锰离子对天然橡胶老化性能的影响
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摘要
研究锰离子含量对天然橡胶(NR)热氧老化、紫外老化和臭氧老化前后性能的影响,并采用核磁交联密度分析仪、DSC分析仪和傅里叶红外分析仪探究老化前后分子链结构的变化。结果表明,在老化之前,含有不同量的锰离子的天然橡胶的物理机械性能基本一致。经3种方式老化后的胶样性能均有不同程度的下降,当锰离子质量分数为0.000 30%时,天然橡胶老化后的拉伸强度、300%定伸应力、700%定伸应力下降程度最小。核磁交联密度测试表明,总交联密度(XLD)与网链分子量(Mc)有很好的对应关系,XLD随着锰离子质量分数的增加而先增大后减小,表明天然橡胶老化过程中交联反应和断裂反应存在竞争关系。示差扫描量热(DSC)测试发现,随着锰离子质量分数的增加,天然橡胶的玻璃化转变温度(Tg)先升高后降低,与核磁交联密度测试结果一致。红外分析(FTIR)发现,天然橡胶老化过程中发生了交联和断裂反应。
The effect of manganese ion content on the properties and molecular chain structure of natural rubber( NR) before and after thermal oxidative aging, UV aging and ozone aging were studied using magnetic crosslink density analyzer, DSC analyzer and Fourier transform infrared analyzer to explore the mechanism of aging. The results showed that the physical mechanical properties of natural rubber containing different amounts of manganese ions were basically consistent with the aging before aging. By the three ways after aging colloid properties had different degrees of decline. When the manganese ion concentration was 0.000 30%, the tensile strength, 300%tensile stress and 700% tensile stress decreased least. Crosslink density test showed that the total crosslinking density(XLD) and net chain molecular weight(Mc) had a good relationship, XLD with the increase of manganese ion mass fraction increased first and decreased in the aging process, showing that the natural rubber crosslinking reaction and breaking reaction in competition. The results of differential scanning calorimetry( DSC) showed that the glass transition temperature(Tg) of natural rubber increased first and then decreased with the increase of Mn ion mass fraction, which was consistent with the results of nuclear magnetic cross link density test. Infrared analysis(FTIR) found that the aging process of natural rubber in the process of crosslinking and fracture.
The effect of manganese ion content on the properties and molecular chain structure of natural rubber( NR) before and after thermal oxidative aging, UV aging and ozone aging were studied using magnetic crosslink density analyzer, DSC analyzer and Fourier transform infrared analyzer to explore the mechanism of aging. The results showed that the physical mechanical properties of natural rubber containing different amounts of manganese ions were basically consistent with the aging before aging. By the three ways after aging colloid properties had different degrees of decline. When the manganese ion concentration was 0.000 30%, the tensile strength, 300%tensile stress and 700% tensile stress decreased least. Crosslink density test showed that the total crosslinking density(XLD) and net chain molecular weight(Mc) had a good relationship, XLD with the increase of manganese ion mass fraction increased first and decreased in the aging process, showing that the natural rubber crosslinking reaction and breaking reaction in competition. The results of differential scanning calorimetry( DSC) showed that the glass transition temperature(Tg) of natural rubber increased first and then decreased with the increase of Mn ion mass fraction, which was consistent with the results of nuclear magnetic cross link density test. Infrared analysis(FTIR) found that the aging process of natural rubber in the process of crosslinking and fracture.
引文
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[13]邓思娟,周衡刚.差示扫描量热法在橡胶材料分析中的应用[J].合成材料老化与应用,2016,45(3):120-123.
[14]徐琳,王乃岩,霸书红,等.傅里叶变换衰减全反射红外光谱法的应用与进展[J].光谱学与光谱分析,2004,24(3):317-319.
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[16]王曙光,宗成中,王春英.顺式-1,4-聚异戊二烯橡胶研究进展[J].中国橡胶,2007,23(5):37-40.
[17]吕明哲,黄茂芳,陈美,等.金属离子对不同品系天然橡胶热稳定性的影响[C]//中国热带作物学会2007年学术年会论文集.2007.
