加工方法对硫化天然橡胶结构与性能影响的研究

对天然胶乳及生胶所制备的硫化胶进行网络结构和性能测试 ,考察不同加工方法对硫化胶结构与性能影响。结果表明 ,胶乳胶膜的交联速率、效率、硫化胶强度及耐老化性能都比相应干胶的大 ;对普通硫化体系 ,生胶硫化胶的单、双硫键密度占总交联键密度的比例随硫化时间的延长有较大幅度增加 ,而配合胶乳胶膜的则变化不明显。     

羧基丁腈胶乳/羧基丁苯胶乳并用胶乳的性能研究

研究不同并用比羧基丁腈胶乳（XNBRL）/羧基丁苯胶乳（XSBRL）并用胶膜的性能以及考察并用胶乳的相容性。结果表明：XNBRL/XSBRL的并用比为90/10时,XNBRL/XSBRL并用胶膜的t90最短,并用硫化胶膜的交联密度较大、拉伸强度最大（33.8 MPa）以及溶胀指数最小（2.10）;XNBRL/XSBRL并用胶乳的粘度略大于XNBRL;随着XSBRL用量的增大,并用胶乳的机械稳定性变差,但变化幅度不大;XNBRL硫化胶膜和XNBRL/XSBRL并用硫化胶膜均仅有1个玻璃化温度,即XNBRL与XSBRL相容性很好,且XNBRL/XSBRL并用胶乳为均相体系;XNBRL/XSBRL并用硫化胶膜的XNBRL相与XSBRL相之间发生了化学键合,产生了共交联。     

氧化锌对硫化天然胶乳性能的影响

研究氧化锌对硫化天然胶乳胶膜和胶体性能的影响,考察在短期贮存中胶乳胶体的稳定性。结果表明,2种新型氧化锌与普通工业氧化锌的硫化胶膜和胶乳胶体性能相差不大,氧化锌用量在0.4～0.6份时胶膜性能最好。     

不同填料对丁苯胶乳硫化特性和力学性能的影响

通过不同种类填料按一定配方与丁苯胶乳配合,考察配合胶乳胶膜的硫化特性、硫化胶膜的物理机械性能.结果表明:填料滑石粉用量越多,胶膜的物理机械性能越差,硫化速度加快;CaCO3作为填料加到丁苯胶乳中时,硫化速度最快,胶膜的物理机械性能最好.     

复合保存剂对不同产地浓缩天然胶乳性能的影响

本文采用0.4%的氨与0.1%的HY复配保存不同产地浓缩天然胶乳(CNRL),研究了保存体系对CNRL保存效果的影响,测定预硫化胶乳粘度的变化及硫化胶膜物理机械性能。结果表明,对于不同产地CNRL,复合保存体系均可使保存效果得到一定程度提高;保存体系对预硫化胶乳粘度的变化无显著影响,并可以明显提高硫化胶膜的物理机械性能,且各产地提升幅度接近。研究结果为HY在橡胶工业中的推广与应用提供了参考。     

不同硫化体系天然胶乳胶膜的热氧降解过程及差异

用热重法，微商法重法和差热分析研究了不同硫化体系天胶乳胶膜的热氧降解过程。试验结果表明，胶乳胶膜的降解反应均分三步进行，但降解过程存在较大差异，过氧化物预硫化胶乳胶膜的热氧降解最为彻底，而硫黄／促进剂ＴＭＴＤ＝氧化锌体系硫化胶乳胶膜的热氧稳定性最好。     

不同硫化体系天然胶乳胶膜的热氧降解过程及差异

用热重法微商热重法（ Ｔ Ｇ Ｄ Ｔ Ｇ） 和差热分析（ Ｄ Ｔ Ａ） 研究了不同硫化体系天然胶乳胶膜的热氧降解过程。试验结果表明,胶乳胶膜的降解反应均分三步进行,但降解过程存在较大差异,过氧化物预硫化胶乳胶膜的热氧降解最为彻底,而硫黄／ 促进剂 Ｔ Ｍ Ｔ Ｄ／ 氧化锌体系硫化胶乳胶膜的热氧稳定性最好。     

天然胶乳/丁基胶乳并用胶乳的性能研究

采用完全随机化试验方法,研究天然胶乳/丁基胶乳并用比和硫化强化包用量（以干量计）对并用胶乳及其硫化胶膜性能的影响。结果表明：并用胶乳的粘度随着停放时间的延长而逐渐增大;并用胶乳硫化胶膜的气密性随着丁基胶乳占比的增大而呈提高趋势;当天然胶乳用量为100份、丁基胶乳用量为5.42份、硫化强化包用量为2.65份时,并用胶乳硫化胶膜的拉伸强度可达到24 MPa左右。     

