端羟基聚丁二烯桥接2,2'-甲撑（或硫代）双（4-甲基-6-叔丁基苯酚）的合成及其对天然橡胶抗热氧老化作用的研究
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摘要
高分子材料在贮存、加工及使用过程中，在热、氧、臭氧及机械力等作用下易发生氧化，引起分子链的降解或交联，导致材料的性能变差而失去使用价值，这种现象称为老化。特别是橡胶分子链中由于含有大量的双键，氧化老化更加突出。为了抑制、阻止或延缓氧化反应的发生，通常加入一些能延缓氧化老化的抗氧剂或防老剂。然而，目前常用的低分子抗氧剂容易从高分子基体中挥发、迁移或被抽提出来，使高分子材料的抗热氧老化性能变差以及可能会污染环境。因此，近年来，具有耐迁移性的聚合物型抗氧剂愈来愈引起人们的重视。本文采用异佛尔酮二异氰酸酯（IPDI）作为桥接剂，制备了两种具有优异抗热氧老化性能的新型聚合物型抗氧剂端羟基聚丁二烯桥接2,2′-甲撑（或硫代）双（4-甲基-6-叔丁基苯酚）（HTPB-IPDI-MPH或HTPB-IPDI-TPH）。研究了HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶硫化胶的抗热氧老化作用及其耐抽提性能的影响，探讨了其抗热氧老化机理。主要研究内容和结果包括：
第一，通过端羟基聚丁二烯（HTPB）与异佛尔酮二异氰酸酯（IPDI）反应合成HTPB-IPDI加成物，再与2,2′-甲撑双（4-甲基-6-叔丁基苯酚）（MPH）或2,2′-硫代双（4-甲基-6-叔丁基苯酚）（TPH）反应，制备了两种新型聚合物型抗氧剂（HTPB-IPDI-MPH或HTPB-IPDI-TPH）。研究了反应物配比和反应条件对合成反应的影响。发现IPDI与HTPB反应的最佳条件：DBTDL用量为IPDI的0.6wt%，反应温度为40°C，反应时间为270min。MPH或TPH与HTPB-IPDI加成物反应的最佳条件均为：MPH或TPH与HTPB-IPDI加成物中-NCO的摩尔比为3：1，催化剂DBTDL用量为反应物总量的1.6wt%，反应温度为75°C，反应时间为360min，此时，MPH和TPH与HTPB-IPDI加成物反应的最终-NCO的残留量分别为0.29wt%和0.43wt%。
第二，采用FT-IR、1H-NMR、13C-NMR和GPC对HTPB-IPDI-MPH和HTPB-IPDI-TPH进行结构表征，并借助TGA研究了其热稳定性。结果表明：在与HTPB-IPDI加成物反应过程中，每个MPH或TPH中只有一个酚羟基参与了反应，在合成产物HTPB-IPDI-MPH和HTPB-IPDI-TPH里各自保留了另一个酚羟基。HTPB-IPDI-MPH和HTPB-IPDI-TPH的热稳定性明显优于相应低分子抗氧剂MPH和TPH。
第三，研究了HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶的硫化特性和加工性能，以及硫化胶的力学性能和动态粘弹性能的影响。结果表明：HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶具有明显的促进硫化作用，但对天然橡胶硫化胶的力学性能影响不大。添加了HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶混炼胶和硫化胶比使用相应低分子抗氧剂MPH和TPH的Payne效应更明显。
第四，研究了HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶硫化胶抗热氧老化性能的影响，结合FTIR-ATR的分析结果，探讨了抗热氧老化机理。发现HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶硫化胶的抗热氧老化性能明显优于相应的低分子抗氧剂MPH和TPH，进一步与自己合成的端羟基聚丁二烯桥接2,6-二叔丁基对甲酚（HTPB-IPDI-BHT）和2,2′-甲撑（或硫代）双（4-甲基-6-叔丁基苯酚）单十二酸酯（MPH-DA或TPH-DA）比较，发现氨基甲酸酯具有抗热氧老化作用，它与酚羟基之间存在协同抗热氧老化作用。
第五，研究了添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶的耐抽提性能，并与低分子抗氧剂MPH和TPH，以及自己合成的十二醇桥接2,2′-甲撑双（4-甲基-6-叔丁基苯酚）（DN-IPDI-MPH）和十二醇桥接2,2′-硫代双（4-甲基-6-叔丁基苯酚）（DN-IPDI-TPH）相比较，发现HTPB-IPDI-MPH和HTPB-IPDI-TPH具有优异的耐抽提性能，添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶经100°C沸水抽提后，再经100°C老化48h的老化系数分别为0.55和0.56，而添加DN-IPDI-MPH和DN-IPDI-TPH的分别为0.37和0.41，添加低分子抗氧剂MPH和TPH的分别为0.28和0.34。添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶经甲醇抽提后，再经100°C老化48h老化系数分别为0.44和0.48，而添加DN-IPDI-MPH和DN-IPDI-TPH的分别为0.40和0.39，添加低分子抗氧剂MPH和TPH的均为0.36。
Polymers are easy to suffer from uncontrolled oxidation in the process of storage, processing and using because of the effects of heat, oxygen, ozone, mechanical stress and so on. It results in crosslinking or degradation of the molecular chain, and leads to deteriorate in structure and properties to lose use value. The phenomenon is referred to as the oxidative aging of the polymer. The oxidative aging is severe especially for