异戊橡胶的老化与防老化研究
摘要
异戊橡胶(IR)泛指顺式-1,4结构含量大于90%的聚异戊二烯橡胶，由于其微观结构接近天然橡胶(NR)，也被称为合成NR。由于异戊橡胶分子链含有大量的不饱和双键，其比饱和碳链的烯烃类橡胶更容易氧化，使得异戊橡胶的老化性能不够理想。因此，对其老化和防老化研究具有很重要的意义。本文研究了稀土异戊橡胶的热氧老化行为和不同防老剂在其防老化方面的应用情况，主要工作如下：
1、对未添加防老剂的稀土异戊橡胶进行了150℃热氧老化，利用GPC和1H-NMR分别考察了其分子量、分子量分布和化学结构的变化，发现老化初期发生降解反应，化学结构没有明显的变化，老化后期发生交联反应，有醛类或者羧酸类、双键类化合物生成，可能有含氧类化合物生成。
2、利用TG对未添加防老剂的稀土异戊橡胶和添加防老剂A4的稀土异戊橡胶的氮气气氛下的热重动力学进行了考察，结果表明随着失重比例的增加，活化能有所增大。在相同的失重条件下，添加防老剂A4时的活化能比未添加时都要相对高一些。
3、通过DSC对添加不同防老剂的异戊橡胶生胶氧化诱导期进行了测定，结果显示防老剂A4、A5单独及复配使用时具有非常优异的抗吸氧性能。对于异戊橡胶生胶防老剂配方而言，防老剂A4、A5是首选的防老剂。在100℃热空气下，不同防老剂对异戊硫化橡胶的防老化效果为：A3>A5>A4>A4/A5>A1，说明A3是异戊硫化橡胶防老剂配方中首选的防老剂。
4、考察了不同防老剂对异戊橡胶生胶热分解的影响，并且对添加不同防老剂的硫化胶进行了ATR-FTIR、SEM、DMA分析。ATR-FTIR分析表明在热氧老化过程中，在橡胶表面发生了明显的降解反应，臭氧老化则没有。SEM分析说明100℃热氧老化24h后出现喷霜但无裂纹生成，热氧老化48h裂纹正在形成，热氧老化72h后明显产生裂纹；臭氧老化12h后表面龟裂的同时也有少量硫磺喷霜。DMA测试表明随着老化时间的增加，最大损耗因子、玻璃化温度Tg和Tan0℃及Tan60℃都显著增大，当添加防老剂时，这种变化的趋势有所减弱。
Isoprene rubber (IR) refers to polyisoprene that the cis-1,4structure content ismore than90%. Due to the same microstructure of IR as natural rubber (NR),it is usually called synthetic NR, Because isoprene rubber contains a largeamount of unsaturated double bond in the molecular chain, it is more easily tobe oxidized, which makes unsightly anti-aging performance. Therefore, theresearches on the aging and anti-aging of IR is significance. In this thesis, thethermal oxidative aging behavior and the application of different antioxidantsin the isoprene rubber have been studied. The original researches have listedas following,
1. Isoprene rubber without antioxidant was carried out in150℃for thethermal oxygen aging. Molecular weight, molecular weight distribution andchanges of chemical structure have been investgated by GPC and1H-NMR. Itis shows that degradation reaction of isoprene rubber happened but nosignificant chemical structure changed at the beginning of ageing. However, inlater stage, crosslinking reaction happened, and aldehyde, carboxylic acid,olefin were generated，maybe oxygen compounds were generated.
2. Thermogravimetric kinetics to isoprene rubbers without antioxidant andwith antioxidant A4have been investigated by TG under N2. It suggested thatwith the increase of proportion of weightlessness, the activation energyincreased. And in the same weightlessness conditions, the activation energy ofIR with antioxidant A4is higher than that without antioxidant relatively.
3. The oxidation induction time of raw isoprene rubber with differentantioxidants was characterized by DSC. When antioxidant A4and A5wereused respectively or together in IR, they showed excellent effects on oxygen resistance performance. So antioxidant A4and A5are the very goodantioxidants for raw IR. For vulcanized IR, the anti-ageing effect of differentantioxidant is A3>A5>A4>A4/A5>A1under air in100℃. So antioxidantA3is the best antioxidant for vulcanized IR.
4. The thermal decomposition reactions of raw isoprene rubbers withdiffenet antioxidants were investigated. The vulcanized isoprene rubbers withdifferent antioxidants were charactered by ATR-FTIR, SEM and DMA.Degradation reaction on the rubber surface was obviously observed in hotoxygen aging process using the ATR-FTIR analysis, but the ozone aging is adifferent process. The SEM analysis shows that the vulcanized isoprene rubberappeared spray frost and did not emerged cracks after thermal-oxidative agingfor24h. The cracks were taking shape during thermal-oxidative aging for48h,and the clearly cracks emerged after thermal-oxidative aging for72h. And thevulcanized isoprene rubbers also had emerged cracks and also have a smallamount of sulfur spray frost after ozone ageing for12h. The DMA resultreveals that with increasing aging time, the cross-linking reaction carried onthe the molecular chain of IR and activity of molecular chain was blocked, sothe Tg, Tan0℃and Tan60℃of IR significant increased. When antioxidantwas added in the isoprene rubber, this trend was weakened.
