丙烯酸酯橡胶合成及应用
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摘要
本论文采用乳液聚合法制备丙烯酸酯橡胶(ACM),探讨了引发剂体系对聚合反应速率的影响及反应条件对凝胶形成的影响；首次采用双螺杆脱挥连续溶液聚合法制备ACM,研究了聚合主单体的组成和脱挥条件对ACM生胶性能的影响；进行了ACM硫化工艺的优化,考察了硫化剂及炭黑用量对硫化胶性能的影响；采用了表面改性白炭黑填充环氧型ACM,对比了不同改性方法的白炭黑在橡胶基体中的分散性及对其力学性能的影响；探讨了环氧型ACM对尼龙6(PA6)的改性,主要研究热性能、结晶性能及力学性能方面的改性。具体包括以下几个方面：
1、乳液聚合法制备ACM：将丙烯酸丁酯(BA)与甲基丙烯酸缩水甘油酯(GMA)进行乳液共聚合以制备环氧型ACM,通过对聚合反应速度和生胶性能的研究,探讨了聚合反应的方法及工艺参数；并通过对聚合物中凝胶含量及环氧基团开环率的对比研究,探讨不同反应条件对凝胶含量的影响。实验结果表明,在反应体系中加入一定量的第二单体丙烯酸乙酯(EA),选择氧化还原复合引发体系,同时将反应温度控制在25-30℃并在饥饿状态下投料可抑制BA的分子内转移和GMA中的环氧基开环,最终可以使聚合物中凝胶含量控制在2.9%以下,达到国外同类产品的水平。
2、连续溶液聚合法制备ACM：分别采用以BA和EA为聚合主单体合成ACM,研究主单体组成和脱挥条件的变化对ACM生胶性能的影响。改变聚合主单体的组成对分子量及分布和脱挥后残留的挥发份影响不大,但随着聚合主单体组成的变化,ACM的玻璃化温度发生变化。脱挥温度和脱挥挤出机转速的变化引起ACM分子量、玻璃化转变温度和脱挥后残留的挥发份的变化,脱挥温度提高,ACM的分子量有所增加,分子量分布宽度变宽,玻璃化转变温度升高；改变脱挥挤出机转速提高,ACM的分子量略有降低,分子量分布稍有变宽,玻璃化转变温度变化不大。脱挥温度和脱挥挤出机转速均使脱挥后残留的挥发份含量下降。
3、ACM硫化技术和配方的研究：从橡胶的硫化机理及填充补强机理入手,将硫化体系和填充体系对ACM的性能进行研究和实验对比。结果表明硫化剂和炭黑用量对ACM的性能有预期的影响,其中邵尔硬度随着硫化剂用量和炭黑用量的增加而增加；耐油性随着硫化剂的引入量的增加而增加；硫化剂和炭黑用量对ACM拉伸强度和断裂伸长率的影响规律基本是一致的,随硫化剂和炭黑用量的增加拉伸强度呈先增加后下降的趋势,而断裂伸长率随硫化剂和炭黑用量的增加呈线性下降；硫化剂与促进剂表现为一种硫化协同效应,硫磺用量有一定的临界值,低于临界值0.5(质量百分数),环氧型ACM不能硫化。实验结果表明硫化剂的最佳用量为2%,炭黑用量为50%。
4、表面改性白炭黑填充ACM性能的研究：将环氧型ACM用不同表面改性的白炭黑进行填充补强,并对其性能进行研究,实验结果表明,在四种不同表面改性白炭黑填充的ACM中,分散剂与偶联剂联合处理的白炭黑和接枝GMA的白炭黑在橡胶基体中分散性较好,且接枝GMA的白炭黑粒子与橡胶基体发生化学作用,粒子被橡胶基体包覆；而力学性能方面则是用接枝GMA的白炭黑填充的ACM性能最好,当白炭黑用量为40%时,其拉伸强度为10.87MPa。
5、环氧型ACM改性尼龙6的性能研究：将环氧型ACM与尼龙6共混并通过差示扫描量热仪(DSC)、X-射线(WAXD)和偏光显微镜(PLM)对环氧型ACM/PA6共混物的热性能和结晶行为及晶体形貌进行研究。结果表明,随着ACM含量的增加,共混体系的融熔温度(Tm)和结晶温度(Tc)都略有下降；PA6的晶型由于环氧型ACM的加入,也由γ晶型转化为α晶型,并且随着橡胶加入量的增加,结晶度逐渐下降,晶粒尺寸逐渐变小,结晶也越来越不完善。力学性能的实验表明,ACM的加入也使得PA6的缺口冲击强度明显提高。
In this dissertation, studies are mainly focused on the copolymerization, vulcanization and the modification of acrylate rubber prepared by emulsion copolymerization and continuous solution polymerization, including the effect of initiator system on the copolymerization rate, influence of the reactive conditions on the gel content; influence of main monomer composition and off volatile condition on raw rubber performance; the optimization of acrylic rubber vulcanization process, including the influence of cure agent and carbon content on vulcanized rubber properties; and also the modification of acrylic rubber with the addition of grafted silica, including the additive dispersion and mechanical properties of the rubber prepared. Furthermore, the systems of nylon6modified with different concentration of acrylic rubber are also studied in the paper, including the thermal dynamics, crystallization behaviors and mechanical properties. The main contents of studies are shown as the following aspects:
1. Emulsion copolymerization of acrylate rubber:The epoxy ACM were prepared by emulsion copolymerization of BA and GMA. The reaction conditions and their effect on the gel content of product are discussed by investigating the influence of initiator system on copolymerization rate and comparing of a series of gel contents and epoxy-opening ratios acquired by different reaction parameters. The results show that the gel content can be less than2.9%, reach the level of foreigh similar product, by the feeding of EA as secondary monomer in a "starve" state in the organic redox complex initiating system, temperature of25-30℃, because the intermolecular transferring of BA and ring-opening of epoxy groups of GMA can be restrained successfully.
