The composition and morphology of epoxidized trans‐1,4‐polyisoprene obtained by heterogeneous synthesis method

The aim of this study is to analyze the structure and morphology of epoxidized trans‐1,4‐polyisoprene (ETPI) obtained by water phase suspension epoxidation. With this objective, the range of epoxy group content of ETPI from 0 to 25 mol% was used. The Fourier transform infrared spectroscopy indicated that the dissoluble parts separated by ethyl acetate were epoxidized molecular chain while the insoluble parts were unreacted TPI segment. In addition, gel permeation chromatography has been used to research the change of the relative molecular weight and the the molecular weight distribution due to the effect of epoxy group content. The decrease of molecular weight states that there have small amounts of chain scission in the epoxidation reaction process. DSC data proved that the glass transition temperature raised because of the increase in rotating free energy. The decrease of ΔH_m, ΔH_c, and T_c indicated that crystallinity and the rate of crystallization are reduced. The mechanical properties of ETPI showed that the tensile strength and hardness reduced gradually. Finally, a morphological study of ETPI has been completed using phase contrast microscope and scanning electron microscopy. POLYM. ENG. SCI., 54:1260–1267, 2014. © 2013 Society of Plastics Engineers     

Multiple shape memory effects of trans‐1,4‐polyisoprene and low‐density polyethylene blends

A novel series of shape memory blends of trans‐1,4‐polyisoprene (TPI) and low‐density polyethylene (LDPE) were prepared using a simple physical blending method. The mechanical, thermal and shape memory properties of the blends were studied and schemes proposed to explain their dual and triple shape memory behaviors. It was found that the microstructures played an important role in the shape memory process. In TPI/LDPE blends, both the TPI crosslinking network and LDPE crystalline regions could work as fixed domains, while crystalline regions of LDPE or TPI could act as reversible domains. The shape memory behaviors were determined by the components of the fixed and reversible domains. When the blend ratio of TPI/LDPE was 50/50, the blends showed excellent dual and triple shape memory properties with both high shape fixity ratio and shape recovery ratio. © 2017 Society of Chemical Industry     

Micro‐ and macrophase separation of thermosetting systems modified with epoxidized styrene‐block‐butadiene‐ block‐styrene linear triblock copolymers and their influence on final mechanical properties

BACKGROUND: The goal of this work was to establish the minimum degree of epoxidation needed to develop nanostructured epoxy systems by modification with poly(styrene‐block‐butadiene‐block‐styrene) (SBS) triblock copolymers epoxidized to several degrees, and also to investigate the effect of polystyrene (PS) content on the final morphologies. By using two SBS copolymers, the influence of the weight ratio of the two blocks on the generated morphologies and mechanical properties was also analysed. RESULTS: Nanostructured thermosets were effectively obtained through reaction‐induced microphase separation of PS blocks from the matrix. A minimum of 27 mol% of epoxidation, which corresponds to 4.8 wt% of epoxidized polybutadiene (PB) units in the overall mixture, was needed to ensure nanostructuring of final mixtures and thus their transparency. Hexagonally ordered nanostructures were achieved for PS contents of around 16–20 wt%, which agrees with our previous results for mixtures with other SBS copolymers with different ratios between blocks. The fracture toughness of the epoxy matrix was improved or at least retained with mixing. CONCLUSION: The degree of epoxidation of PB blocks needed to switch epoxy/SBS mixtures from a macrophase‐separated to a nanostructured state has been established. The generated morphologies in the epoxy systems are mainly dependent on the PS content in the mixture. Copyright © 2008 Society of Chemical Industry     

Block copolymer of trans‐polyisoprene and urethane segment: Crystallization behavior and morphology

A new type of urethane segmented copolymer was prepared from hydroxyl‐terminated trans‐polyisoprene (HTTPI) and toluene diisocyanate (TDI). The structures of the copolymer were characterized by FTIR and GPC. Crystalline properties of trans‐polyisoprene (TPI) segments were investigated using WAXD and DSC techniques. The crystals of TPI segments are inclined to exist in low‐melting form (LM). The melting temperature of TPI shifts to a lower temperature as the urethane segment was introduced. DMA studies show that, when TPI crystals were at the melting state, the storage modulus of the copolymer depended on the content of urethane segment. The hard segment here serves as physical crosslinkage. Nonisothermal crystallization kinetics of TPI segment was studied on the basis of the Ozawa equation. It was found that the hard segment suppresses the crystallization of the TPI segment. Morphology of two‐phase separation was observed in the copolymer by SEM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2286–2294, 2004     

