Cs2SO4-C2H5OH-H2O三元体系30℃和50℃的平衡溶解度研究

The solubilities of Cs₂SO₄-C₂H₅OH-H₂O ternary system at 30℃ and 50℃ have been studied using microe-quipment for solubility determination. There appears two phases, alcoholic phase, water phase in the liquid phase. The solubilities of Cs₂SO₄ in water, C₂H₅OH and mixed solvent have been determined. The phase diagram indicated that C₂H₅OH might be salted out by Cs₂SO₄ from this system and the equilibrium solid phase is Cs₂SO₄.     

质谱新技术在高聚物分析中的应用

本文综述了高聚物质谱分析的基本类型和基本原理及其在高分子结构分析中的应用。     

碲在汞中的扩散系数和溶解度

用阴极溶出计时安培法测定了碲在汞中的扩散系数和溶解度.在1 mol/L NH_3-NH_4 Cl和10~(-3)mol/L TeO_3~(2-)溶液中,用悬汞电极于-0.90 V进行预电解,使Te(Ⅳ)还原到元素Te.然后在另一个电解池中阴极溶出使Te还原为Te~(2-).阴极溶出是在0.1 mol/L NaOH溶液中,用计时安培法于-1.40 V测定.根据下列方程式计算了碲在汞中的扩散系数D及溶解度S:D=r_0~2/πt_0,S=(4nFπ~(3/2)D~(3/2)t_0)~(-1)(Δi_1/Δt~(-1/2).D和S的测定值分别为:1.52×10~(-5)cm~2/s及2.34×10~(-3)wt％.实验结果表明碲在汞中以单原子态存在.     

钕铁合金在氯化钕熔盐中的溶解度

本文用电化学方法确定了钕铁合金在含氯化钕熔盐中的溶解度及其与温度、熔盐组成间的关系。所得的数据与急冷熔盐试样的化学分析法的结果有良好的一致性。     

傅立叶变换红外光谱法在高聚物分析中的进展

本文综述了漫反射傅立叶变换红外光谱法，傅立叶谱换红外光声光谱法，显微傅立叶变换红外光谱法，傅立叶变换红外光谱仪与各种仪器的联用，以及计算机技术等在高聚物分析中的应用。     

三元体系LiCl-LiNO3-H2O 273.15 K和323.15 K等温溶解度的测定

Solubility of the ternary system LiCl-LiNO₃-H₂O was measured at 273.15 K and 323.15 K by analyzing the equilibrated phase composition. Experimental result shows that there are three solubility branches at 273.15 K, corresponding to the solid phases LiCl·2H₂O，LiNO₃ and LiNO₃·3H₂O, respectively, while there are two solubility branches at 323.15 K, corresponding to the solid phase LiCl·H₂O and LiNO₃. The invariant point compositions are (1) 33.68wt% LiCl, 14.32wt% LiNO₃ and (2) 27.70wt% LiCl, 20.60wt% LiNO₃ at 273.15 K and (3) 39.07wt% LiCl, 16.89wt% LiNO₃ at 323.15 K. Also, the experimental results show that the solid phases in equilibrium with the solution {x(2.8LiCl+LiNO₃)-(1-x)H₂O} are LiNO₃·3H₂O or LiNO₃ at 273.15 K and LiNO₃ at 323.15 K.     

空气在二甲基硅油和液压油中的溶解度

对于诸多工程运用场合, 获得空气在硅油以及液压油中溶解度可靠的数据至关重要. 针对已有测量装置及方法的不足, 建立了一种基于理想气体状态方程来确定气体溶解量的新型精密活塞式装置. 获得了温度为293.2及353.2 K, 压力在0-350 kPa范围内, 空气在500cSt 二甲基硅油中的本生溶解度表达式. 测量了298.2 K时20cSt二甲基硅油及国产32#抗磨液压油在多种气相压力下的本生溶解度. 精度及可靠性分析表明实验数据的误差范围为6%. 本生溶解度与气相压力呈较好的线性关系, 以摩尔分数表示的溶解度与压力呈非线性关系, 但可用Krichevsky-Ilinskaya方程拟合. 发现空气在相对分子质量差异很大的两种二甲基硅油中的本生溶解度很接近, 由此提出, 对于小分子的非极性溶质在聚合物溶剂中的溶解度, 用聚合物单体的摩尔数而不是聚合物分子摩尔数来表示摩尔浓度更有利于实验数据的外推和工程应用. 对于相对分子质量差别较大或无法确定相对分子质量的溶剂, 工程应用中适宜采用本生溶解度.     

