硫化天然橡胶的本征自修复与固相回收加工

通过小分子模拟试验和应力松弛,发现甲基丙烯酸铜(MA-Cu)比氯化铜(CuCl_2)更适合用作硫化天然橡胶中二硫键交换反应催化剂,并且硫化天然橡胶中的二硫键交换反应需要在高于120°C的温度下才能高效进行,这保障了相关制品在较低温工作时的结构与性能稳定.进一步的实验结果表明,硫化天然橡胶在MA-Cu辅助作用下获得了多次自修复与固相回收加工性能,损伤自修复后的硫化天然橡胶与固相回收加工的再生硫化天然橡胶,其拉伸强度均可恢复到原始材料强度的80%左右.     

橡胶弹性模型的新进展

传统橡胶弹性模型存在一定的局限性,例如不能真实地反映橡胶的交联网络结构,不能解释多个网络结构参数对橡胶力学性能的影响,也不能很好地描述大变形条件下橡胶的弹性.为了解决上述科学问题,崔树勋等提出了一个新的模型(TCQMG模型),在该模型中橡胶交联网络同时包含顺-1,4-聚异戊二烯和聚硫,并且高分子链的弹性同时包含了熵弹性和焓弹性.研究表明,新的模型不仅可以很好地描述硫化橡胶的弹性,还可以解释硫含量等参数对橡胶性能的影响.考虑到天然橡胶与其他橡胶甚至超分子水凝胶在网络结构上的相似性,新模型也可能用于描述这些材料的力学性能.     

High-temperature Thermo-oxidative Aging of Vulcanized Natural Rubber Nanocomposites: Evolution of Microstructure and Mechanical Properties

The aging of natural rubber(NR) at high temperatures will seriously affect its service lifetime in many key applications. In the present work, the changes in microstructure and mechanical properties of semi-efficient vulcanized NR/carbon black(CB) vulcanizates during thermooxidative aging at high temperatures(150-200 °C) and a moderate temperature(95 °C) were compared. At high temperatures, a two-stage aging behavior, which was characteristic of a first rapid decline and then a continuous rise i...     

丁腈橡胶/聚氯乙烯/酚醛树脂/受阻酚AO60共混阻尼材料研究

主要研究了丁腈橡胶(NBR)/聚氯乙烯(PVC)/酚醛树脂(PR)/受阻酚AO60共混体系中PR、AO60和增塑剂癸二酸二丁酯(DS)的用量对硫化橡胶力学性能和阻尼性能的影响。在共混体系中添加不超过50phr的AO60,其硫化胶损耗因子-温度曲线仍呈现单峰特征,体系相容性良好。随着AO60含量的增加,硫化胶的玻璃化转变温度提高,阻尼峰值增大。拉伸强度及动态模量先随之增高,然后降低。随着PR含量的增加,硫化胶的拉伸强度随之增加,tanδ峰值温度升高,而阻尼峰值则先提高后降低。加入增塑剂,硫化胶的力学性能、储能模量及玻璃化转变温度都有不同程度的降低。     

Morphology and Mechanical Properties of Palm Based Fly Ash Reinforced Dynamically Vulcanized Natural Rubber/Polypropylene Blends

Palm based fly ash (PFA) is a solid waste of palm oil processing industry which contains silica components. These components are typically used to improve the mechanical properties of rubber-based products. This research aims to study the effect of the PFA as a filler on the morphology and properties of thermoplastic vulcanizate (TPV) based on a mixture of natural rubber (NR) and polypropylene (PP). TPV samples were prepared using the internal mixer at a mass ratio of NR/PP 70/30. Maleated polypropylene (MA-g-PP) 5% mass was added as a compatibilizer, filler content was varied from 15 to 45 per hundred rubber (phr). Paraffin and palm oil were added as a plasticizer with contents of 5 to 50 phr. Other additives include ZnO 5 phr, stearic acid 2 phr, trimethylquinone 1 phr, mercaptodibenzo-thiozyldisulfide 0.6 phr and 3 phr sulfur. The results showed that the use of PFA provides good tensile strength properties, a relatively homogeneous morphology, and low water absorption rate. The use of paraffin plasticizer produces a higher tensile strength compared to palm oil, but the elongation at break which produced the contrary. The best morphology and tensile properties of TPV (NR/PP 70/30) are on PFA and paraffin contents of 30 phr and 25 phr, respectively.     

Study on Dynamic Vulcanized EPDM/PP Thermoplastic Elastomer

Based upon the THE,HAAK RHEOCORD 90 and Wx-ray observation,a study was made on the structure and property of ethylene-propylene-ethlidene norborene (EPDM)/polyprolene (PP) blending systems ,and the experimental results were fully explained. (1) The effect of Mooney viscosity (ML)of EPDM、 melt flow rate(MFR) of peroxide(DCP) and mixing steps on mechanical properties of EPDM/PP blends was studied. The results showed that the mechanical and process properties of EPDM?PP thermoplastic elastomers were better using EPDM with the ML of 60 and PP with MFR of 7.5g/10min as matrix,DCP with the content of 1.2 per cent with the help of twostep curing process at the temperature of 170-175 ℃.     