rubbers containing a large amount of unsaturated C=C bonds in their molecular chain. In order to prevent or retard oxidative reaction, various antioxidants are usually added into the polymers. However, low molecular weight antioxidants are easy to volatilize, migrate, or be extracted from the polymer substrate, which makes the thermo-oxidative aging resistance of polymer worse and could results in environment pollution. In recent years, polymeric antioxidant has increasingly attracted attention in order to avoid the loss of antioxidant from the substrate. In this dissertation, two kinds of novel polymeric antioxidants hydroxyl terminated polybutadiene bound2,2'-methylenebis (4-methyl-6-tert-butylphenol) or2,2'-thiobis (4-methyl-6-tert-butylphenol)(HTPB-IPDI-MPH or HTPB-IPDI-TPH) were prepared through isophorone diisocyanate (IPDI) as bridging agent. The effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on thermo-oxidative aging resistance for NR vulcanizates and their extraction resistance were investigated, and the mechanism of thermo-oxidative aging resistance was discussed. The main research contents and results are listed as following:
Firstly, two kinds of novel polymeric antioxidants HTPB-IPDI-MPH and HTPB-IPDI-TPH were synthesized by the reactions between2,2-methylenebis (4-methyl-6-tert-butylphenol)(MPH) or2,2'-thiobis (4-methyl-6-tert-butylphenol)(TPH) and an adduct (HTPB-IPDI) from hydroxyl terminated polybutadiene (HTPB) and isophorone diisocyanate (IPDI). The effects of reactants ratio and the reaction condition on the reaction were investigated by measuring the content of the residual-NCO groups of the reactants during the reaction. The optimal reaction condition between IPDI and HTPB was that the amount of dibutyltin dilaurate (DBTDL) was0.6wt%based on IPDI, and the temperature and time were40℃and270min, respectively. The reaction condition between MPH or TPH and HTPB-IPDI was that the molar ratio of MPH or TPH to-NCO in HTPB-IPDI was3:1, and the amount of DBTDL was1.6wt%based on the total of reactants, and the temperature and time were75℃and360min, respectively. The content of the residual-NCO groups of the reactants were0.29wt%or0.43wt%under this condition, respectively.
Secondly, the structures of HTPB-IPDI-MPH and HTPB-IPDI-TPH were characterized by FT-IR,1H-NMR,13C-NMR and GPC, and the thermal stability of HTPB-IPDI-MPH and HTPB-IPDI-TPH was investigated by TGA. The results showed that only one of phenolic-OH in MPH or TPH reacted with-NCO in HTPB-IPDI, while another phenolic-OH in MPH or TPH remained in HTPB-IPDI-MPH and HTPB-IPDI-TPH, respectively. The thermal stability of HTPB-IPDI-MPH and HTPB-IPDI-TPH were obviously superior to corresponding low molecualar weigth antioxidant MPH and TPH, respectively.