1、对未添加防老剂的稀土异戊橡胶进行了150℃热氧老化，利用GPC和1H-NMR分别考察了其分子量、分子量分布和化学结构的变化，发现老化初期发生降解反应，化学结构没有明显的变化，老化后期发生交联反应，有醛类或者羧酸类、双键类化合物生成，可能有含氧类化合物生成。
2、利用TG对未添加防老剂的稀土异戊橡胶和添加防老剂A4的稀土异戊橡胶的氮气气氛下的热重动力学进行了考察，结果表明随着失重比例的增加，活化能有所增大。在相同的失重条件下，添加防老剂A4时的活化能比未添加时都要相对高一些。
3、通过DSC对添加不同防老剂的异戊橡胶生胶氧化诱导期进行了测定，结果显示防老剂A4、A5单独及复配使用时具有非常优异的抗吸氧性能。对于异戊橡胶生胶防老剂配方而言，防老剂A4、A5是首选的防老剂。在100℃热空气下，不同防老剂对异戊硫化橡胶的防老化效果为：A3>A5>A4>A4/A5>A1，说明A3是异戊硫化橡胶防老剂配方中首选的防老剂。
4、考察了不同防老剂对异戊橡胶生胶热分解的影响，并且对添加不同防老剂的硫化胶进行了ATR-FTIR、SEM、DMA分析。ATR-FTIR分析表明在热氧老化过程中，在橡胶表面发生了明显的降解反应，臭氧老化则没有。SEM分析说明100℃热氧老化24h后出现喷霜但无裂纹生成，热氧老化48h裂纹正在形成，热氧老化72h后明显产生裂纹；臭氧老化12h后表面龟裂的同时也有少量硫磺喷霜。DMA测试表明随着老化时间的增加，最大损耗因子、玻璃化温度Tg和Tan0℃及Tan60℃都显著增大，当添加防老剂时，这种变化的趋势有所减弱。
Isoprene rubber (IR) refers to polyisoprene that the cis-1,4structure content ismore than90%. Due to the same microstructure of IR as natural rubber (NR),it is usually called synthetic NR, Because isoprene rubber contains a largeamount of unsaturated double bond in the molecular chain, it is more easily tobe oxidized, which makes unsightly anti-aging performance. Therefore, theresearches on the aging and anti-aging of IR is significance. In this thesis, thethermal oxidative aging behavior and the application of different antioxidantsin the isoprene rubber have been studied. The original researches have listedas following,
1. Isoprene rubber without antioxidant was carried out in150℃for thethermal oxygen aging. Molecular weight, molecular weight distribution andchanges of chemical structure have been investgated by GPC and1H-NMR. Itis shows that degradation reaction of isoprene rubber happened but nosignificant chemical structure changed at the beginning of ageing. However, inlater stage, crosslinking reaction happened, and aldehyde, carboxylic acid,olefin were generated，maybe oxygen compounds were generated.
2. Thermogravimetric kinetics to isoprene rubbers without antioxidant andwith antioxidant A4have been investigated by TG under N2. It suggested thatwith the increase of proportion of weightlessness, the activation energyincreased. And in the same weightlessness conditions, the activation energy ofIR with antioxidant A4is higher than that without antioxidant relatively.
3. The oxidation induction time of raw isoprene rubber with differentantioxidants was characterized by DSC. When antioxidant A4and A5wereused respectively or together in IR, they showed excellent effects on oxygen resistance performance. So antioxidant A4and A5are the very goodantioxidants for raw IR. For vulcanized IR, the anti-ageing effect of differentantioxidant is A3>A5>A4>A4/A5>A1under air in100℃. So antioxidantA3is the best antioxidant for vulcanized IR.
4. The thermal decomposition reactions of raw isoprene rubbers withdiffenet antioxidants were investigated. The vulcanized isoprene rubbers withdifferent antioxidants were charactered by ATR-FTIR, SEM and DMA.Degradation reaction on the rubber surface was obviously observed in hotoxygen aging process using the ATR-FTIR analysis, but the ozone aging is adifferent process. The SEM analysis shows that the vulcanized isoprene rubberappeared spray frost and did not emerged cracks after thermal-oxidative agingfor24h. The cracks were taking shape during thermal-oxidative aging for48h,and the clearly cracks emerged after thermal-oxidative aging for72h. And thevulcanized isoprene rubbers also had emerged cracks and also have a smallamount of sulfur spray frost after ozone ageing for12h. The DMA resultreveals that with increasing aging time, the cross-linking reaction carried onthe the molecular chain of IR and activity of molecular chain was blocked, sothe Tg, Tan0℃and Tan60℃of IR significant increased. When antioxidantwas added in the isoprene rubber, this trend was weakened.
引文
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