2. Continuous solution polymerization of acrylate rubber:In order to obtain the influences of main composition monomer and off volatile condition on raw rubber performance, ACM were prepared by continuous solution polymerization with the main composition monomer of BA and EA, respectively. The molecular weights and distributions obtained are almost the same with different aggregate of main composition monomers, while the glass transition temperature (Tg) of the product varies obviously. The variety of the off-volatile temperature and the revolutions speed results in changes of glass transition temperature (Tg) and molecular weight. The higher temperature off volatile are together with increased molecular weight and widen distribution as well higher glass transition temperature(Tg), while, higher off-volatile revolutions speed leads to lower molecular weight and also wider distribution, as the glass transition temperature(Tg) does not change. The variety of the off-volatile temperature and the revolutions speed results in the droping off-volatile components.
3. Optimization of acrylic rubber cure process parameter and technique formula: Comparison performed among a series of vulcanization and additive systems designed based on the vulcanization and filling strengthen mechanism. From the experiments results it shows that the vulcanization agent and carbon black volume added are related to the acrylic rubber performance as expected, the more vulcanization agent and carbon black added, the higher Shore hardness and the better oil resistance property obtained, while the tensile strength first increases after declining. The break elongation rate keeps droping. The effect of vulcanization agent and accelerant show a cooperation action and the volume of sulfur shows a critical value of0.5shares. From the experimental results, it is shown that the best usage of vulcanization is2%, carbon black volume is50%.
4. The effect of grafted silica reinforcing fillers on the performance of acrylic rubber: Experiments of reinforcing the acrylic rubber by the grafted silica with four kinds of different surface modification performed in order to get the information of the effect of the additive on the acrylic rubber mechanical properties. The result indicates that the dispersion property of the GMA grafted silica modified with dispersant and coupling agent is better and more homogeneous, in which there is some chemical reaction between the GMA grafted silica and the rubber substrate, and the particles are covered by the rubber substrate perfectly; in the meantime, the mechanical properties of the grafted silica filled acrylic rubber is best among the four different modified silica-filled rubbers. When the amount of silica is40%, the tensile strength reaches10.87MPa.
5. The thermal behaviors of nylon6/acrylate rubber (ACM)) blends:Nylon6/acrylate rubber (ACM)) blends are prepared by melt processing and the thermal behaviors have been investigated by differential scanning calorimetry (DSC), The DSC result indicates that the melting temperature, Tm, and the crystallization temperature, Tc, of blends decrease slightly with the increasing of ACM concentration in the blends. The crystallization behavior of the blends studied by wide angle X-ray diffraction (WAXD), and it is revealed that a y→a crystal phase transformation occurs upon addition of ACM into the nylon6, and the crystallinity and crystal size decrease with addition of more ACM into the nylon6. Furthermore, morphologies of nylon6and nylon6/ACM blends are also observed by Polarizing microscope (PLM). It was found that crystal size of nylon6/ACM becomes smaller and crystals of nylon6/ACM are not so perfect any more while the content of ACM increases in the blends. Mechanical experiments show that the notched impact strength of Nylon6/acrylate rubber (ACM)) blends are also enhanced by the addition of modified rubber plastic.