Rb2CO3—C2H5OH—H2O三元体系在40℃的溶解度及其应用

铷和铯是稀有分散的成盐元素,以往研究工作甚少,近年来铷和铯及其化合物在高新技术中的应用正受到人们的关注^[1]。钾、铷和铯的化学性质十分相似,尤其是铷与铯的分离和纯化难度很大,从矿物、盐卤和地热水资源中分离提取铷和铯的过程中,通常很难获得纯度较高的产品,开展铷盐纯化技术的研究具有重要的实际意义。混合溶剂用于盐类的分离和纯化,一直受到重视。文献^[2]中仅报道了对碱金属碳酸盐－醇－水在20℃时两相的分层关系,没有研究过饱和状态下的三相关系。根据碳酸铯在30℃乙醇中的溶解度比碳酸铷大5倍以上,我们采用国产碳酸铷商品作为试验物料,在测定了40℃时Rb2CO3-C2H5OH-H2O三元体系平衡溶解度相关系的基础上,进行简单的纯化处理,使该产品纯度得到进一步提高。     

Ln(ClO~4)~3-PCBAAP-H~2O系统在30℃时的溶解度研究

测定了两个三元系统Ln(ClO~4)~3-PCBAAP-H~2O(Ln=La,Yb;PCBAAP：4-(对氯苯酰基)氨基安替比林,C~1~8H~1~6O~2N~3Cl)在30℃时的溶解度,发现两系统各有一个组成为Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Yb,n=2)的不一致溶解化合物生成。参考系统的溶解度研究结果,合成了系列化合物Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Pr,Nd,Sm,Gd,Yb,n=2),通过化学分析及元素分析,IR光谱,TG-DTG,XRD和密度测定对其进行了表征。     

氯乙烯/邻苯二甲酸二烯丙基酯悬浮共聚特征

对４５℃时的氯乙烯／邻苯二甲酸二烯丙基酯（ＶＣ／ＤＡＰ）的悬浮共聚进行了研究，得到表观竞聚率ｒＶＣ＝０７６９、ｒＤＡＰ＝０３７４．凝胶点对应的ＤＡＰ临界起始浓度在０４６６～０４９３ｍｍｏｌ／ｍｏｌＶＣ之间（聚合转化率为８０～８５％），当ＤＡＰ起始浓度小于临界浓度时，ＶＣ／ＤＡＰ共聚物均为溶胶，溶胶平均聚合度随ＤＡＰ起始浓度和聚合转化率的提高而增大；当ＤＡＰ起始浓度大于临界浓度时，共聚物由溶胶和凝胶组成，凝胶含量随ＤＡＰ浓度和聚合转化率的提高而增加，溶胶聚合度则随ＤＡＰ浓度的提高而减小．在凝胶点前，共聚物的分子量分布随ＤＡＰ浓度的增加而变宽；凝胶点以后，分子量分布随ＤＡＰ浓度的增加而变窄．     

KINETICS OF VINYL CHLORIDE (CO) POLYMERIZATION AT HIGH CONVERSION

This paper provides a summarized review on the kinetics of vinyl chloride homopolymerization inthe absence and presence of chain transfer agents, of VC/DAP(diallyl phthalate) copolymerization with chainextension and/or slightly crosslinking functions, and of vinylidene chloride/VC random copolymerization.Models of rate, degree of polymerization or molecular weight, copolymer composition, gel fraction andcrosslinking density were proposed and interpreted mechanistically.     

PHASE EQUILIBRIUM FOR THE TERNARY SYSTEM VINYL CHLORIDE-CHLORINATED POLYETHYLENE-POLY(VINYL CHLORIDE)

Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.     

