Kinetic modelling of the thermal oxidation of polyisoprene elastomers. Part 1: Unvulcanized unstabilized polyisoprene

The thermal oxidation of an unvulcanized, unstabilized polyisoprene rubber (IR) has been studied in the 40-140 °C temperature range. Ageing was monitored by FTIR determination of double bonds and carbonyl groups, mass uptake measurement, and weight average molar mass determination. A mechanistic scheme based on the standard scheme for radical chain oxidation, but taking into account the diversity of initiation processes and the existence of inter- and intramolecular radical additions to double bonds, was built. The kinetic model derived from this scheme is composed of seven differential equations to be solved in discrete thickness layers to take into account the kinetic control by oxygen diffusion. This system was numerically solved using a Matlab program dedicated to stiff systems of differential equations. The elementary rate constants and other kinetic parameters were then determined from experimental data, using an inverse approach. A set of physically reasonable parameter values was obtained, thus allowing us to envisage lifetime predictions at low temperature (long term). The results led to observations difficult to make from classical analytical studies, for instance the predominance of bimolecular hydroperoxide decomposition among other initiation modes or the competition between intermolecular hydrogen abstraction and intramolecular addition of peroxy radicals to double bonds.     

Kinetic modelling of the thermal oxidation of polyisoprene elastomers. Part 2: Effect of sulfur vulcanization on mass changes and thickness distribution of oxidation products during thermal oxidation

Thermal oxidation of sulfur vulcanized polyisoprene samples was studied by gravimetry and IR mapping of carbonyl groups (to determine the oxidized layer thickness (TOL)) at temperatures ranging from 60 to 150 °C in air. Oxidation appears noticeably lower than that for the starting non-vulcanized polyisoprene, revealing a stabilizing effect of sulfur-containing species. After a short period where mass loss presumably due to water evaporation predominates, the sample mass increases until a plateau corresponding to 6.3% (at 60 °C) to 0.5% (at 140 °C) mass gain. Practically no weight gain (∼0.1%) was observed at 150 °C. The mass uptake is due to oxygen grafting to the chains. TOL varies from about 4.6 mm (70 °C) to about 1 mm (150 °C).A kinetic model, derived from a mechanistic scheme of radical chain oxidation including stabilizing events due to hydroperoxide reduction by sulfur-containing groups and taking into account the diffusion-reaction coupling, was established and numerically resolved. The model predictions for mass changes and TOL values are in good agreement with experimental data.     

Synthesis of N,N-diethyldithiocarbamate functionalized 1,4-polyisoprene, from natural rubber and synthetic 1,4-polyisoprene

N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices.     

Nd（OPr~i）_2Cl－AlEt_3均相二元催化剂异戊二烯聚合动力学 Ⅱ．动力学参数的测定

用动力学方法测定了本体系不同温度下（３０℃，４０℃，５０℃）的平均增长链寿命τ，活性增长链浓度［Ｃ＊］，催化剂效率ＥＬＣＵ和绝对增长速度常数ｋｐ等主要动力学参数；求算了本体系增长反应活化能Ｅｐ＝５７．４ｋＪｍｏｌ．研究结果表明：该体系催化活性低的主要原因是其绝对增长速度常数太低．     

SYNTHESIS OF TRIBLOCK COPOLYMERS OF STYRENE AND ISOPRENE BY A NITROXIDE-MEDIATED LIVING FREE RADICAL POLYMERIZATION

The controlled free radical polymerization of styrene and isoprene initiated with benzoyl peroxide (BPO) in the presence of 2,2,6,6-tetramethyl piperidine-N-oxyl (TEMPO) at 125 ℃ were performed. The obtained polyisoprene and polystyrene homopolymers served as macroinitiators for block copolymerization of isoprene and styrene to synthesize poly(styrene-b-isoprene) and poly(isoprene-b-styrene) diblock copolymers. Diblock copolymers with well-defined structures as well as controlled and narrow molecular weight distribution wereobtained from the lower-mass polystyrene and polyisoprene homopolymers. These copolymers were found to be active as macroinitiators in the synthesis of the poly(styrene-b-isoprene-b-styrene) and poly(isoprene-b-styrene-b-isoprene) triblock copolymers. 1H-NMR spectroscopy and gel permeation chromatography (GPC) were used for the investigation of polymer strucmre, molecular weight and polydispersity (PD).     