Thirdly, the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on curing characteristics and processing properties of NR compounds, mechanical properties and dynamic viscoelastic properties of NR vulcanizates were investigated. The results showed that HTPB-IPDI-MPH and HTPB-IPDI-TPH could promote the vulcanization, but the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on mechnical properties of NR vulcanizates was slight. The NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH exhibited more obvious payne effect than that of the low molecular weight antioxidant MPH and TPH.
Fourthly, the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on the thermo-oxidative aging resistance was investigated, and the mechanism of thermo-oxidative aging resistance was discussed combining with results of FTIR-ATR spectra. The results showed that the thermo-oxidative aging resistance of NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH were superior to that of MPH and TPH. Compared with hydroxyl terminated polybutadiene bound2,6-dibutyl-4-methylphenol (HTPB-IPDI-BHT),2,2'-methylenebis (4-methyl-6-tert-butylphenol) dodecanoic acid ester (MPH-DA) and2,2'-thiobis (4-methyl-6-tert-butylphenol) dodecanoic acid ester (TPH-DA) which were synthesized by our team, it was found that-NHCOO-groups in HTPB-IPDI-MPH and HTPB-IPDI-TPH had thermo-oxidatve aging resistance and synergistic effect with phenolic hydroxy group.
Lastly, the extraction resistance of NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH was investigated by compared with MPH, TPH, dodecanol bound2,2'-methylenebis (4-methyl-6-tert-butylphenol)(DN-IPDI-MPH) and dodecanol bound2,2-thiobis (4-methyl-6-tert-butylphenol)(DN-IPDI-TPH). The results showed that HTPB-IPDI-MPH and HTPB-IPDI-TPH had excellent extraction resistance. The aging coefficien of the NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH which was extracted in100℃boiling water were0.55and0.56after aging at100℃for48h, respectively. The aging coefficien of DN-IPDI-MPH and DN-IPDI-TPH were0.37and0.41, respectively, while the aging coefficien of MPH and TPH were0.28and0.34, respectively. The aging coefficien of the NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH which was extracted in methanol were0.44and0.48after aging at100℃for48h, respectively. The aging coefficien of DN-IPDI-MPH and DN-IPDI-TPH were0.40and0.39, respectively, while the aging coefficien of MPH and TPH were0.36.
第一，通过端羟基聚丁二烯（HTPB）与异佛尔酮二异氰酸酯（IPDI）反应合成HTPB-IPDI加成物，再与2,2′-甲撑双（4-甲基-6-叔丁基苯酚）（MPH）或2,2′-硫代双（4-甲基-6-叔丁基苯酚）（TPH）反应，制备了两种新型聚合物型抗氧剂（HTPB-IPDI-MPH或HTPB-IPDI-TPH）。研究了反应物配比和反应条件对合成反应的影响。发现IPDI与HTPB反应的最佳条件：DBTDL用量为IPDI的0.6wt%，反应温度为40°C，反应时间为270min。MPH或TPH与HTPB-IPDI加成物反应的最佳条件均为：MPH或TPH与HTPB-IPDI加成物中-NCO的摩尔比为3：1，催化剂DBTDL用量为反应物总量的1.6wt%，反应温度为75°C，反应时间为360min，此时，MPH和TPH与HTPB-IPDI加成物反应的最终-NCO的残留量分别为0.29wt%和0.43wt%。
第二，采用FT-IR、1H-NMR、13C-NMR和GPC对HTPB-IPDI-MPH和HTPB-IPDI-TPH进行结构表征，并借助TGA研究了其热稳定性。结果表明：在与HTPB-IPDI加成物反应过程中，每个MPH或TPH中只有一个酚羟基参与了反应，在合成产物HTPB-IPDI-MPH和HTPB-IPDI-TPH里各自保留了另一个酚羟基。HTPB-IPDI-MPH和HTPB-IPDI-TPH的热稳定性明显优于相应低分子抗氧剂MPH和TPH。
第三，研究了HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶的硫化特性和加工性能，以及硫化胶的力学性能和动态粘弹性能的影响。结果表明：HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶具有明显的促进硫化作用，但对天然橡胶硫化胶的力学性能影响不大。添加了HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶混炼胶和硫化胶比使用相应低分子抗氧剂MPH和TPH的Payne效应更明显。