胶膜的显微结构

用于检测干胶硫化胶联范围的电子显微技术,目前已被用于胶乳。此种方法涉及苯乙烯溶胀胶膜,再聚合苯乙烯。样品初切割后,用四氧化铁染色,再通过电子显微镜观察橡胶网状结构。与一种加硫的预硫化胶膜做比较时,显微照片显示的结果是在一种加硫的后硫化胶膜中粒间与粒间的交联比较高。他们同样显示,在干胶膜内可视橡胶网状结构的网状大小与该橡胶的交联密度有关。该技术问题揭示过氧化硫化胶乳（ＰＰＶＬ）内的交联分配明显的区别于使用硫化或辐射硫化胶乳内的交联分配。     

无氨天然胶乳性能研究

研究采用超速促进剂PX/硫黄/氧化锌硫化体系的无氨天然胶乳贮存性能、工艺性能、胶膜拉伸性能及自硫化机理。结果表明:无氨天然胶乳用异噻唑啉酮类衍生物保存剂对促进剂PX/硫黄/氧化锌硫化体系具有硫化协同效应;异噻唑啉酮类衍生物会使无氨配合胶乳在室温贮存时产生自硫化;适当调整促进剂PX/硫黄/氧化锌用量,可得到贮存性能、成膜性能和胶膜拉伸性能较好的无氨配合胶乳。     

Photo-vulcanization using thiol-ene chemistry: Film formation,morphology and network characteristics of UV crosslinked rubber latices

The photo-vulcanization with versatile thiol-ene chemistry represents an innovative approach to crosslink diene-rubber materials both in latex and in solid film state. In this work, the structure of elastomer-based thiol-ene networks and the morphology after film formation are studied in detail using electron microscopic techniques, atomic force microscopy and multiple-quantum solid-state NMR spectroscopy. Additionally, film formation properties and corresponding macroscopic properties of photo-vulcanized natural rubber (NR) latex and its synthetic counterpart, isoprene rubber (IR) latex, are determined in dependence on the curing procedure (pre- and post-vulcanization). The results reveal that thiol-ene cured elastomers comprise homogenously distributed crosslinks with a low amount of short chain defects. Whilst photochemically pre-cured NR latex particles provide coherent films, the film formation and mechanical properties of IR are strongly governed by the crosslink density of the latex particles. In film state, photo-vulcanization promotes narrow crosslink distributions and excellent tensile properties of both NR and IR.     

纳米氧化锌对天然胶乳膜干燥及硫化性能影响研究

采用失重法和溶胀法研究了普通氧化锌和纳米氧化锌活化的天然胶乳膜的干燥动力学,以及干燥过程中胶乳膜交联密度变化.结果表明:天然胶乳厚胶膜在成膜后仍含有大量水分并且去除困难.纳米氧化锌活化胶膜的干燥速率明显高于普通氧化锌胶膜.干燥温度对干燥过程影响显著,干燥时间随干燥温度升高明显降低.随着干燥的进行,2种氧化锌活化的胶乳膜的交联密度均迅速上升,在相同条件下,纳米氧化锌活化胶乳膜交联密度均比普通氧化锌的大.纳米氧化锌对天然胶乳膜的干燥及硫化过程均有促进作用.     

Transport of styrene monomer through natural rubber

The diffusion and transport of inhibitor-free styrene through crosslinked natural rubber (NR) have been studied at various temperatures. NR has been vulcanized by conventional, efficient, peroxide and mixed vulcanization techniques. The dependence of diffusion coefficient on the crosslinking system has been studied for all the systems. The influence of temperature on the sorption and the activation energies of sorption have been calculated. The interaction parameter, permeability, sorption coefficient and molecular weight between crosslinks have been evaluated using the diffusion data. The effect of degree of crosslinking on the sorption characteristics of styrene through NR has also been investigated for the different crosslinking systems. The peroxide system showed lowest uptake and the conventional system showed highest uptake.     

促进剂ZBEC对天然胶乳胶膜的硫化及力学性能的影响

研究了二苄基二硫代氨基甲酸锌(ZBEC)、二乙基二硫代氨基甲酸锌(ZDC)以及氧化锌(ZnO)和硫化温度对天然胶乳配合胶膜的硫化及力学性能的影响。结果表明,随着促进剂ZBEC、ZDC、ZnO用量的增加和硫化温度的提高,天然胶乳配合胶膜的硫化速度显著提高,且与ZDC相比,ZBEC略快。当ZBEC用量从0.5份增加到1.5份时,定伸应力、拉伸强度、撕裂强度先增加后减小。当ZDC用量从0.5份增加到1.5份时,定伸应力、拉伸强度随之增大,撕裂强度先增大后减小。随硫化温度的提高,以ZBEC为促进剂的硫化体系及以ZDC为促进剂的硫化体系的硫化胶膜的定伸应力、拉伸强度及撕裂强度均先增大后减小。     