[18]李昂.阻止橡胶等高分子老化的其他助剂[J].橡胶参考资料,2009(3):67-70.
[19]陈美,敖宁建,卞军,等.变价金属离子对医用胶乳制品老化性能的影响[J].橡胶工业,2003,50(7):418-420.
[20]敖宁建,陈鹰.粘土中金属组分对天然橡胶/粘土复合材料老化性能的影响[J].热带作物学报,1999(3):16-20.
[21]李思东,彭政,余和平,等.用红外差谱表征橡胶的热老化[J].橡胶工业,1998(8):494-498.)
[22]Kumar A,Commereuc S,Verney V.Ageing of elastomers:a molecular approach base d on rheological characterization[J].Polymer Degradation&Stability,2004,85(2):751-757.
[2]杨清芝.现代橡胶工艺学[M].北京:中国石化出版社,1997.
[3]邓本诚.橡胶工艺原理[M].北京:化学工业出版社,1984.
[4]Haber F,Weiss J.The catalytic decomposition of hydrogen peroxide by iron salts[J].Proceedings of the Royal Society A Mathematical Physical&Engineering Sciences,1934,147:332-351.
[5]Reich L,Jadrnicek B R,Stivala S S.Effect of oxidationreduction potential on the metal salt-catalyzed autoxidation of atactic polypropylene[J].Journal of Polymer Science Part A-1Polymer Chemistry,1971,9(1):231-233.
[6]Villain H.The action of copper and its derivatives on the aging of rubber[J].Rubber Chemistry&Technology,1950,5(2):352-361.
[7]Albert H E,Smith G E P,Gottschalk G W.Effect of iron on aging of GR-S[J].Ind Eng Chem,1948,40(3):482-487.
[8]朱敏.橡胶化学与物理[M].北京:化学工业出版社,1984:266-267.
[9]陈美,敖宁建,卞军,等.变价金属离子对医用胶乳制品老化性能的影响[J].橡胶工业,2003,50(7):418-420.
[10]刘杨,邸明伟,张彦华,等.极性化SBS的热氧老化——(I)微观结构变化[J].高分子材料科学与工程,2010,26(7):74-77.
[11]邸明伟,刘杨,张彦华,等.极性化SBS的热氧老化——(Ⅱ)表面元素分析[J].高分子材料科学与工程,2010,26(7):82-85.
[12]李普旺,吕明哲,杨子明,等.环氧化天然橡胶生胶加速贮存老化期间交联结构变化[J].合成材料老化与应用,2015,13(1):1-4.
[13]邓思娟,周衡刚.差示扫描量热法在橡胶材料分析中的应用[J].合成材料老化与应用,2016,45(3):120-123.
[14]徐琳,王乃岩,霸书红,等.傅里叶变换衰减全反射红外光谱法的应用与进展[J].光谱学与光谱分析,2004,24(3):317-319.
[15]Tomer N S,Delor-Jestin F,Singh R P,et al.Cross-linking assessment after accelerated ageing of ethylene propylene diene monomer rubber[J].Polymer Degradation&Stability,2007,92(3):457-463.
[16]王曙光,宗成中,王春英.顺式-1,4-聚异戊二烯橡胶研究进展[J].中国橡胶,2007,23(5):37-40.
[17]吕明哲,黄茂芳,陈美,等.金属离子对不同品系天然橡胶热稳定性的影响[C]//中国热带作物学会2007年学术年会论文集.2007.
[18]李昂.阻止橡胶等高分子老化的其他助剂[J].橡胶参考资料,2009(3):67-70.
[19]陈美,敖宁建,卞军,等.变价金属离子对医用胶乳制品老化性能的影响[J].橡胶工业,2003,50(7):418-420.
[20]敖宁建,陈鹰.粘土中金属组分对天然橡胶/粘土复合材料老化性能的影响[J].热带作物学报,1999(3):16-20.
[21]李思东,彭政,余和平,等.用红外差谱表征橡胶的热老化[J].橡胶工业,1998(8):494-498.)
[22]Kumar A,Commereuc S,Verney V.Ageing of elastomers:a molecular approach base d on rheological characterization[J].Polymer Degradation&Stability,2004,85(2):751-757.