion, average particle size, and average molecular weights. The CTA concentration strongly affects the average molecular weights but has a negligible effect on conversion, average particle diameter, and average branching. Due to the combined effects of chain transfers to the polymer and to the CTA, the final molar mass distributions exhibited dispersity indexes higher than 10. The polymerization model predictions on the average degree of branching was combined with an ideal SEC model for adjusting the branching exponent of PI in tetrahydrofuran at 25°C that resulted ε = 2.5. A sensitivity analysis showed that +20% errors in _w induced variations in ε lower than ?10%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinetic Correlation for the Hindered Diffusion of Proteins in a Porous Packing Column*

Abstract Hindered diffusion of proteins in a porous packing plays an important role in proteinchromatographic purification.The HETP method was adopted to analyze the influence of axialdispersion, film mass transfer and hindered diffosion in the porous packing employing a size-exclusionchromatography(SEC)process.The retention behavior with eight proteins of different relativemolecular mass was experimentally detected with a commercial SEC column.A correlation basedon the relative molecular mass of the proteins and the packing porosity was developed and used topredict the effective diffusion coefficient of a protein in the Porous packing.The predicted valuesof effective diffusion coefficient were very consistent with the experimental results with the averageerror of 8.6%.     

相对分子质量对膦酰基聚丙烯酸阻垢率的影响

通过调节丙烯酸和亚磷酸的比例合成了一系列不同相对分子质量的膦酰基聚丙烯酸,并对其进行了纯化。同时研究了不同相对分子质量的膦酰基聚丙烯酸对碳酸钙的抑制能力。结果表明:聚合物相对分子质量太大或太小均对抑制碳酸钙垢不利,最佳的丙烯酸与亚磷酸的质量比为2∶1,粘均相对分子质量约3000,投加量4mg/L时阻垢率可达80%以上;较高的相对分子质量对提高聚合物抑制磷酸钙的能力有利,丙烯酸与亚磷酸质量比应大于4∶1,粘均相对分子质量应大于4000,投加量16mg/L时阻垢率可达50%。     

低聚GAP中引发剂残基的结构鉴定及其残余氯分析

为确定部分结构未知的工业级聚叠氮缩水甘油醚(GAP)中的残余氯含量,通过工业级低聚GAP(GAP-R)充分叠氮化制备了无氯低聚GAP(GAP-P)。采用电喷雾四级杆飞行时间质谱(ESI-Q-TOF-MS)、核磁共振定量碳谱(13C NMR)、傅里叶变换红外光谱(FT-IR)对GAP-R和GAP-P进行了精细的结构分析。确定了GAP-R中引发剂残基、残余氯含量、氯原子位置、平均聚合度和数均分子质量的分析方法。结果表明,GAP-R中引发剂残基为丙撑基,残留氯原子存在于GAP中间的结构单元上,氯含量为3.39%,平均聚合度为3.70,数均分子质量为439.57g/mol。     

现代分析技术解析未知聚合物的分子信息

概述了光谱、色谱和质谱等技术应用于未知聚合物分子信息的分析,介绍了各技术在分子组成、结构、相对分子质量及分布、端基、序列和构型等信息上的解析依据。     

Study of the reaction of maleic anhydride with Illinois bituminous coal

Maleic anhydride reacted with Illinois No. 6 bituminous coal (mf) at 200 and 250 °C resulted in a 22.5 and 39.3% increase in weight, respectively, which was based on the benzene-insoluble residue. The carboxyl group content of this coal residue, after it had been refluxed with water and demineralized, was 2.01 meq g^?1 (459% increase) at 200 °C, and 2.74 meq g^?1 at 250 °C (626% increase). If one assumes an average molecular weight of 2000 for bituminous coal, these results correspond to approximately 2 mol dienophile reacting with each mol of coal. Carboxyl group content of the insoluble coal residue was determined by the barium acetate method.     

固相缩聚PET相对分子质量及其分布研究

建立了 PET固相缩聚反应的数学模型 ,对相对分子质量及粒子内部相对分子质量的梯度分布的模拟与实验结果相符。实验假定粒子内任一微小体积元内聚合物的相对分子质量服从 F lory分布 ,计算产物相对分子质量多分散系数 MWD ,发现粒子内相对分子质量的梯度分布对产物相对分子质量分布的加宽无明显的贡献。认为相对分子质量分布的加宽是由于晶区被排除在反应体系以外造成的 ,且反应条件越苛刻 ,相对分子质量分布越宽。     

Synthesis of Poly-L-Lactide for Scaffold Materials by Melt-Solid Polycondensation

Poly-L-lactide (PLLA) with low viscosity average molecular mass for scaffold materials was synthesized by melt-solid condensation polymerization and characterized by IR, XRD, and ¹H-NMR. The influences of catalyst (LaCl₃/C₇H₈SO₃) concentration, polymerization temperature and polymerization time on the viscosity average molecular mass of poly-L-lactide acid (PLLA) were investigated. Poly-L-lactide with a viscosity average relative molecular mass of about 7.2 × 10⁴ was obtained when melt-solid polycondensation was conducted with first preheating at 110°C for 4 h and solid polycondensation at 150°C for 20 h; the catalyst concentration was 0.4 wt. %. PLLA was made into porous materials by using sodium hydrogen carbonate particulates as the porogen to foam. Scanning electron microscope observation indicates that the sample is highly porous and well distributed with good interconnections between pores and the pore size of porous materials in the range of 300–500 μm and it can be used as scaffold for bone tissue engineering.     

