原位合成甲基丙烯酸锌增强氢化丁腈橡胶

用ZnO和甲基丙烯酸(MAA)经原位反应合成了甲基丙烯酸锌(ZDMA),将其作为增强剂用以增强氢化丁腈橡胶(HNBR),研究了ZnO／MAA(摩尔比,下同)、过氧化二异丙苯(DCP)用量和ZDMA用量对硫化胶力学性能的影响。结果表明,当ZnO／MAA为0．8,DCP用量为4份(质量,下同)时,原位合成ZDMA能够显著地提高HNBR的力学性能。随着ZDMA理论生成量的增加,硫化胶的拉伸强度先增加后减少,当ZDMA理论生成量为30份时,硫化胶的最大拉伸强度为47.2MPa．而扯断伸长率保持在393％以上;100％定伸应力随ZDMA理论生成量的增加而增加。经傅里叶变换红外光谱法和广角X光衍射法分析表明,在HNBR混炼过程中,ZnO和MAA可以原位生成ZDMA。     

原位合成甲基丙烯酸锌改性三元乙丙橡胶/聚丙烯热塑性弹性体

以过氧化二异丙苯(DCP)为交联剂,研究了ZnO与甲基丙烯酸原位合成的甲基丙烯酸锌(ZDMA)为助交联剂对动态硫化三元乙丙橡胶/聚丙烯热塑性弹性体(EPDM/PPTPV)性能的影响。结果表明,当交联剂DCP的用量为1份时,含有ZDMA的EPDM/PPTPV具有较佳的力学性能;当EPDM/PPTPV中填充5~20份ZDMA时,其力学性能较佳;随着ZDMA填充量的增加,PP的结晶度不断下降。     

甲基丙烯酸锌对EPDM的补强作用

研究了在过氧化物硫化体系中,甲基丙烯酸锌[Zn(MAA)2]和硫化剂DCP的用量对EPDM胶料性能的影响。试验结果表明,Zn(MAA)2用量的增大对EPDM胶料粘度的影响不大,但可显提高硫化速度和硫化程度;随着Zn(MAA)2用量的增大,EPDM硫化胶的邵尔A型硬度逐渐增大,拉伸强度和扯断伸长率都是先升高再下降。当硫化剂DCP用量为1．0份时,EPDM硫化胶具有最佳的综合性能。Zn(MAA)2的补强效果与EPDM的物理化学性质有关,乙烯质量分数和第三单体ENB质量分数高时补强效果好。     

原位生成甲基丙烯酸锌增强天然橡胶的结构和性能

用ZnO与甲基丙烯酸(MAA)在天然橡胶(NR)基体中原位生成甲基丙烯酸锌(ZDMA),并在硫化剂过氧化二异丙苯(DCP)作用下制备了NR／ZnO／MAA纳米复合材料。用傅里叶变换红外光谱法、X射线衍射法、能量色散X射线法和扫描电子显微镜法分析了NR在混炼和硫化过程中的结构和形态变化,并研究了硫化胶的力学性能。结果表明,在NR混炼过程中加入摩尔比为0．5的ZnO／MAA。可以原位生成ZDMA;在硫化过程中,ZDMA在DCP作用下发生复杂化学反应,形成界面紧密结合的纳米复合材料,导致硫化胶的力学性能显著提高。当ZnO／MAA为加份时,硫化胶的拉伸强度、撕裂强度、扯断伸长率分别为30．6MPa,54．7kN／m,410％,其增强效果优于直接添加ZDMA。     

原位生成甲基丙烯酸镁对天然橡胶的补强研究

在天然橡胶混炼过程中加入氢氧化镁[Mg(OH)2]与甲基丙烯酸(MAA)，在橡胶基体中原位生成甲基丙烯酸镁(MDMA)，并在硫化剂DCP作用下制备NR／Mg(OH)2／MAA硫化胶。用FTIR、XRD研究了胶料在混炼和硫化过程中的结构变化，并研究了硫化胶的力学性能，结果表明，在NR混炼过程中加入摩尔比为0．5的Mg(OH)2／MAA，可以原位生成MDMA；在硫化过程中，MDMA在DCP作用下，一方面自聚生成PMDMA，另一方面与橡胶发生化学结合，从而形成紧密结合的复合材料，导致硫化胶的力学性能显著提高。     

