胶乳粒子之间的静电作用

胶乳粒子之间的静电作用与各种胶乳体系的稳定性研究及胶乳微细化机理的探讨均有关联．从胶乳粒子的最简化模型着手，用Ｄｅｒｊａｎｇｕｉｎ近似法处理球型胶乳颗粒之间的相斥作用，计算了具有相同尺寸的两球型胶乳颗粒之间的静电排斥势能，作为进而使用其他种类模型研究胶乳颗粒之间静电作用的第一步．     

应用电子显微镜测定丁苯吡胶乳和丁苯胶乳中胶乳粒子的平均粒径及粒径分布

丁苯吡胶乳和丁苯胶乳粒子的直径一般在1000(?)以下,这样微小的粒子,只有用电子显微镜才能看清它的形态和外貌。我们用电子显微镜观察丁苯吡胶乳及丁苯胶乳中的胶乳粒子,测定了胶乳粒子的平均粒径及粒径分布,为改进工艺、提高质量提供了资料。实验方法简介如下:     

国内外天然浓缩胶乳品质差异性分析

由于橡胶树品系、种植气候与土壤、田间管理以及加工工艺等因素的影响导致国内外天然胶乳品质存在较大差异。本文选取国产海南宝岛牌、海南美联牌、茂名广垦-1、阳江广垦-2、进口泰国黄春发和泰国三棵树的浓缩胶乳,比较分析其分子量及其分布、橡胶粒子粒径、脂肪酸种类及含量、金属离子含量、Zeta电位、机械稳定性和挥发脂肪酸的差异。结果表明,国产胶乳相对分子质量较低,分子量分布较宽;进口胶乳平均粒径较大,粒径分布相对较窄;进口胶乳中不饱和脂肪酸及饱和脂肪酸含量均高于国产胶乳;黄春发牌胶乳的Ca2+、Mg2+、Zn2+浓度较低,Zeta电位绝对值较大,其胶乳稳定性较好;贮存过程中进口胶乳机械稳定度较高,胶乳挥发脂肪酸值较低。     

关于天然胶乳应用性质的几个基本問題

天然胶乳是天然橡胶的胶体水分散体系。近年来,国内外胶乳工业发展十分迅速。从胶乳直接制成气象气球、探空气球、海棉制品、手套、胶管、各种卫生用品等几百种制品。从二十世纪三十年代到现在世界天然胶乳的产量已增加三十倍。随着胶乳工业的发展世界各国天然胶乳应用性质与应用理论的研究在不少方面也有了一定的进展,这些工作不仅对胶乳工业具有重要的意义,而且对于高聚物分散体系学科的发展也有相当的影响。     

合成胶乳和人造胶乳外科手套发展概况

橡胶外科手套用于无菌手术室的操作,是使用量较大的乳胶手套品种之一.天然胶乳外科手套拥有较好的综合性能而应用历史悠久,但天然胶乳含有过性敏蛋白质,部分医护人员对天然胶乳外科手套产生过敏症,推动了无蛋白质过敏风险的合成胶乳外科手套和以合成橡胶通过乳化工艺转化而得的人造胶乳外科手套的发展.以羧基丁腈胶乳为主要原材料加工而成的...     