三种不同基体中玻璃微球悬浮体系的流变行为

三种不同基体中玻璃微球悬浮体系的流变行为吴大诚，陈军武，徐建军，杜鹏，顾群，李玉景（成都科技大学纺织工学院成都６１００６５）关键词高分子流变学，Ｂｏｇｅｒ流体，悬浮体，聚异戊二烯悬浮体的流体动力学研究始于本世纪初，Ｅｉｎｓｔｅｉｎ“对极稀悬浮体粘度的...     

完全交替结构乙烯-丙烯共聚物的制备与表征

对顺-1,4含量为100%的高顺式聚异戊二烯(HCPI)进行加氢反应,得到了序列结构高度规整的乙烯-丙烯交替共聚物(alt-EP).所用的HCPI有适当的分子量(Mn=41×104)和极窄的分子量分布(Mw/Mn=1.02).HCPI的加氢反应以环烷酸镍和三异丁基铝为催化剂,在60℃和4.0MPa氢压的条件下反应3h,加氢产物的加氢度为100%.GPC测试结果显示所得乙烯-丙烯交替共聚物保持了窄分布的特点,表明HCPI加氢后未发生交联和降解反应;NMR,FTIR和广角X射线衍射测试结果表明此乙烯-丙烯交替共聚物具有高度规整的序列结构,为完全交替结构的乙烯-丙烯共聚物.并通过TGA和DSC对乙烯-丙烯交替共聚物的热性能进行了表征.     

Elastomeric Compounds with Silica. Lower Hysteresis in the Presence of Functionalised Isoprene Oligomers

Silica as reinforcing filler brings about a low hysteresis in elastomeric compounds. Aim of this work was to promote a better silica-elastomer interaction by using, as minor ingredients of a compound, isoprene oligomers having a functional group as the chain end. The effect of the functionality was investigated by analysing the complex viscosity of silica-oligomers binary mixtures as well as the morphological and rheological properties of masterbatches and compounds based on isoprene rubbers. A better silica dispersion and a lower Payne effect were clearly observed in the presence of functionalized oligomers.     

反式-/顺式-1,4-聚异戊二烯共混体系的结晶动力学

采用差示扫描量热(DSC)法对反式-/顺式-1,4-聚异戊二烯共混体系的等温及非等温结晶动力学进行了研究,分别采用Avrami方程和莫志深法对其动力学参数进行了解析.研究结果表明,在反式-/顺式-1,4-聚异戊二烯共混体系的等温及非等温结晶过程中,顺式-1,4-聚异戊二烯(CPI)组分的存在会降低反式-1,4-聚异戊二烯(TPI)组分的结晶速率;在等温结晶过程中,CPI组分会提高TPI组分自身的结晶度;而非等温结晶过程中,CPI则提高了共混物中β晶型的相对含量.     

稀土催化制备窄分子量分布高顺式聚异戊二烯及聚合反应动力学

由稀土羧酸钕盐(Nd)、三异丁基铝(Al)、含氯活化剂(CE)及醇(OH)组成的均相稀土羧酸盐催化体系,用于异戊二烯(Ip)定向聚合,其中含氯活化剂(CE)为氯代烃(CE1)或氯代羧酸酯(CE2).研究了CE和OH的化学结构及Al用量对Ip聚合及聚异戊二烯(PIp)微观结构、分子量及分子量分布的影响,将原位全反射傅立叶红外光谱(in situ ATR-FTIR)技术应用于研究稀土催化Ip配位聚合反应过程及聚合反应动力学,采用FTIR、GPC、NMR及DSC等测试手段表征PIp的微观结构、分子量及其分布、序列分布及热性能.实验结果表明,在稀土催化异戊二烯聚合反应中,少量的CE2和OH有助于提高催化活性、降低分子量分布和提高顺式含量.聚合速率对单体浓度呈现一级动力学关系,表观增长活化能(Ea)为69.5 kJ/mol.通过调节催化剂组分配比及聚合工艺条件,可制备出顺-1,4结构含量可达98%以上、窄分子量分布(Mw/Mn=1.6～2.4)的高顺式聚异戊二烯.