原位生成ZDMA补强HNBR性能的研究

对氧化锌和甲基丙烯酸（MAA）发生中和反应原位生成甲基丙烯酸锌（ZDMA）补强氢化丁腈橡胶（HNBR）进行研究。结果表明，原位生成ZDMA对HNBR具有良好的补强作用；硫化剂DCP用量和ZDMA生成量增大，硫化胶的总交联密度和离子键交联密度均增大；氧化锌／MAA摩尔比为0．8、ZDMA理论生成量为30份、硫化荆DCP用量为4份时，硫化胶的综合物理性能较好。     

原位合成丙烯酸钠改性三元乙丙橡胶制备吸水膨胀橡胶

通过氢氧化钠(NaOH)和丙烯酸(AA)的中和反应,在三元乙丙橡胶(EPDM)中原位合成丙烯酸钠(NaAA),并在有机过氧化物的作用下将所得混炼胶进行硫化。比较了原位生成NaAA、直接添加NaAA和直接添加聚丙烯酸钠(PNaAA)等三种不同制备吸水膨胀橡胶方法对混炼胶硫化性能和硫化胶吸水膨胀性能的影响,主要研究了原位合成NaAA改性EPDM混炼胶的硫化特性和硫化胶的吸水膨胀性能及其力学性能。结果表明,原位合成NaAA改性EPDM的性能优于直接添加NaAA或PNaAA的EPDM,它不但具有良好的力学性能,而且还具有良好的吸水膨胀性能;随着NaAA含量的增大,硫化速度、硫化程度和吸水膨胀性能均有提高;吸水膨胀橡胶,在NaAA为30质量份时,力学性能具有最大值。过氧化二异丙苯(DCP)用量增大,吸水膨胀率下降,但仍可提高硫化胶的力学性能。     

原位生成甲基丙烯酸锌对天然橡胶补强的研究

在天然橡胶(NR)混炼过程中加入氧化锌与甲基丙烯酸(MAA),在橡胶基体中原位生成甲基丙烯酸锌(ZDMA),并在硫化剂过氧化二异丙苯作用下制备NR/ZnO/MAA硫化胶。用扫描电镜、透射电镜研究了硫化胶的形态,并研究了制备条件对硫化胶力学性能的影响,结果表明,在155℃硫化温度,DCP用量为1.5～2 0质量份(phr)条件下,NR硫化胶具有较佳的力学性能。随着ZnO/MAA用量的增加,硫化胶定伸应力、拉伸强度和撕裂强度显著增加,表现出显著的补强作用。     

Improved mechanical properties and special reinforcement mechanism of natural rubber reinforced by in situ polymerization of zinc dimethacrylate

The peroxide‐cured natural rubber (NR) was reinforced by in situ polymerization of zinc dimethacrylate (ZDMA). The experimental results showed NR could be greatly reinforced by ZDMA. The tensile strength and the hardness of NR/ZDMA composites increased with the content of ZDMA. The reinforcement mechanism was studied further. Both high crosslinking density provided by ionic crosslinking and strain‐induced crystallization improved the mechanical properties. The crosslinking density was determined by an equilibrium swelling method and the crystallization index was measured by Wide‐angle X‐ray diffraction (WXRD). When the amount of ZDMA was high, the ability of strain‐induced crystallization decreased, due to the strong interactions between the rubber phase and the hard poly‐ZDMA (PZDMA) nanodispersions. At the moment, the increasing ionic crosslinking density made up for the effect of the drop of the strain‐induced crystallization, and played a more important role in the reinforcement. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