Strain‐induced crystallization behavior of natural rubber and trans‐1,4‐polyisoprene crosslinked blends

The strain‐induced crystallization (SIC) behaviors of crosslinked blends based on natural rubber (NR) and trans‐1,4‐polyisoprene (TPI) with different content of TPI were probed explored by using synchrotron two‐dimensional wide angle X‐ray diffraction and dynamic mechanical analysis. The results showed that when TPI content is less than 70% no reflection peak of TPI but NR crystallite diffractions can be observed and the diffractions of TPI βform appear when TPI content is 70 wt % in the cocured blend. SIC of cocured blends started at smaller strain ratio than the pure NR. By calculating ΔS_def, it is found that the drop in entropy upon strain decreased when TPI is incorporated into NR due to the reduction of molecular mobility of NR. The degree of SIC and crystallization rate index in crosslinked blends monotonously decreased with the increase of TPI content. The apparent crystallite size exhibited some surprising variations. L₂₀₀ and L₁₂₀ decreased with the increase of TPI content in the cocured blends. These observations were usually caused by two factors: (i) Less number of polymer chains could involve in crystal growth due to the lower mobility of polymer chains in the cocured blends which is proved by dynamic mechanical analysis results; (ii) The mean distance between nuclei decreases, which was caused by the fluctuation of crosslink density in NR phase derived from the heterogeneous distribution of curatives in two phases supported by the varying tendency of curing degree and crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

ETPI用量和环氧度对NR/ETPI并用胶性能的影响

研究NR/环氧化反式1,4-聚异戊二烯（ETPI）并用比和ETPI环氧度对NR/ETPI并用胶性能的影响。结果表明,加入适量的ETPI,可以明显地提高NR胶料与钢丝的粘合性能。当NR/ETPI并用比为85/15时,NR/ETPI并用胶的耐磨性能和抗湿滑性能较好,抽出力的增幅较大;当ETPI的环氧度为15%时,NR/ETPI并用胶的性能最优异。     

Observation of phase separation of epoxidized trans-1,4-polyisoprene and mechanism exploration through 13C-NMR

Selectively epoxidized trans-1,4-polyisoprene (SETPI) and randomly epoxidized trans-1,4-polyisoprene (RETPI) were fabricated successfully through modified surface water-phase suspension epoxidation and solution random epoxidation, respectively. The effects of fabricated method and epoxy degree of ETPI on the glass transition temperature (T _g), dynamic mechanical properties and phase separation phenomenon of the as-fabricated polymer have been investigated by different scanning calorimetry, dynamic mechanical analyzer and phase contrast microscope. The double bonds and epoxy groups sequence structure distribution of different ETPI have been observed and analyzed by ¹³C-NMR. There is a great deal of difference in the microstructure and sequence distribution of epoxy group in ETPI with different synthesis methods and epoxy degree. The results show that distribution of epoxy group in SETPI is nonuniform which brings about the phase separation.     

Progress of synthesis and application of trans-1,4-polyisoprene

A new technology to synthesize trans-1,4-polyisoprene (TPI) with bulk precipitation polymerization in the presence of a supported Ti catalysts was introduced. The termination of polymerization, stabilization of the polymer, and the adjustment of the molecular weight of TPI and its quality index are discussed. The blending and covulcanization of TPI with natural rubber (NR), styrene butadiene rubber (SBR), and butadiene rubber (BR) were studied. The blending compounds had outstanding dynamic mechanical properties, especially the rolling resistance, heat buildup, and wet skid resistance. Tread and sidewall compounds that contained TPI had a higher modulus, longer fatigue life, better abrasion resistance, lower rolling resistance, and lower buildup, which indicates that TPI is suitable for high-performance tire. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 81–89, 2001     

