离子交联磺化丁基胶与几种聚合物的共混效果

研究了磺化丁基胶离聚体与几种聚合物共混产物的力学性质与结构间的关系。结果表明,磺化丁基胶高聚体与聚丙烯或SBS的共混物呈现抗张强度方面的协同效应。用示差扫描量热计测得的聚丙烯熔点随离聚体用量增加而下降。透射电镜表明,在磺化丁基胶离聚体与SBS共混物中存在二个连续相,离聚体与高密度聚乙烯共混物的抗张强度服从加和关系,而与氯醇橡胶或顺式聚丁二烯的共混物则呈现抵消效应。     

磺化丁基橡胶离聚体与其他聚合物的共混

研究了磺化丁基橡胶(IIR)离聚体与苯乙烯-丁二烯嵌段共聚物、聚丙烯、高密度聚乙烯、氯醚橡胶及顺丁橡胶的共混。结果表明，磺化IIR离聚体与苯乙烯-丁二烯嵌段共聚物或聚丙烯的共混物在拉伸强度方面呈现协同效应，随着磺化IIR离聚体质量分数的增加，聚丙烯的熔点下降。磺化IIR离聚体与高密度聚乙烯的共混物在拉伸强度方面呈现加和效应，而其与氯醚橡胶或顺丁橡胶的共混物在拉伸强度方面则呈现抵销效应。     

热塑性弹性体在合成及性能方面的进展

引言 自从1957年聚氨酯热塑性弹性体(TPU)及1965年SBS三嵌段共聚物问世以来,热塑性弹性体的技术开发以及生产进展很快。目前,陆续出现了聚酯类热塑性弹性体(TPEE)、聚烯烃类热塑性弹性体(TPO)、氯化聚乙烯热塑性弹性体(TCPE)、聚氯乙烯热塑性弹性体(TPVC)、加氢的SBS(SEBS)、聚酰胺热塑性弹性体(TPAE)以及磺化乙丙离聚体等。 就热塑性弹性体而言,形成物理交联的硬链段聚集态可分为四种类型:一、玻璃化微区;二、结晶微区;三、离子簇微区;     

氢化羧基丁苯橡胶离聚体的表征及其与聚乙烯共混

从氢化羧基丁苯胶乳出发，与钠、钾、锂、镁、锌和铅等金属离子中和，生成羧基丁苯离聚体胶乳。用IR，DSC，TEM对试样进行了表征，同时测定了不同离子中和及不同氢化度的离聚体物理机械性能，还将钾离聚体与聚乙烯以不同比例共混。结果表明，该离聚体既含有离子微区，又含有结晶微区；各种离聚体均呈现热塑性弹性体性能，其中铅及锂的离聚体拉伸强度最大；钾离聚体与聚乙烯以质量比为25／75-50／50共混时，试样拉伸强度呈现协同效应。     

磷酸盐基(苯乙烯-丁二烯-苯乙烯)嵌段共聚物离聚体的结构、性能及应用

由环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)与磷酸氢二钠通过开环反应制备了含磷酸二钠基的SBS离聚体(PSBS),研究了PSBS的形态结构、混炼胶力学性能的影响因素、PSBS/聚丙烯(PP)共混物的力学性能以及PSBS对SBS/氯醚橡胶(CHR)共混物的增容作用.结果表明,磷酸盐基SBS离聚体呈大小不一、形状不规则的离子微区;当硬脂酸锌用量为PSBS质量分数的10%、离子基团含量为0.95 mmol/g时,PSBS混炼胶的力学性能最佳,且呈现热塑性弹性体行为;PSBS与PP共混,其拉伸强度与组成呈现协同效应,且耐甲苯性提高;PSBS可作为SBS/CHR共混物的增容刺,其最佳质量分数为3%,离聚体的加入有助于改善共混物的耐油性和相客性.     

磺化SBS离聚体与结晶聚烯烃的共混物

研究了磺化SBS离聚体与聚丙烯或高密度聚乙烯在质量分数为10％的硬脂酸锌存在下熔融共混得到的共混物的力学性能。结果表明,共混物的拉伸强度均呈协同效应,这是因为生成了热塑性互穿网络结构。随着聚烯烃含量的增加,共混物由热塑性橡胶变成增韧树脂。     

热塑性橡胶—磺化丁苯橡胶离聚体的性能及其共混

丁苯橡胶（SBR）作为高不饱和度的橡胶被成功地用硫酸乙酸酐作为磺化剂在石油醚及丁酮混合溶剂配成的溶液中磺化，并用乙酸盐中和成离聚体。研究了离聚体及其他聚合物的共混物的熔融流动及力学性能。结果表明，SBR离聚体能很容易在硬脂酸锌存在下熔融加工，其行为象热塑性橡胶，硬脂酸锌能降低布拉本特(Brabender)混和机的扭矩所表示的熔融粘度，并增加流动活化能和离聚体的拉伸强度。离聚体的磺酸基含量能增加熔融粘度及拉伸强度。用于中和的阳离子的种类明显地影响离聚体的性能。离聚与聚丙烯或SBS的共混物在拉伸强度上表现出协同效应，而它与聚苯乙烯或顺－1，4聚丁二烯则呈现抵消效应。     