甲基丙烯酸锌与炭黑共同补强天然橡胶的研究

在开放式炼胶机上,分别以直接添加和原位生成2种方法向天然橡胶(NR)基体中添加甲基丙烯酸锌(ZDMA),制备了2种类型的ZDMA与炭黑共同补强的NR硫化胶,X射线衍射(XRD)分析证实,成功制备了ZDMA。扫描电镜(SEM)研究表明,原位生成ZDMA硫化胶的断面比直接添加ZD-MA硫化胶的粗糙很多,表现出更强的界面结合力。力学性能研究表明,用ZDMA部分替代炭黑,可以有效提高硫化胶的力学性能。在相同添加量下,原位生成ZDMA硫化胶的力学性能优于直接填充ZD-MA硫化胶的。     

Stress softening of NR reinforced by in situ prepared zinc dimethacrylate

The stress softening effect of nature rubber (NR) reinforced by in situ prepared zinc dimethacrylate (ZDMA) was studied. Degree of stress softening effect (Ds) in the 4th stress–strain cycle of the NR with 10 phr (parts per hundreds of rubber) ZDMA was only 2.23 (strain = 100%), whereas it reached to 59.98 at 50 phr ZDMA (strain = 200%). The stress softening effects of carbon black filled into NR, and compared with the ZDMA effect, was also studied here. Mooney–Rivlin semiempirical equation was introduced here to analysis the stress–strain behavior of the NR vulcanize filled with in situ prepared ZDMA, and the results showed that the ZDMA/NR system has an obvious Payne effect which is in good agreement with the stress softening effect. Crosslink density analysis indicated a high ionic crosslink density in the NR filled with high content ZDMA, which contributed to the low elastic recovery of the stress softening. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

原位生成甲基丙烯酸锌对天然胶/气相法白炭黑纳米复合材料力学性能及加工性能的作用

研究了气相法白炭黑及甲基丙烯酸锌（ZDMA）对天然胶的力学性能、加工性能的影响.ZDMA采用原位生成的方法制备.力学性能的结果表明：ZDMA和气相法白炭黑对NR有协同补强的效应.橡胶加工性能分析（RPA）表明：ZDMA的加入,不仅能使天然胶/气相法白炭黑体系的加工性能得到很好的改善,而且能降低60 ℃时硫化胶的损耗因子.     

Infrared study on in situ polymerization of zinc dimethacrylate in poly(α‐octylene‐co‐ethylene) elastomer

An infrared spectroscopic method was used to follow the course of in situ polymerization of zinc dimethacrylate (ZDMA) in poly(α‐octylene‐co‐ethylene) elastomer (POE). The integral intensity of the 831 cm^?1 band, ie the out‐of‐plane deformation mode of ?CH, was used to determine the residual amount of ZDMA in composites cured at 165°C for different times, through which the course of in situ polymerization of ZDMA in POE was traced and the dynamic curve determined. The curing course of the ZDMA/POE/peroxide system at 165°C was examined with a rheometer and compared with the course of in situ polymerization. The results surprisingly show that the in situ polymerization of ZDMA is almost complete at the beginning stage of curing, and that substantial crosslinking starts subsequently. Scanning electron microscopy and transmission electron microscopy observations on morphologies of ZDMA/POE composites cured at 165°C for different times were carried out and confirmed the results of infrared experiments. Combining all the investigations, it was deduced that a competition exists between in situ polymerization and crosslinking in the composites. Covalent crosslinking rather than ionic bond crosslinks are the major types of crosslinks structures in ZDMA/POE composites, and its total density is lower than that of carbon‐ black‐reinforced POE. Copyright © 2004 Society of Chemical Industry     

N234/三元乙丙橡胶复合材料的制备与研究

对N234新工艺法炭黑与三元乙丙橡胶复合材料的性能进行了研究,实验发现随着N234用量的增加,门尼粘度逐渐增大,焦烧时间和正硫化时间有缩短的趋势,而最小扭矩与最大扭矩均逐渐增大,胶料的抗返原性提高;硫化胶的定伸应力和撕裂强度随N234用量的增加而增加;伸长率逐渐减小;拉伸强度在50份达到最大值。     

Combined effect of VA content and pH level of filler on properties of EPDM/SmBO3 and EPDM/ATO composites reinforced by three types of EVA