第四，研究了HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶硫化胶抗热氧老化性能的影响，结合FTIR-ATR的分析结果，探讨了抗热氧老化机理。发现HTPB-IPDI-MPH和HTPB-IPDI-TPH对天然橡胶硫化胶的抗热氧老化性能明显优于相应的低分子抗氧剂MPH和TPH，进一步与自己合成的端羟基聚丁二烯桥接2,6-二叔丁基对甲酚（HTPB-IPDI-BHT）和2,2′-甲撑（或硫代）双（4-甲基-6-叔丁基苯酚）单十二酸酯（MPH-DA或TPH-DA）比较，发现氨基甲酸酯具有抗热氧老化作用，它与酚羟基之间存在协同抗热氧老化作用。
第五，研究了添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶的耐抽提性能，并与低分子抗氧剂MPH和TPH，以及自己合成的十二醇桥接2,2′-甲撑双（4-甲基-6-叔丁基苯酚）（DN-IPDI-MPH）和十二醇桥接2,2′-硫代双（4-甲基-6-叔丁基苯酚）（DN-IPDI-TPH）相比较，发现HTPB-IPDI-MPH和HTPB-IPDI-TPH具有优异的耐抽提性能，添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶经100°C沸水抽提后，再经100°C老化48h的老化系数分别为0.55和0.56，而添加DN-IPDI-MPH和DN-IPDI-TPH的分别为0.37和0.41，添加低分子抗氧剂MPH和TPH的分别为0.28和0.34。添加HTPB-IPDI-MPH和HTPB-IPDI-TPH的天然橡胶硫化胶经甲醇抽提后，再经100°C老化48h老化系数分别为0.44和0.48，而添加DN-IPDI-MPH和DN-IPDI-TPH的分别为0.40和0.39，添加低分子抗氧剂MPH和TPH的均为0.36。
Polymers are easy to suffer from uncontrolled oxidation in the process of storage, processing and using because of the effects of heat, oxygen, ozone, mechanical stress and so on. It results in crosslinking or degradation of the molecular chain, and leads to deteriorate in structure and properties to lose use value. The phenomenon is referred to as the oxidative aging of the polymer. The oxidative aging is severe especially for rubbers containing a large amount of unsaturated C=C bonds in their molecular chain. In order to prevent or retard oxidative reaction, various antioxidants are usually added into the polymers. However, low molecular weight antioxidants are easy to volatilize, migrate, or be extracted from the polymer substrate, which makes the thermo-oxidative aging resistance of polymer worse and could results in environment pollution. In recent years, polymeric antioxidant has increasingly attracted attention in order to avoid the loss of antioxidant from the substrate. In this dissertation, two kinds of novel polymeric antioxidants hydroxyl terminated polybutadiene bound2,2'-methylenebis (4-methyl-6-tert-butylphenol) or2,2'-thiobis (4-methyl-6-tert-butylphenol)(HTPB-IPDI-MPH or HTPB-IPDI-TPH) were prepared through isophorone diisocyanate (IPDI) as bridging agent. The effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on thermo-oxidative aging resistance for NR vulcanizates and their extraction resistance were investigated, and the mechanism of thermo-oxidative aging resistance was discussed. The main research contents and results are listed as following:
Firstly, two kinds of novel polymeric antioxidants HTPB-IPDI-MPH and HTPB-IPDI-TPH were synthesized by the reactions between2,2-methylenebis (4-methyl-6-tert-butylphenol)(MPH) or2,2'-thiobis (4-methyl-6-tert-butylphenol)(TPH) and an adduct (HTPB-IPDI) from hydroxyl terminated polybutadiene (HTPB) and isophorone diisocyanate (IPDI). The effects of reactants ratio and the reaction condition on the reaction were investigated by measuring the content of the residual-NCO groups of the reactants during the reaction. The optimal reaction condition between IPDI and HTPB was that the amount of dibutyltin dilaurate (DBTDL) was0.6wt%based on IPDI, and the temperature and time were40℃and270min, respectively. The reaction condition between MPH or TPH and HTPB-IPDI was that the molar ratio of MPH or TPH to-NCO in HTPB-IPDI was3:1, and the amount of DBTDL was1.6wt%based on the total of reactants, and the temperature and time were75℃and360min, respectively. The content of the residual-NCO groups of the reactants were0.29wt%or0.43wt%under this condition, respectively.