顺丁烯二酸钾基(苯乙烯-丁二烯-苯乙烯)嵌段共聚物离聚体的力学性能及其应用

用环氧化(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(SBS)开环反应合成了含顺丁烯二酸钾基的SBS离聚体,考察了离子基团不同含量对含顺丁烯二酸钾基的SBS离聚体力学性能的影响,研究了离聚体/聚丙烯(PP)共混物的力学性能和耐溶剂性能,以及离聚体对氯醇橡胶(CHR)/SBS共混物的增容效果。结果表明,该离聚体呈现热塑性弹性体行为;随着离子基团含量的增加,离聚体的拉伸强度及扯断伸长率增大,但当离子基团含量超过1.69mmol/g时,离聚体的力学性能又有所下降,离子基团最佳含量为1.23~1.69mmol/g;该离聚体与PP共混,在拉伸强度方面呈现协同效应;离聚体作为增容剂提高了SBS与CHR的相容性,当离聚体质量分数为3%时,力学性能达到最佳,共混物的耐溶剂性能也得到了改善。     

硫酸盐基离聚体的形态结构、力学性能及其共混

由环氧化（苯乙烯-丁二烯-苯乙烯）三嵌段共聚物（SBS）与硫酸氢钠水溶液反应制备了新型含硫酸盐基的SBS离聚体，研究了离聚体的形态结构、力学性能、离聚体时SI玛／氯醇橡胶（CHR）共混物的增容作用以及离聚体／聚丙烯（PP）共混物的力学性能。结果表明：在透射电镜下硫酸铅基离聚体呈现黑色圆柱状或四方晶形离子微区，硬脂酸锌作为离子增塑剂能提高钠离聚体的力学性能；随着离子基含量的提高，离聚体的拉伸强度及扯断伸长率增加；少量离聚体可以提高SBS／CHR共混物的力学性能，减小共混物的吸煤油率；扫描电镜图片显示二者的相容性增加；离聚体／PP共混物在拉伸强度与组成的关系方面呈现协同效应，并且其耐甲苯性能提高。     

磺化丁苯橡胶离聚体与一些聚合物的熔融共混及产物性能

将磺化丁苯橡胶镁离子交联聚合体（简称离聚体）在增塑剂硬脂酸锌存在下分别与聚丙烯（ＰＰ）、高密度聚乙烯（ＨＤＰＥ）、丁苯嵌段共聚物（ＳＢＳ）、聚苯乙烯（ＰＳ）、顺丁橡胶（ＢＲ）在Ｂｒａｂｅｎｄｅｒ塑性仪密炼机中熔融共混，考察了共混比对平衡扭矩及物理机械性能的影响。结果表明，磺化丁苯橡胶镁离聚体与ＳＢＳ或ＰＰ共混，其拉伸强度呈协同效应，与ＨＤＰＥ共混呈加和效应，而与ＰＳ或ＢＲ共混则呈抵销效应。透射电镜     

Behavior of ionomers of sulfonated styrene–butadiene–styrene triblock copolymer in polymer blends with crystalline polyolefins and as compatibilizer

The blends of ionomers of sulfonated (styrene–butadiene–styrene) triblock copolymer with two polyolefins as well as the blends of polystyrene (PSt) with two polar, oil‐resistant elastomers, i.e., chlorohydrin rubber (CHR) and chlorosulfonated polyethylene (CSPE), using the ionomer as compatibilizer were studied. The blends of the ionomer with polypropylene or high density polyethylene showed synergistic effects with respect to tensile strength. With increasing PSt content, the blends change their behavior from thermoplastic elastomer to toughened plastics. The synergism is probably because of the thermoplastic interpenetrating polymer networks formed in the blend. The blends exhibited high resistance against diesel oil or toluene. When PSt was blended with CHR or CSPE using the ionomer as compatibilizer, only 2 or 3% ionomer was needed to enhance the mechanical properties of the blends. The effect is due to the ion–polar interaction of the ionomer with the polar polymer. The enhanced compatibility of the blends by the ionomer was demonstrated by DSC and Scanning electron micrograph. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1887–1894, 2006     

Poly(arylene-ethynylene) with tuned rigidity/flexibility as reinforcing component in polystyrene-based ionomer blends