Study on mechanical and thermal properties of composites of cis‐ and trans‐polyisoprene blends filled with polyaniline

In this study, the effect of polyaniline (PANI) as filler has been investigated on the mechanical and thermal properties of blends of cis‐polyisoprene (CPI) and trans‐polyisoprene (TPI) by dynamic mechanical analyzer and transient plane source technique, respectively. The samples blend composites with different concentration of PANI have been prepared by solution casting method and characterized through X‐ray diffraction. Experimental results from mechanical and thermal measurements show that incorporation of PANI in CPI/TPI blends increases glass transition temperature, mechanical properties and thermal properties whereas decreases damping property. This increase in different properties is only upto a certain amount of PANI and over this amount an entirely apposite behavior is observed. This observed behavior of mechanical and thermal properties is explained on the basis of crystallinity and crosslink density. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis of sulfonated rubber ionomers by the ring‐opening reaction of epoxidized styrene–butadiene rubber,their characterization,and their properties

A novel method for the synthesis of the sulfonate ionomer of styrene‐co‐butadiene rubber (SBR) was developed. SBR was first epoxidized by performic acid formed from hydrogen peroxide and formic acid in situ in solution, and this was followed by a ring‐opening reaction with an aqueous solution of NaHSO₃. The optimum conditions for the epoxidation of SBR in the presence of a phase‐transfer catalyst and for the ring‐opening reaction of epoxidized SBR with an aqueous solution of NaHSO₃ were studied. During the epoxidation of SBR, a phase‐transfer catalyst, such as poly(ethylene glycol), could enhance the conversion of double bonds to epoxy groups. During the ring‐opening reaction, both the phase‐transfer catalyst and ring‐opening catalyst were necessary to enhance the conversion of the epoxy groups to ionic groups. The addition of Na₂SO₃ to the reaction mixture was important to obtain 100% conversion. The products were characterized with Fourier transform infrared spectrophotometry, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). DSC showed that the sodium sulfonate SBR ionomer possessed a dissociation temperature of ionic domains at 110°C, which appeared as black spots under TEM, after the sodium ions of the ionomer were substituted by lead ions. Some properties of the sodium ionomer, such as the water absorbency, oil absorbency, and dilute solution behavior, were studied. With increasing ionic groups, the water absorbency of the ionomer increased, whereas the oil absorbency decreased. The dilute solution viscosity of the ionomer increased abruptly with increasing ionic group content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3090–3096, 2006     

Thermal and mechanical properties of acrylated expoxidized‐soybean oil‐based thermosets

A series of epoxidized‐soybean oil (ESO) with different epoxyl content were synthesized by in situ epoxidation of soybean oil (SBO). The acrylated epoxidized‐soybean oil (AESO) was obtained by the reaction of ring opening of ESO using acrylic acid as ring opener. The acrylated expoxidized‐soybean oil‐based thermosets have been synthesized by bulk radical polymerization of these AESOs and styrene. The thermal properties of the resins were characterized by differential scanning calorimetry (DSC) and thermo‐gravimetric analysis (TG). The results showed that these resins possess high thermal stability. There were two glass transition temperature of each resin due to the triglycerides structure of the resins. The tensile strength and impact strength of the resins were also recorded, and the tensile strength and impact strength increased as the iodine value of ESO decreased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Retardation of cold flow in immiscible rubber blends by tailoring their microstructures

Cold flow is a well‐known characteristic and also an unresolved drawback for uncured rubber materials. In this paper, a simple approach of retarding the cold flow of cis‐1,4‐polybutadiene rubber (BR) elastomer is reported by controlling the phase separation and crystallization that occurs in immiscible BR/trans‐1,4‐polyisoprene (TPI) blends. The BR/TPI blends showed an untypical phase diagram below 150 ^oC. Upon crystallization the amorphous BR facilitates the nucleation of TPI. The higher the BR content is, the less the surface roughness of the TPI crystals, and then a larger dendritic pattern that resulted from the cold flow of BR was observed in the microstructure. BR/TPI blends with the highest resistance to cold flow were obtained by optimizing the composition and thermal treatment in such a way that small soft amorphous BR domains were entrapped in the rigid TPI crystalline phase. It is expected that this study could provide a simple way for the prevention of cold flow of rubber materials. © 2017 Society of Chemical Industry     