Thermogravimetric behavior of perfluoropolyether

In this article, two kinds of perfluoropolyether (PFPE) with different terminal groups were investigated using thermogravimetric analysis (TGA), infrared (IR) spectroscopy, gel permeation chromatography (GPC), and gas chromatography/gas mass spectrum (GC/MS) analysis. PFPEs with a hydroxyl or carboxylic acid terminal group were more heat stable than was PFPE with carboxylic methyl ester. Perfluoropropylene oxide-type PFPE with a perfluoroethyl terminal group at one end tends to lose weight more rapidly than does copolymer-type PFPE with dihydroxyl or dicarboxyl methyl ester terminal groups at both ends. The residual weight fraction of PFPE with a perfluoroethyl terminal group was dependent on the average molecular weight. The number-average molecular weight of PFPE can be calculated from the peak intensity ratio between the polar group and C F stretching by measuring the IR spectrum of PFPE. The number-average molecular weight of PFPE increased because of the evaporation loss of its low molecular weight fraction and the crosslinking reaction of PFPE with increase in temperature. GC/MS analysis showed that the main product of the pyrolysis of PFPE was hexafluoropylene. We speculated on the PFPE degradation mechanism and the optimum PFPE chemical structure in terms of heat stability. © 1996 John Wiley & Sons, Inc.     

单组分热固化聚氨酯涂料的合成及性能研究

以不同相对分子质量聚醚多元醇、甲苯二异氰酸酯、苯酚、2,2’-二氯-3,3’-二甲基-4,4’-二氨基二苯基甲烷等为主要原料合成了单组分热固化聚氨酯涂料,讨论了不同游离NCO含量、聚醚多元醇平均相对分子质量、扩链系数对涂膜的附着力、冲击强度、柔韧性、硬度、耐酸性、耐热性、耐低温性等各项性能的影响,同时研究了所合成涂料的贮存稳定性。结果表明,游离NCO质量分数在5%～6%、聚醚多元醇平均相对分子质量在600～700、扩链系数在0.85～0.90之间时,制得涂膜性能良好,涂料贮存稳定性好,使用方便。     

右旋糖酐-阿司匹林偶联物的合成

以右旋糖酐和乙酰水杨酰氯为原料,合成了高分子偶联物右旋糖酐 阿司匹林,并用FTIR、1HNMR对其结构进行了表征。考察了缚酸剂、右旋糖酐重均相对分子质量、反应温度和物料比对酯化反应的影响。结果表明,三乙胺和吡啶均可作为该酯化反应的缚酸剂,而浓氢氧化钠水溶液则不适合;乙酰水杨酰基的接入率随右旋糖酐重均相对分子质量的增大而减小,但随乙酰水杨酰氯与右旋糖酐的质量比的增加而增大;当选用Mw=20 000的右旋糖酐、缚酸剂三乙胺,反应温度在 60℃左右、m(乙酰水杨酰氯) /m(右旋糖酐 ) =3. 06时,乙酰水杨酰基的接入率和其有效转化率分别为 9. 30%和 3 .07%。     

预测复杂高沸点重质油馏分平均沸点的基团贡献法

采用超临界流体萃取分馏技术,在较低温度下(<250℃)将重质油分离成多个窄馏分,结合物性及¹H-NMR、¹³C-NMR分析确定其化学结构,构建重质油馏分的等价分子模型,并采用高温模拟蒸馏测定馏分的平均沸点至950K.以Rarey提出的预测纯化合物的基团贡献沸点新方法为基础,依据重质油馏分结构参数确定了12种基团类型,原模型基团贡献值保持不变.用原模型预测俄罗斯渣油馏分沸点,与C₅₀以下的馏分沸点实验值有较好的一致性,但对更重馏分误差大.对原模型沸点与总原子数的变化关系进行了修正,修正模型对两种不同基属原油的常压渣油和减压渣油馏分的沸点预测与实验值的平均误差为1.4%,同时能较准确估算高沸点正构烷烃的沸点,进一步验证了重质油馏分结构模型的合理性.结合改进的基团贡献法和超临界流体萃取分馏技术,可将重质油沸点预测延伸到1050K,碳原子数范围扩展到100个碳原子,为重质油馏分沸点估算提供了一种新的方法.     

端羧基聚苯乙烯的合成及其应用

以巯基乙酸为链转移剂,通过本体聚合得到低相对分子质量含端羧基的聚苯乙烯(PSCOOH),并将其用作聚苯乙烯(PS)/纳米CaCO3复合材料的分散改性剂。在链转移剂作用下可获得数均分子量约为850的PSCOOH。随着PSCOOH相对分子质量的减小,用它分散改性的PS/纳米CaCO3复合材料的拉伸强度提高,其中PSCOOH-4改性复合材料的拉伸强度提高了约15％,缺口及无缺口冲击强度略有下降。低相对分子质量分散剂有较好的增强作用。