Poly(pyridylene/phenylene-ethynylene) polymers of controlled rigidity/flexibility were synthesized and used as molecularly dispersed reinforcing components in ionomer blends with partially sulfonated polystyrene. Homogeneous ionomer blends were formed due to acid-base interactions between the two blend components. The complete protonation of the poly(pyridylene/phenylene-ethynylene) in the acid/base ionomer blends has been proven by UV-VIS absorption and emission spectroscopy. Furthermore, the complete miscibility of the blend components in the ionomer blends was revealed from DSC analysis and transmission electron microscopy. The mechanical properties of the synthesized ionomer blends were determined by stress-strain measurements. The Young modulus of the blends was found to systematically vary with the rigidity/flexibility of the reinforcing polymer i.e. the molecular conformation of the reinforcing polymers as determined by small angle X-ray scattering.     

The control of miscibility of PP/EPDM blends by adding lonomers and applying dynamic vulcanization

The control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na⁺ and ZN⁺⁺) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.     

不同金属离子及胺中和的磺化丁基橡胶离聚体的性能

研究了不同金属离子及胺中和的磺化丁基橡胶离聚体的熔融流动性及力学性能。结果表明,随着硬脂酸锌加入量的增加,锂离聚体的熔融黏度降低,拉伸强度增大;随离聚体中磺酸基含量的增加,锂离聚体的熔融黏度和拉伸强度增大。对于一价金属离子中和的离聚体,其熔融黏度及拉伸强度随着离子电位的降低而减小;对于二价金属离子中和的离聚体,随着离子电位的下降及共价性的增加,熔融黏度下降而拉伸强度增大。用胺中和的离聚体,硬脂酸锌的影响较小,未加硬脂酸锌的离聚体具有较高的扯断伸长率及较低的永久变形,是良好的热塑性弹性体;随离聚体中磺酸基含量的增加,乙胺离聚体的拉伸强度增大。对于不同胺中和的离聚体,其拉伸强度按下列顺序依次降低：乙胺,三乙胺,二乙胺;乙胺,己胺,十二胺,十八胺。     

Ionomer blends: Morphology and mechanical properties

Polymer blends, having one component as an ionomer, can develop an interesting combination of mechanical properties. These properties give such blends some specific advantages as compared to non-ionic homo-polymers. Primary attention is given to blends involving an ionomer and the ionomer precursor polymer. In such blends, synergistic effects can occur in several of the mechanical properties, such as modulus, strength and fracture energy. The enhanced mechanical properties, which occur for relatively low concentrations of the ionomer in the blends, are well above values predicted by the rule of mixtures. This behavior is attributed to the presence in the ionomer component of a higher chain entanglement density and to good adhesion between the dispersed ionomer particles and the polymer matrix. Some discussion, with examples, is also given of other blends having an ionomer as one component and of blends in which a small amount of ionomer is added in order to enhance the miscibility of two otherwise incompatible polymers.     

The role of specific interactions and transreactions on the compatibility of polyester ionomers with poly(ethylene terephthalate) and nylon 6,6

The compatibility of polyester ionomers with polar polymers (i.e., poly(ethylene terephthalate) and nylon 6,6) is under investigation for their potential use as minor component compatibilizers. Binary blends have been prepared by both solution and melt-mixed methods to determine the effect of melt-processing on blend compatibility. The effect of the sulfonate group and counterion type on compatibility was evaluated by blending sulfonated and nonsulfonated forms of the amorphous polyester ionomer with both nylon 6,6 and poly(ethylene terephthalate). The melting point and phase behavior of the blends were determined by differential scanning calorimetry (DSC) and environmental scanning electron microscopy (ESEM), respectively. A comparison of the melting behavior between the melt and solution blends suggests compatibility due to specific interactions for the ionomer/nylon 6,6 blends, and transesterification for the ionomer/poly(ethylene terephthalate) blends. The phase morphology of the melt blends is consistent with the results obtained by DSC analysis.     

磺酸钠基苯乙烯-丁二烯-苯乙烯嵌段共聚物离聚体的力学性能及其应用

由环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)与NaHSO3开环反应合成了磺酸钠基SBS离聚体。研究了离聚体力学性能的影响因素、离聚体对SBS/氯醇橡胶(CHR)的增容作用、质量比对离聚体/聚丙烯(PP)共混物性能的影响。结果表明:硬脂酸锌能提高离聚体的力学性能;随着离聚体离子含量的增加,拉伸强度及扯断伸长率增加。加入少量离聚体,使离聚体/CHR共混物的力学性能提高,扫描电镜显示两者的相容性增加;离聚体与PP共混,在拉伸强度方面呈现协同效应。质量比各为1/1的离聚体增容SBS/CHR和离聚体/PP共混物的耐油性均较SBS大为改善。