环氧化反式-1,4-聚异戊二烯的结构与性能

研究了水相悬浮法合成环氧化反式－1，4－聚异戊二烯（ETPI）的结构与性能。结果表明，反式－1，4－聚异戊二烯TPI粉粒的晶区和无定形区均能发生环氧化反应，但因二者反应性不同，导致环氧基团在同一分子链无定形区链段部分数目较多而在晶区链段部分数目较少，形成类嵌段结构，在微观上整个分子链的环氧化不均匀；随环氧度的增加，ETPI分子链的刚性、极性增加，结晶性变差，生胶在非极性溶剂中的溶解性变差，在甲苯中的特性黏数降低，熔点降低，邵尔A型硬度先降低后升高，密度、凝胶质量分数增加，门尼黏度升高，加工性变差。     

预处理法合成环氧化反式-1,4-聚异戊二烯及其结构与性能

采用预处理法对反式-1,4-聚异戊二烯(TPI)进行环氧化改性,合成了具有不同环氧度的环氧化TPI( ETPI),考察了预处理剂/水(体积比,下同)、投料比[过氧乙酸/TPI(摩尔比,下同)]对ETPI环氧度的影响,并对ETPI的结构及性能进行了表征.结果表明,预处理法合成的ETPI其环氧度显著提高,当预处理剂/水为7...     

Preparation of poly(1,4‐cyclohexylenedimethylene phthalate)s and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol⁻¹) led to an 80% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry     

Cure kinetics and thermal stability of micro and nanostructured thermosetting blends of epoxy resin and epoxidized styrene‐block‐butadiene‐block‐styrene triblock copolymer systems

The compatibility of styrene‐block‐butadiene‐block‐styrene (SBS) triblockcopolymer in epoxy resin is increased by the epoxidation of butadiene segment, using hydrogen peroxide in the presence of an in situ prepared catalyst in water/dichloroethane biphasic system. Highly epoxidized SBS (epoxy content SBS >26 mol%) give rise to nanostructured blends with epoxy resin. The cure kinetics of micro and nanostructured blends of epoxy resin [diglycidyl ether of bisphenol A; (DGEBA)]/amine curing agent [4,4′‐diaminodiphenylmethane (DDM)] with epoxidized styrene‐block‐butadiene‐block‐styrene (eSBS 47 mol%) triblock copolymer has been studied for the first time using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as kinetic constants and activation energy. The cure reaction rate is decreased with increasing the concentration of eSBS in the blends and also with the lowering of cure temperature. The compatibility of eSBS in epoxy resin is investigated in detailed by Fourier transform infrared spectroscopy, optical and transmition electron microscopic analysis. The experimental data of the cure behavior for the systems, epoxy/DDM and epoxy/eSBS(47 mol%)/DDM show an autocatalytic behavior regardless of the presence of eSBS in agreement with Kamal's model. The thermal stability of cured resins is also evaluated using thermogravimetry in nitrogen atmosphere. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Synthesis and Physicochemical Properties of Partially and Fully Epoxidized Methyl Linoleate Derived from Jatropha curcas Oil

Partial epoxidation of methyl linoleate was carried out at room temperature (30 °C) using a methyltrioxorhenium catalyst in the presence of pyridine and urea‐hydrogen peroxide. Full epoxidation of methyl linoleate was carried out using the Prilezhaev method. The reactions were monitored using the oxirane oxygen content value. The products from partial and full epoxidation were analyzed using GC‐FID, FTIR, NMR and GC–MS. Methyl 9,10‐epoxy‐12Z‐octadecenoate and methyl 12,13‐epoxy‐9Z‐octadecenoate were obtained as the major products from partial epoxidation, with a percent yield of 46 %. The product from full epoxidation afforded 97 % yield with methyl 9,10‐12,13‐diepoxyoctadecanoate as the major component. Physicochemical properties such as kinematic viscosity, viscosity index, crystallization temperature and oxidative stability were examined. Fully epoxidized methyl linoleate exhibits superior kinematic viscosity and oxidative stability due to the complete conversion of double bonds to epoxy groups. Partially epoxidized methyl linoleate exhibits intermediate kinematic viscosity, viscosity index, crystallization temperature and oxidative stability.     