This study investigates the interaction of vinyl acetic (VA) content of ethylene‐vinyl acetate (EVA), pH level of Samarium borate (SmBO₃), and Sb‐doped SnO₂ (ATO) on reinforcement of peroxide‐cured ethylene‐propylene‐diene rubber (EPDM)/SmBO₃ and EPDM/ATO composites. It was found that EVA could both reinforce mechanical properties of EPDM, and enhance fluidity of gum during processing. During vulcanization, the interaction of VA groups and pH value of filler particles can influence the crosslink density of EPDM composites. In alkaline EPDM/SmBO₃/EVA, VA groups could hydrolyze to produce polyvinyl alcohol and reduce pH level of medium by consuming OH⁻. When dispersed in acidic EPDM/ATO/EVA, VA groups could generate polyunsaturated bonds and acetic acid during vulcanization. The double bonds could react with dicumyl peroxide (DCP) and then boost crosslink efficiency of EPDM composites. Moreover, acetic acid and reduction of pH value could make DCP decompose into ions, and lower crosslink density of EPDM composites. In addition to the contribution of crosslink density, EVA could crystallize in EPDM composites to reinforce EPDM composites. Electric properties of EPDM were also affected. Surface and volume resistivity of EPDM composites decreased with the rise of VA content. As for EPDM/SmBO₃/EVA composites, the growth of VA groups could boost dielectric constant and loss, decrease dielectric strength, due to the enhancement of polarity and reduction of crosslink density. In terms of EPDM/ATO/EVA composites, the EPDM/ATO/EVA14 possesses the highest dielectric constant and loss, and the lowest dielectric strength, because of the competing effect of VA content and crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

原位生成甲基丙烯酸钠补强EVA的研究

对氢氧化钠和甲基丙烯酸(MAA)发生中和反应原位生成甲基丙烯酸钠补强乙烯—乙酸乙烯酯橡胶(EVA)进行了研究。结果表明，在EVA用量为100份、硫化剂DCP用量为3份、氢氧化钠/MAA摩尔比为l／l的条件下，甲基丙烯酸钠理论生成量为30份时，EVA硫化胶物理性能较好；甲基丙烯酸钠理论生成量不超过50份时，EVA硫化胶透明性较好；EVA硫化胶离子键交联密度随甲基丙烯酸钠理论生成量增大而显著提高。     

In situ preparation of zinc salts of unsaturated carboxylic acids to reinforce NBR

Through the neutralization reaction of zinc oxide (ZnO) and methacrylic acid (MAA) or acrylic acid (AA), zinc methacrylate (ZMA) or zinc acrylate (ZA) was in situ prepared in nitrile rubber (NBR). The mechanical properties and crosslinking structure of the resulting peroxide‐cured NBR vulcanizates were studied. The results showed that ZnO/MAA (AA) had a great reinforcing effect for NBR, and their amounts and ratio played important roles in influencing the mechanical properties. Such vulcanizate contains both covalent crosslinks and salt crosslinks, and the change in the tensile strength of the vulcanizate was related to the variation of the salt crosslink density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2740–2748, 2000     

磺化乙丙橡胶离聚体的熔融流动性及力学性能

研究了不同因素包括相转移催化剂、磺化度、中和度、中和用阳离子及增塑剂等对磺化乙丙橡胶离聚体的熔融流动性及力学性能的影响。结果表明,在合适条件下可得到Ｂｒａｂｅｎｄｅｒ扭矩为３５～４０Ｎｍ、拉伸强度为２０～２８ＭＰａ、断裂伸长率为５００％～６００％、永久变形小于１０％的热塑性弹性体     

用校准曲线法测定EPDM硫化胶的交联密度及交联键结构

根据“每消耗3mol二硫化四甲基秋兰姆（TMTD）分子产生1mol交联键”理论,建立了EPDM纯胶和炭黑N326（50phr)增强EPDM体系的化学交联密度－溶胀因子校准曲线,以此测定了硫黄硫化EPDM的交联密度和交联键类型,TMTD硫化EPDM的交联键类型,用溶胀法测定了EPDM／TMTD的纯胶体系和炭黑增强体系的总交联密度,结果表明,溶胀法测得的交联密度要比由TMTD质量摩尔浓度计算得到的值小。