氯化石蜡共混改性天然胶乳的研究

分别采用氯化石蜡、氯化石蜡／Sb2O3共混改性天然胶乳．考察了改性胶乳硫化胶膜的力学性能及阻燃性能．并进行了TG·DTG和DSC分析。结果表明：改性胶乳的阻燃效果比未改性天然胶乳的高．且氯化石蜡／Sb2O3共混改性天然胶乳可产生协同阻燃效果；随Sb2O3用量的增加．硫化胶膜撕裂强度增加．而拉伸强度下降。氯化石蜡／Sb2O3改性胶乳的热降解过程为二步反应．且起始热降解温度比天然胶乳的低．玻璃化转变温度提高。     

硫化温度对NR高温下拉伸／撕裂性能的影响

采用74个不同的硫化温度硫化NR,并测试其高温下拉伸／撕裂性能、交联密度和炭黑分散情况。结果表明：随测试温度的提高,NR的拉伸强度和撕裂强度均呈现逐渐下降的趋势,且在同-测试温度下,硫化胶的拉伸强度随着硫化温度的升高而逐渐降低;在测试温度小于100℃时,硫化胶的撕裂强度随硫化温度的升高而逐渐升高,测试温度大于100℃时,硫化胶的撕裂强度随硫化温度的升高而逐渐降低。     

Dual crosslinking of carboxylated nitrile butadiene rubber latex employing the thiol‐ene photoreaction

At present, the most common used crosslinking process for carboxylated nitrile butadiene rubber (XNBR) latex is an accelerated sulfur curing system with zinc oxide. To avoid allergenic reactions related to residual accelerator levels in dipped XNBR latex articles such as medical gloves, a dual curing process has been developed combining thermal and photochemical crosslinking reactions. The two‐step procedure involves the formation of covalent and ionic bonds to ensure good mechanical properties of the final products. The photochemical thiol‐ene reaction is used to generate covalent crosslinks between the remaining C?C double bonds of the butadiene units whereas the carboxylic moieties are conventionally cured with divalent metal oxides (ZnO) under elevated temperature (formation of ionic crosslinks). The photochemical curing step is carried out both in the latex phase using a falling film photoreactor (prevulcanization) as well as in the solid phase by UV irradiation of dried XNBR films (postvulcanization). The mechanical properties and crosslink densities of the cured XNBR films are determined and the influence of selected curing parameters is assessed. The results give evidence that a combined approach of thermal prevulcanization and photochemical postvulcanization makes the production of latex articles (e.g., gloves) with tailored properties and good skin compatibility feasible. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

两种品系天然橡胶的结构与性能研究

通过对比两种品系（热研7—33—97和热研8—79）的天然胶乳中橡胶粒子的粒度、生胶理化性能、相对分子质量及其分布以及硫化胶的性能，研究了两种品系天然橡胶的结构与性能。结果表明，热研7—33—97的胶乳粒度比热研8—79的小，胶粒分布窄；热研8—79的相对分子质量分布较热研7—33—97宽，其力学性能、耐老化性能及硫化胶稳定性均好于热研7—33—97。     

The Effect of Dicumyl Peroxide Vulcanization on the Properties & Morphology of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber Blends

ABSTRACT

This article discusses some properties such as tensile properties, chemical and oil resistance, gel content, crystallinity, and morphology of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends. Dicumyl peroxide (DCP) was applied as a crosslinking agent. In terms of tensile properties, peroxide vulcanized blend shows higher tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) as compared with the unvulcanized blend. The elongation at break of the peroxide vulcanized blend is higher for the blend with NR rich content compared with the EPDM rich content. The improvements in chemical and oil resistance as well as gel content of peroxide vulcanized blends have also proved the formation of crosslinks in the rubber phase. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the crosslinks have occurred during dynamic vulcanization. Dynamical vulcanization with DCP has decreased the percent crystallinity of blends that can be attributed to the formation of crosslinks in the rubber.     

Novel dynamic vulcanization of polyethylene and ozonolysed natural rubber blends: Effect of curing system and blending ratio

Dynamic vulcanization was studied in terms of the change in α‐relaxation temperatures of the LDPE matrix, morphology, and mechanical properties of LDPE/ozonolysed NR blends which were vulcanized at various blend ratios and with different curing systems, i.e., peroxide and sulfur systems. The ozonolysed NR with M _w = 8.30 × 10⁵ g mol⁻¹ and M _n = 2.62 × 10⁵ g mol⁻¹, prepared by the in situ ozonolysis reaction of natural rubber latex, was used in this study. The significant change in the α‐relaxation temperature of LDPE in the LDPE/ozonolysed NR, dynamically vulcanized using the sulfur system, suggested that sulfur vulcanization of the blend gave a higher degree of crosslink density than using peroxide and corresponded with the improved damping property and homogenous phase morphology. However, the peroxide cured blends of LDPE/ozonolyzed NR gave more improvement of tensile strength and elongation at break than the sulfur cured system. Furthermore, the mechanical properties of tensile strength, elongation at break, and damping were improved by increasing the ozonolyzed natural rubber content in both DCP and sulfur cured blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011