Synthesis and characterization of maleated ionomers via ring‐opening reaction of epoxidized styrene‐butadiene rubber with potassium hydrogen maleate and study of their behavior as compatibilizer

A novel method for synthesizing maleate ionomer of (styrene‐co‐butadiene) rubber (SBR) from epoxidized SBR was developed. The epoxidized SBR was prepared via epoxidation of SBR with performic acid formed in situ by H₂O₂ and formic acid in cyclohexane. The maleated ionomer was obtained by ring‐opening reaction of the epoxidized SBR solution with an aqueous solution of potassium hydrogen maleate. The optimum conditions were studied. It was found that it is necessary to use phase transfer catalyst and ring‐opening catalyst for enhancing the epoxy group conversion. To obtain 100% conversion addition of dipotassium maleate is important. The product was characterized by FTIR spectrophotometry and transmission electron microcroscopy (TEM). The results showed that the product was really an ionomer with domains of maleate ionic groups. Some properties of the ionomer, such as water absorbency, oil absorbency and dilute solution behavior were studied. With increasing ionic groups, the water absorbency of the ionomer increases, whereas the oil absorbency decreases. The dilute solution viscosity of the ionomer increases abruptly with increasing ionic group content. The ionomer can be used as a compatibilizer for the blends of SBS and chlorosulfonated polyethylene (CSPE). Addition of a small amount of the ionomer to the blend can enhance the mechanical properties of the blends. 3 wt % ionomer based on the blend can increase the tensile strength and ultimate elongation of the blend nearly twice. The compatibility of the blends enhanced by adding the ionomer was shown by scanning electron microscopy. The blend of equal parts of SBS and CSPE compatibilized by the ionomer behaves as an oil resistant thermoplastic elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 792–798, 2006     

Synthesis and characterization of low relative molecular weight trans‐1,4‐poly(isoprene)

Low relative molecular weight trans‐1,4‐polyisoprene oligomers were synthesized successfully by bulk precipitation and solution polymerization with supported titanium catalyst using hydrogen as relative molecular weight modifier. The effects of polymerization conditions on intrinsic viscosity ([η]), catalyst efficiency (CE) and structure of polymer were studied. Increasing the hydrogen pressure resulted in the decrease of [η] of the polymer. With the increasing of hydrogen pressure and reaction temperature, CE decreased but still maintained above 2500 g polymer/g Ti. The percentage composition of (trans‐1, 4‐unit) in the polymer was over 90% in all results. The crystallinity of polymer was about 50–60% with T_m being about 60°C. The relative molecular weight distribution index (MWD) was quite difference according to the polymerization method. While number average molecular weight (M_n) exceeded 860, polymer turned from viscous materials to fragile wax materials, and then to toughness materials at 1800. Dynamic property testing showed that the additional of this oligomer could increase the wet‐skid resistance of the rubber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Regulation of trans‐1,4‐polyisoprene crystallinity and mechanical properties of styrene‐butadiene rubber/trans‐1,4‐polyisoprene vulcanizate

The effects of processing temperature and bis‐[γ‐(triethoxysilyl)‐propyl]‐tetrasulfide (Si69) on crystallization, morphology, and mechanical properties of styrene‐butadiene rubber (SBR)/trans‐1,4‐polyisoprene (TPI) vulcanizate are investigated. The crystallinity and crystalline melting temperature (T_m) of TPI in the vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C are much lower than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the presence of 1 phr Si69 leads to a decreased crystallinity and T_m. The TPI domains with phase size of about 1 μm and silica are well dispersed in the vulcanizate, and TPI crystals get smaller in size and less in amount by pre‐mixing TPI, silica and Si69 at 150 °C. The vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C have decreased tensile strength and modulus at a given extension than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the tensile strength and modulus of the vulcanizate increase with the addition of 1 phr Si69. The crystallinity of TPI component in SBR/TPI vulcanizate is effectively controlled by changing processing temperature and adding Si69, which is important for theoretical research and practical application of TPI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44395.