Secondly, the structures of HTPB-IPDI-MPH and HTPB-IPDI-TPH were characterized by FT-IR,1H-NMR,13C-NMR and GPC, and the thermal stability of HTPB-IPDI-MPH and HTPB-IPDI-TPH was investigated by TGA. The results showed that only one of phenolic-OH in MPH or TPH reacted with-NCO in HTPB-IPDI, while another phenolic-OH in MPH or TPH remained in HTPB-IPDI-MPH and HTPB-IPDI-TPH, respectively. The thermal stability of HTPB-IPDI-MPH and HTPB-IPDI-TPH were obviously superior to corresponding low molecualar weigth antioxidant MPH and TPH, respectively.
Thirdly, the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on curing characteristics and processing properties of NR compounds, mechanical properties and dynamic viscoelastic properties of NR vulcanizates were investigated. The results showed that HTPB-IPDI-MPH and HTPB-IPDI-TPH could promote the vulcanization, but the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on mechnical properties of NR vulcanizates was slight. The NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH exhibited more obvious payne effect than that of the low molecular weight antioxidant MPH and TPH.
Fourthly, the effect of HTPB-IPDI-MPH and HTPB-IPDI-TPH on the thermo-oxidative aging resistance was investigated, and the mechanism of thermo-oxidative aging resistance was discussed combining with results of FTIR-ATR spectra. The results showed that the thermo-oxidative aging resistance of NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH were superior to that of MPH and TPH. Compared with hydroxyl terminated polybutadiene bound2,6-dibutyl-4-methylphenol (HTPB-IPDI-BHT),2,2'-methylenebis (4-methyl-6-tert-butylphenol) dodecanoic acid ester (MPH-DA) and2,2'-thiobis (4-methyl-6-tert-butylphenol) dodecanoic acid ester (TPH-DA) which were synthesized by our team, it was found that-NHCOO-groups in HTPB-IPDI-MPH and HTPB-IPDI-TPH had thermo-oxidatve aging resistance and synergistic effect with phenolic hydroxy group.
Lastly, the extraction resistance of NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH was investigated by compared with MPH, TPH, dodecanol bound2,2'-methylenebis (4-methyl-6-tert-butylphenol)(DN-IPDI-MPH) and dodecanol bound2,2-thiobis (4-methyl-6-tert-butylphenol)(DN-IPDI-TPH). The results showed that HTPB-IPDI-MPH and HTPB-IPDI-TPH had excellent extraction resistance. The aging coefficien of the NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH which was extracted in100℃boiling water were0.55and0.56after aging at100℃for48h, respectively. The aging coefficien of DN-IPDI-MPH and DN-IPDI-TPH were0.37and0.41, respectively, while the aging coefficien of MPH and TPH were0.28and0.34, respectively. The aging coefficien of the NR vulcanizates with HTPB-IPDI-MPH and HTPB-IPDI-TPH which was extracted in methanol were0.44and0.48after aging at100℃for48h, respectively. The aging coefficien of DN-IPDI-MPH and DN-IPDI-TPH were0.40and0.39, respectively, while the aging coefficien of MPH and TPH were0.36.
引文
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