Surface Modifications Produced by N2 and O2 RF Plasma Treatment on a Synthetic Vulcanized Styrene-Butadiene Rubber

A low-pressure gas RF plasma-treatment has been used to improve the adhesion of a synthetic vulcanized rubber to polyurethane adhesive as an environmentally friendly alternative surface treatment to the conventional chemical treatments. A sulfur vulcanized styrene-butadiene rubber (R2) containing a noticeable amount of zinc stearate and paraffin wax (both providing a lack of adhesion) in its formulation was used. Two different gases (oxygen and nitrogen) were used to generate the RF plasma, which was performed at 50 Watt for 1–15 min. The modifications produced on the R2 rubber surface by the RF plasma treatments were assessed by using advancing and receding contact angle measurements, ATR-IR spectroscopy, X-ray Photoelectron Spectroscopy (XPS), Scanning Force Microscopy (SFM), and Scanning Electron Microscopy (SEM). Adhesion evaluation was obtained from T-peel tests of joints produced between plasma treated R2 rubber and a polyurethane adhesive. The plasma treatment produced a decrease in advancing and receding contact angle values on R2 rubber, irrespective to the gas used to generate the RF plasma. The treatment with RF plasma produced the partial removal of hydrocarbon moieties from the rubber surface and the generation of oxygen moieties. An increase in surface roughness was also produced. The degree of oxidation and the amount of hydrocarbon-rich layer removed from the R2 rubber surface was more important by treating with oxygen plasma. The treatment of rubber in oxygen plasma for 1 minute was enough to noticeably increase adhesion of R2 rubber to polyurethane adhesive. However, an extended treatment (15 min.) was needed when nitrogen plasma was applied to R2 rubber. The loci of failure in the joints produced between the plasma treated R2 rubber and the polyurethane adhesive was assessed by using ATR-IR spectroscopy. A mixed failure (partially adhesional and partially cohesive failure in the rubber) in the joints produced with plasma treated R2 rubber joints was always obtained.     

Influence of Carbon Black,Calcium Carbonate and Dioctyl Phthalate Compositions on the NBR Vulcanized Rubber Properties Through Experiments Design

Summary: In industrial practice involving mixtures of raw materials, it is desirable to be able to predict how a change in their proportions will affect the product's properties. In this work the effect of three major vulcanized rubber raw materials was investigated. All other raw materials, as well as processing conditions, were kept constant. Ten formulations were vulcanized by compression moulding (175 °C, ∼17 MPa, during 5 minutes) and characterized. The statistically valid property equations calculated from the characterization results show that a range of compositions exists within which the final product has the desired properties and can still be comfortably manufactured.     

三元乙丙橡胶的13C-NMR定量分析

用13C核磁共振波谱法对三元乙丙橡胶进行了研究，通过图谱中各个峰的积分值，并用特定的计算公式测定了三元乙丙橡胶中乙烯及第三单体乙叉降冰片烯的含量，为红外光谱批量的定量分析建立了基准化的标定。     

A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques

A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative was carried out using NMR spectroscopy techniques. The overlapping ¹H-NMR signals of ENR-50 at δ 1.56, 1.68-1.70, 2.06, 2.15-2.17 ppm were successfully assigned. In this work, the ¹³C-NMR chemical shift assignments of ENR-50 were consistent to the previously reported work. A cyclic dithiocarbonate derivative of ENR-50 was synthesized from the reaction of purified ENR-50 with carbon disulfide (CS₂), in the presence of 4-dimethylaminopyridine (DMAP) as catalyst at reflux temperature. The cyclic dithiocarbonate formation involved the epoxide ring opening of the ENR-50. This was followed by insertion of the C-S moiety of CS₂ at the oxygen attached to the quaternary carbon and methine carbon of epoxidized isoprene unit, respectively. The bands due to the C=S and C-O were clearly observed in the FTIR spectrum while the ¹H-NMR spectrum of the derivative revealed the peak attributed to the methylene protons had split. The ¹³C-NMR spectrum of the derivative further indicates two new carbon peaks arising from the >C=S and quaternary carbon of cyclic dithiocarbonate. All other ¹H- and ¹³C-NMR chemical shifts of the derivative remain unchanged with respect to the ENR-50.     