橡胶胶乳的硫化——Ⅰ.胶乳硫化基本规律的初步探讨

本文系统地研究了胶乳种类、胶乳浓度、硫化温度、硫磺用量以及促进剂用量等五个主要因素对天然胶乳硫化过程的影响,并且阐明了在硫化过程中胶乳胶膜物理性能、结合硫量以及橡胶交联度之间的相互关系。 实验结果说明,胶乳中非橡胶成分在硫化初期不仅不促进硫化而且还阻碍硫化进程,在硫化的中期与后期它的促进效果才明显地显示出来。非橡胶成分含量愈高其硫化胶乳胶膜物理性能愈低。在一定范围内随着胶乳浓度的降低硫化速度稍有增加。随着硫化温度的升高胶乳硫化速度将相应加速,但在我们使用的硫化体系条件下温度过低与过高时其对硫化速度的影响减弱,最适宜的硫化温度是60—70℃。硫磺用量增加到一定程度后它对胶乳硫化速度即不再产生影响,在胶乳硫化过程中所能达到的结合硫量远远低于硫磺在橡胶中的溶解度。在通常用量下促进剂S.D.C.用量愈大其硫化促进效果亦愈大,在用量为0.125—0.25％之间其促进效果有一明显的转折。 硫化胶乳胶膜性能与橡胶交联度及结合硫量之间有一定的依赖关系。各种不同的影响胶乳硫化的因素都不改变这一依赖关系。在胶乳硫化过程中硫磺的交联效率是不恒定的,胶乳在硫化时主要是形成多硫键。在胶乳硫化时结合硫磺中的相当一部分并不对交联键的形成作出贡献。 胶乳硫化动力学基本     

硫化胶乳的研究——硫化天然胶乳的离子沉积法凝胶及胶膜的物理性能

本文研究了硫化胶乳离子沉积过程,着重探讨了硫化胶乳离子沉积凝胶及胶膜的性能。 胶乳硫化程度的不同,对其沉积速度影响不大,后者主要取决于胶乳的胶体性质,而与胶乳粒子内部橡胶的结构状况关系不大。硫化天然胶乳的沉积动力学与非硫化胶乳相似,可用q=0.01070 t~(1/3) 式近似地表达(式中q为橡胶沉积量,t为沉积时间)。 随着硫化程度的增加,离子沉积凝胶性能亦随之增高,只是当硫化达到相当程度时凝胶性能始下降。这一特异规律可以用凝胶中粒子间交联分子链节及末端的相互扩散及交联结构的部分重分布来解释。 离子沉积法制得的硫化胶乳胶膜性能的变化规律与凝胶相同。     

顶空固相微萃取/气相色谱-质谱法检测胶乳中痕量甲苯的研究

合成胶乳是合成橡胶的一个重要组成部分,而合成胶乳中丁苯胶乳又占主导地位。丁苯胶乳是由丁二烯(B)和苯乙烯(S)经过乳液聚合得到的一种固体含量为30％～50％的水性乳液。由于这种水性乳液具有橡胶的韧性,所以作为增强剂被广泛应用于造纸、涂料、纺织、建筑和粘合剂等各个领域,与人们的生活环境密切相关。对于胶乳性能的研究和改进也吸引了研究者的注意。但是生产原料如苯乙烯中普遍含有甲苯,所以造成胶乳产品含有痕量的甲苯,对人们健康形成潜在的威胁。     

热老化对丁苯胶乳体系机械稳定性的影响

研究了热老化处理对丁苯胶乳体系机械稳定性的影响.发现丁苯胶乳在高温老化过程中,胶粒容易团聚并形成凝胶,老化处理温度越高,凝胶出现时间越短,但是它的机械稳定性却随着老化处理时间的延长和老化处理温度的升高反而不断提高.为了阐明这种异常现象,测试了不同老化处理温度下胶乳的粒子尺寸、剪切作用下的凝胶比率、丁苯分子的结构与分子量分布,以及胶粒的力学强度随老化时间的变化规律,分析了影响机械稳定性的可能因素.结果表明,胶乳体系中丁苯分子在高温老化过程中发生了轻度的交联反应,导致胶乳干膜的300%定伸模量提高.进一步研究还发现,这个定伸模量与胶乳的机械稳定性具有对应关系,胶乳干膜的定伸模量越大,胶乳的机械稳定性越高,因此造成机械稳定性大幅上升的主要原因很可能是热老化交联后刚性较大的胶粒在高速剪切碰撞时难以及时融合.     