1、乳液聚合法制备ACM：将丙烯酸丁酯(BA)与甲基丙烯酸缩水甘油酯(GMA)进行乳液共聚合以制备环氧型ACM,通过对聚合反应速度和生胶性能的研究,探讨了聚合反应的方法及工艺参数；并通过对聚合物中凝胶含量及环氧基团开环率的对比研究,探讨不同反应条件对凝胶含量的影响。实验结果表明,在反应体系中加入一定量的第二单体丙烯酸乙酯(EA),选择氧化还原复合引发体系,同时将反应温度控制在25-30℃并在饥饿状态下投料可抑制BA的分子内转移和GMA中的环氧基开环,最终可以使聚合物中凝胶含量控制在2.9%以下,达到国外同类产品的水平。
2、连续溶液聚合法制备ACM：分别采用以BA和EA为聚合主单体合成ACM,研究主单体组成和脱挥条件的变化对ACM生胶性能的影响。改变聚合主单体的组成对分子量及分布和脱挥后残留的挥发份影响不大,但随着聚合主单体组成的变化,ACM的玻璃化温度发生变化。脱挥温度和脱挥挤出机转速的变化引起ACM分子量、玻璃化转变温度和脱挥后残留的挥发份的变化,脱挥温度提高,ACM的分子量有所增加,分子量分布宽度变宽,玻璃化转变温度升高；改变脱挥挤出机转速提高,ACM的分子量略有降低,分子量分布稍有变宽,玻璃化转变温度变化不大。脱挥温度和脱挥挤出机转速均使脱挥后残留的挥发份含量下降。
3、ACM硫化技术和配方的研究：从橡胶的硫化机理及填充补强机理入手,将硫化体系和填充体系对ACM的性能进行研究和实验对比。结果表明硫化剂和炭黑用量对ACM的性能有预期的影响,其中邵尔硬度随着硫化剂用量和炭黑用量的增加而增加；耐油性随着硫化剂的引入量的增加而增加；硫化剂和炭黑用量对ACM拉伸强度和断裂伸长率的影响规律基本是一致的,随硫化剂和炭黑用量的增加拉伸强度呈先增加后下降的趋势,而断裂伸长率随硫化剂和炭黑用量的增加呈线性下降；硫化剂与促进剂表现为一种硫化协同效应,硫磺用量有一定的临界值,低于临界值0.5(质量百分数),环氧型ACM不能硫化。实验结果表明硫化剂的最佳用量为2%,炭黑用量为50%。
4、表面改性白炭黑填充ACM性能的研究：将环氧型ACM用不同表面改性的白炭黑进行填充补强,并对其性能进行研究,实验结果表明,在四种不同表面改性白炭黑填充的ACM中,分散剂与偶联剂联合处理的白炭黑和接枝GMA的白炭黑在橡胶基体中分散性较好,且接枝GMA的白炭黑粒子与橡胶基体发生化学作用,粒子被橡胶基体包覆；而力学性能方面则是用接枝GMA的白炭黑填充的ACM性能最好,当白炭黑用量为40%时,其拉伸强度为10.87MPa。
5、环氧型ACM改性尼龙6的性能研究：将环氧型ACM与尼龙6共混并通过差示扫描量热仪(DSC)、X-射线(WAXD)和偏光显微镜(PLM)对环氧型ACM/PA6共混物的热性能和结晶行为及晶体形貌进行研究。结果表明,随着ACM含量的增加,共混体系的融熔温度(Tm)和结晶温度(Tc)都略有下降；PA6的晶型由于环氧型ACM的加入,也由γ晶型转化为α晶型,并且随着橡胶加入量的增加,结晶度逐渐下降,晶粒尺寸逐渐变小,结晶也越来越不完善。力学性能的实验表明,ACM的加入也使得PA6的缺口冲击强度明显提高。
In this dissertation, studies are mainly focused on the copolymerization, vulcanization and the modification of acrylate rubber prepared by emulsion copolymerization and continuous solution polymerization, including the effect of initiator system on the copolymerization rate, influence of the reactive conditions on the gel content; influence of main monomer composition and off volatile condition on raw rubber performance; the optimization of acrylic rubber vulcanization process, including the influence of cure agent and carbon content on vulcanized rubber properties; and also the modification of acrylic rubber with the addition of grafted silica, including the additive dispersion and mechanical properties of the rubber prepared. Furthermore, the systems of nylon6modified with different concentration of acrylic rubber are also studied in the paper, including the thermal dynamics, crystallization behaviors and mechanical properties. The main contents of studies are shown as the following aspects:
1. Emulsion copolymerization of acrylate rubber:The epoxy ACM were prepared by emulsion copolymerization of BA and GMA. The reaction conditions and their effect on the gel content of product are discussed by investigating the influence of initiator system on copolymerization rate and comparing of a series of gel contents and epoxy-opening ratios acquired by different reaction parameters. The results show that the gel content can be less than2.9%, reach the level of foreigh similar product, by the feeding of EA as secondary monomer in a "starve" state in the organic redox complex initiating system, temperature of25-30℃, because the intermolecular transferring of BA and ring-opening of epoxy groups of GMA can be restrained successfully.