NMR对苯并噁嗪类化合物结构的研究

利用'H、'13CNMR谱及HMBC、HMQC二维谱对10种苯并噁嗪类化合物的结构进行了研究,初步得出了它们的NMR谱特征,分析了化学位移的影响因素。     

聚丙烯／顺丁橡胶动态硫化共混物的交联行为和结晶性能的研究

研究了聚丙烯／顺丁橡胶动态硫化共混物橡胶相的交联行为、动态硫化共混物的结晶行为和结晶结构。结果表明，顺丁橡胶的加入对ＰＰ的熔点无明显影响，但结晶度降低。动态硫共化共混物在低于熔点处另有一熔化转变。动态硫化使共混物中ＰＰ的结晶速率提高。     

Study of the Impact Resistance of Physically and Dynamically Vulcanized Mixtures of PP/EPDM

Physically and dynamically vulcanized (TPV) mixtures of polypropylene (PP) and ethylene propylene diene terpolymer (EPDM) are prepared by extrusion in order to improve the impact resistance of PP. To enhance the chemical compatibility and provide better interaction between the PP and EPDM in the physical mixtures, both polymers are modified with maleic anhydride (MAH) in solution using xylene as solvent and dicumyl peroxide (DCP) as initiator. The qualitative and quantitative determination of the degree of grafting is study by Fourier Transform Infrared Spectroscopy (FTIR) and varying the amount of DCP and/or amount of MAH in order to determine the optimum amounts to obtain the highest degree of grafting. The effect of the relation of PP/EPDM, the amount of reinforcement filler and mix rate are studied for modified polymer mixtures (PP-g-MAH/EPDM-g-MAH). For the TPV of PP/EPDM the effects of amount and triallylisocyanurate (TAC) as coupling agent in presence of different amounts of DCP are studied. The physical mixtures of modified polymers prepared with a PP/EPDM ratio of 80/20 and the TPVs blends prepared with a PP/EPDM ratio of 70/30 and containing 15% filler at 60 rpm show the highest impact resistance. The impact resistance, melt flow index and hardness of the different mixtures are measured to determine their possible applications to prepare front panels and bumpers for automobiles by injection molding.     

动态硫化EPDM／PP共混体系中PP相的结晶度及晶体结构的研究

研究了动态硫化ＥＰＤＭ／ＰＰ共混物中ＰＰ相的结晶度及晶体结构,同时讨论了制备工艺条件以共混物中ＰＰ相的结晶度和晶体结构的影响。结果表明：在动态硫化ＥＰＤＭ／ＰＰ共混物中,硫化的ＥＰＤＭ的分子键没有穿入ＰＰ的晶区,ＰＰ的结晶度随ＥＰＤＭ含量的增加而下降。提高共混温度,加入软化剂或碳黑均使共混物中ＰＰ的结晶度降低,共混时间１５ｍｉｎ时,共混物中ＰＰ相的结晶度最低,但ＰＰ的晶格不受制备工艺条件的影响。     

硫化类聚乙炔电池的研究

用硫化类聚乙炔材料作正极活性物质,锂为负极,2 mol/L LiClO_4的二氧戊环溶液作电解液,制成了二次电池.对电池的性能进行了研究.实验结果表明,此电池具有很高的比能量,按正极活性物质计算高达1500～2000 W·h/Kg.     

Preparation and Study of Epoxidized Natural Rubber

Epoxidized natural rubbers (ENRs) with different extents of epoxidation (B) were prepared under various reaction conditions. The effects of the amount of H₂O₂ and the reaction time on B are discussed. The glass transition temperature T_g, the thermal degradation temperature and the activation energy of thermal degradation of the ENRs increase with B. The results indicate that the thermal stability of the ENRs increases with B.This revised version was published online in November 2005 with corrections to the Cover Date.     

Characterization of the Chemical Structure of Sulphur Vulcanizates of Natural Rubber Using 1H NMR Spectroscopy

Abstract

Vulcanizates containing only di- and poly-suiphidic crosslinks can be transformed into soluble rubber by treatment with hexane-1-thiol/piperidine, enabling examination of the crosslink sites by ¹H NMR spectroscopy in solution.     

Spectroscopic Study of Di-Imide Hydrogenation of Natural Rubber

The diimide hydrogenation of natural rubber (NR) was studied by using p-toluenesulfonylhydrazide (TSH) as a diimide-releasing agent. The microstructure and the percentage of hydrogenation were studied by Raman, ¹H-NMR and ¹³C-NMR spectroscopic techniques. Quantitative measurements on fraction of hydrogenated part gave the results in good agreement by using these techniques. The results indicated that percent hydrogenation increased with increasing of reaction time and about 80-85 % hydrogenation was achieved when a two-fold excess of TSH was used. The vibrational characteristic of C=C bond of NR is strongly Raman active and noted at 1663 cm⁻¹. The decrease of this signal was clearly observed during the progress of hydrogenation but the vibrational frequency of the cis and trans structures of the trisubstituted olefin unit of NR can not be differentiated by this technique. While ¹H- and ¹³C-NMR analysis showed that cis-trans isomerization of carbon-carbon unsaturation of NR occurred during hydrogenation.