天然胶乳中蛋白质和磷脂对橡胶分子结构的影响

采用碱性蛋白酶和磷脂酶处理天然胶乳,制备脱蛋白胶乳和脱脂胶乳,结合原子吸收光谱仪、核磁共振交联密度仪、凝胶色谱(GPC)等仪器对处理前后的天然胶乳进行了分析。通过对比分析,发现酶处理后胶乳分子量降低,分子量分布变宽,金属离子浓度、凝胶含量和交联密度均降低。结果表明,金属离子与天然橡胶中的蛋白质、磷脂间存在着物理的或化学的作用力;蛋白质、磷脂在天然橡胶中起到节点的作用,有利于形成分子间交联,增大天然橡胶分子量,形成分子间网络结构。     

偏氯乙烯-氯乙烯悬浮共聚物的结晶与熔融性能

研究了聚合温度、共聚物组成、低分子助剂用量等对偏氯乙烯 (VDC) 氯乙烯 (VC)悬浮共聚树脂的结晶度、熔融峰温度的影响 ,并用Florry的聚合物熔点降低理论预测共聚树脂熔点随共聚组成、低分子助剂用量的变化规律 ,为VDC VC悬浮共聚树脂的合成工艺条件和加工性能的改善提供理论基础 .     

Effects of acrylonitrile water solubility on limiting conversion and copolymer composition in suspension polymerization

The effects of acrylonitrile (AN) water solubility on the limiting conversion and copolymer composition of the AN and AN/vinylidene chloride (VDC) suspension polymerization were investigated. It was found that AN dissolved in aqueous phase does not transfer back to oil phase in AN suspension homopolymerization but partially does in AN/VDC suspension copolymerization, and thus the limiting conversion is lowered and decreases with water/oil ratio increasing in both AN and AN/VDC suspension polymerization. For the continuous transport of AN in aqueous phase to oil phase during suspension polymerization, the composition distribution of AN/VDC copolymer prepared by suspension polymerization is narrower than that by bulk polymerization. The calculated composition of AN/VDC suspension copolymer with considering AN water solubility is consistent with the experimental data.     

Determination of gelation dose of a vinylidene chloride/acrylonitrile copolymer irradiated with gamma-rays by a spectrophotometric technique

The gelation dose of a vinylidene chloride (VDC)/acrylonitrile (AN) random copolymer irradiated with γ-rays in vacuum is first determined by conventional techniques, such as viscometry and solubility. The onset of gelation was determined to be 5.8 Mrad for this copolymer of composition 20% AN/80% VDC. The same gelation dose is also determined by a spectrophotometric method which is based on the recording of u.v.-vis spectra of solutions of this copolymer in THF. The advantages of this new technique for determination of gelation dose over the conventional methods are discussed.     

偏氯乙烯-丙烯腈悬浮共聚物的组成研究

研究了偏氯乙烯 丙烯腈 (VDC AN)悬浮共聚体系中AN的水溶性对单体相组成和树脂组成的影响 .结果表明 :由于AN部分地溶于水 ,使有机相AN的含量降低 ,导致共聚树脂的组成明显地不同于本体聚合模型的计算预测值 .为了准确地计算预测VDC AN共聚树脂的组成 ,本文假设溶于水的AN向有机相迁移的速度比聚合反应速度快得多 ,AN在两相的溶解分配近似为平衡态 .计算中先用描述AN在VDC/水系统中溶解分配的Marker式校正有机相AN的含量 ,然后根据校正后的AN含量用Mayo Lewis式计算预测VDC AN悬浮共聚物的组成 ,计算中有关的竞聚率值取自于文献中本体聚合的值 .计算结果与实验值一致     

Composition of vinylidene chloride/phenylacetylene (VDC/PA) copolymers and vinylidene chloride/methyl acrylate/phenylacetylene (VDC/MA/PA) terpolymers from analysis by 13C-NMR spectroscopy

¹³C-NMR spectroscopy has been utilized to characterize Saran polymers containing polyene segments generated by incorporating phenylacetylene (PA) units into either poly(vinylidene chloride) (PVDC) or a typical Saran copolymer of 91% vinylidene chloride (VDC) and 9% methyl acrylate (MA). The incorporation of PA could not be defined in the usual statistical way because the presence of the PA double bond in the polymer backbone appeared to cause the dehydrohalogenation of units next to it. Thus, sequences of PA next to VDC were not observed. Rather, sequences of olefinic units next to VDC units were present at a level equal to the level of PA incorporation. The level of unsaturation in the PA copolymers is approximately four times the level of PA incorporation. These observations are consistent with the random incorporation into the copolymer of PA which then initiates the dehydrohalogenation in adjacent VDC units. This dehydrohalogenation reaction appears to propagate from one unit to the next along the backbone of the polymer such that polyene segments containing the PA unit are formed.     