2. Continuous solution polymerization of acrylate rubber:In order to obtain the influences of main composition monomer and off volatile condition on raw rubber performance, ACM were prepared by continuous solution polymerization with the main composition monomer of BA and EA, respectively. The molecular weights and distributions obtained are almost the same with different aggregate of main composition monomers, while the glass transition temperature (Tg) of the product varies obviously. The variety of the off-volatile temperature and the revolutions speed results in changes of glass transition temperature (Tg) and molecular weight. The higher temperature off volatile are together with increased molecular weight and widen distribution as well higher glass transition temperature(Tg), while, higher off-volatile revolutions speed leads to lower molecular weight and also wider distribution, as the glass transition temperature(Tg) does not change. The variety of the off-volatile temperature and the revolutions speed results in the droping off-volatile components.
3. Optimization of acrylic rubber cure process parameter and technique formula: Comparison performed among a series of vulcanization and additive systems designed based on the vulcanization and filling strengthen mechanism. From the experiments results it shows that the vulcanization agent and carbon black volume added are related to the acrylic rubber performance as expected, the more vulcanization agent and carbon black added, the higher Shore hardness and the better oil resistance property obtained, while the tensile strength first increases after declining. The break elongation rate keeps droping. The effect of vulcanization agent and accelerant show a cooperation action and the volume of sulfur shows a critical value of0.5shares. From the experimental results, it is shown that the best usage of vulcanization is2%, carbon black volume is50%.
4. The effect of grafted silica reinforcing fillers on the performance of acrylic rubber: Experiments of reinforcing the acrylic rubber by the grafted silica with four kinds of different surface modification performed in order to get the information of the effect of the additive on the acrylic rubber mechanical properties. The result indicates that the dispersion property of the GMA grafted silica modified with dispersant and coupling agent is better and more homogeneous, in which there is some chemical reaction between the GMA grafted silica and the rubber substrate, and the particles are covered by the rubber substrate perfectly; in the meantime, the mechanical properties of the grafted silica filled acrylic rubber is best among the four different modified silica-filled rubbers. When the amount of silica is40%, the tensile strength reaches10.87MPa.
5. The thermal behaviors of nylon6/acrylate rubber (ACM)) blends:Nylon6/acrylate rubber (ACM)) blends are prepared by melt processing and the thermal behaviors have been investigated by differential scanning calorimetry (DSC), The DSC result indicates that the melting temperature, Tm, and the crystallization temperature, Tc, of blends decrease slightly with the increasing of ACM concentration in the blends. The crystallization behavior of the blends studied by wide angle X-ray diffraction (WAXD), and it is revealed that a y→a crystal phase transformation occurs upon addition of ACM into the nylon6, and the crystallinity and crystal size decrease with addition of more ACM into the nylon6. Furthermore, morphologies of nylon6and nylon6/ACM blends are also observed by Polarizing microscope (PLM). It was found that crystal size of nylon6/ACM becomes smaller and crystals of nylon6/ACM are not so perfect any more while the content of ACM increases in the blends. Mechanical experiments show that the notched impact strength of Nylon6/acrylate rubber (ACM)) blends are also enhanced by the addition of modified rubber plastic.
引文
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