氯乙烯/N-苯基马来酰亚胺共聚物组成控制和优化

研究了氯乙烯 /N 苯基马来酰亚胺 (VC/PMI)共聚物组成随转化率的变化 ,体系中共聚物的累积组成偏差小于 0 0 5或 0 1的单体配比范围很小 ,采用加入第三单体丙烯腈 (AN)的方法进行改善 ,并以PMI在共聚物中的累积组成偏差作为控制参数 ,得到了PMI在共聚物中的累积组成偏差小于 0 0 5和 0 1的VC/PMIlAN较优的配比范围 .结合悬浮聚合工艺的特点 ,确定了VC/PMI/AN悬浮共聚的最佳单体配比范围为f1=0 72～ 0 84 ,f2 =0 0 2～ 0 0 4 ,f3 =0 1 2～ 0 2 4 .     

废聚对苯二甲酸乙二酯瓶片中氯乙烯共聚物的测定

采用加热显色法、傅立叶红外光谱法和称量法对废聚对苯二甲酸乙二酯中的氯乙烯共聚物进行定量检测。讨论了加热温度和加热时间对聚氯乙烯颜色和质量的影响,选择了样品加热处理的温度和时间。样品测定的平均回收率为99.8%。方法简单、实用、准确。     

PARTICLE MORPHOLOGY OF POLY(VINYL CHLORIDE)RESIN PREPARED BY SUSPENDED EMULSION POLYMERIZATION

Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.     

THE COMPATIBILITY OF BLENDS OF POLY(VINYL CHLORIDE) OR CHLORINATED POLY(VINYL CHLORIDE) WITH POLY(METHYL METHACRYLATE)

IR spectral shifts of carbonyl vibrational absorption for ethyl acetate, which acts analogically as the structural unit of poly(methyl methacrylate), in cyclohexane, chloroform, chlorinated paraffins, poly(vinyl chloride) and chlorinated poly(vinyl chloride) were measured. The results suggest that there are specific interactions between the carbonyl groups and the chlorinated hydrocarbons which could be responsible for the apparent compatibility of poly(vinyl chloride)—poly(methyl methacrylate) and chlorinated poly(vinyl chloride)—poly(methyl methacrylate) blends. Additionally, the effects of the preparation mode of blend films on phase separation and observed compatibility are discussed.     

聚苯胺在一些有机溶剂中溶解性

本文通过改变反应条件用化学方法制得了不同分子量的聚苯胺，考察了它们在有机溶剂中的溶解性．实验结果表明：分子量的大小是影响它们在有机溶剂中溶解度的主要因素，能在有机溶剂中溶解的只是聚苯胺中分子量较小的级分．我们还用聚苯胺（［η］＝０．４９ｄｌ／ｇ）与－ＣＯＣＩ封端的果对苯二甲酰对苯二胺（ＰＰＴＡ）进行嵌段共聚，经过产物的元素分析与计算结果比较，确定出特性黏数为０．４９ｄｌ／ｇ的聚苯胺平均分子量．     

季铵盐固相催化使聚氯乙烯脱HCl

通过将季铵盐与聚氯乙烯(PVC)混溶成膜,使其在固相脱HCl,研究了催化剂对PVC脱HCl反应速度和产物结构的影响以及固相反应与温度、时间的关系.发现在催化性能上下基铵盐比乙基铵盐好得多,根据实验结果提出了季铵盐通过分解成叔胺实现催化的机理.     

单体结构和聚合条件对大体积乙烯基聚合物旋光性质的影响

合成了3种手性大体积烯类单体——(+)-4,4″-二[(S)-2-甲基丁氧基]-2′-乙烯基对三联苯(p-BMVT)、(+)-3,3″-二[(S)-2-甲基丁氧基]-2′-乙烯基对三联苯(m-BMVT)和(+)-2,2″-二[(S)-2-甲基丁氧基]-2′-乙烯基对三联苯(o-BMVT),其中后两个为新化合物.系统研究了单体结构对其聚合反应活性以及单体结构和反应条件对所得聚合物旋光性质的影响.p-和m-BMVT在合适的条件下可以顺利地进行自由基聚合,形成某一旋向占优的手性二级结构;手性取代基在单体分子上移动一个共价键的距离导致聚合物的旋光方向相反.单体o-BMVT的合成产率低且不能进行自由基聚合.提高芳烃类或者降低非芳烃类聚合溶剂的极性、升高反应温度、减少单体浓度有利于得到旋光度大的聚合物.