高阻隔材料——偏氯乙烯悬浮共聚树脂

本文介绍偏氯乙烯悬浮共聚树脂的优异阻隔性能、合成配方与工艺。     

THE EFFECT OF MONOMERS FEEDING METHODS ON EMULSION COPOLYMERIZATION OF VINYLIDENE CHLORIDE AND ACRYLATES

The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.     

Preparation and characterization of novel thermal-stable vinylidene chloride–methyl acrylate–glycidyl methacrylate copolymer

A novel copolymer was synthesized by vinylidene chloride (VDC)/methyl acrylate (MA)/glycidyl methacrylate (GMA). The Fourier transform infrared (FTIR) and ¹H-nuclear magnetic resonance analyses indicated that the copolymer of VDC/MA/GMA (PVMG) was synthesized successfully. The influences of GMA on the molecular weight, melting point, and thermal stability of copolymer were investigated by gel permeation chromatograph, differential scanning calorimeter, thermogravimetric analysis–FTIR, respectively. The copolymerization eliminated the phenomenon of “double melting peaks” for poly(vinylidene chloride), and the melting point was reduced to 165°C. The GMA also enhanced the thermal stability of copolymer, which was proved by the increased decomposition temperature of copolymer. The existence of GMA caused the cross-linking of the copolymer, which contributed to the improvement of barrier performance of PVMG.     

BARRIER PROPERTIES OF VINYLIDENE CHLORIDE COPOLYMERS

The permeability coefficients of a series of copolymers of vinylidene chloride (VDC)with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer)to oxygen and carbon dioxide have been measured at 1.0 MPa and 30℃, while those towater vapor have been measured at 30℃ and 100% relative humidity All the copolymersare semicrystalline. VDC/MA copolymers have lower melting temperature compared withVDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higherthan that of VDC/acrylate copolymers with the same VDC content. The barrier propertyof the copolymers is predominantly controlled by crystallite, free volume fraction, andcohesive energy The permeability coefficients of VDC/MA copolymers to oxygen, carbondioxide, and water vapor were successfully correlated with the ratio of free volume tocohesive energy.     

Core–shell morphology as a model for the study of gas permeation in composite systems

Structured latex particles prepared by emulsion polymerization were used as a model to simulate the interphase region between two phases. Multiphase polymer films comprised of high and low permeability polymers of various compositions were used. The model system consisted of a poly(n-butyl methacrylate) (PBMA) matrix and a discontinuous phase with core and shell morphology. The structured particle had a PBMA core and a vinylidene chloride – n-butyl methacrylate (VDC–BMA) copolymer shell. The shell transport characteristics wer altered by changing the (VDC–BMA) copolymer molar ratio. The physical and transport properties for each individual component were measured. Nitrogen was the probe gas. Films used for permeation experiments were prepared by latex casting. The results showed that the morphology of a heterogeneous polymeric system and the transport characteristics of their components had a considerable effect on the magnitude of the transport properties. Experimental data also showed the dependence of the gas global permeability coefficient on the nature of the simulated interphase region, the shell, and the weight percentage of such interphase in the heterogeneous polymeric films. Upon increasing the VDC content in the VDC–BMA copolymer, the gas permeability decreased. The data were fitted to the electrical analogs of conductivity in composite systems. For the matrix filled with structured particles the overall permeability coefficient could best be described when the individual permeabilities were considered as the inverse resistances in parallel.