聚丙烯官能化及其分子结构的研究
摘要
本文采用溶液接枝法，以过氧化物(DCP)为引发剂，制备了马来酸酐(MAH)接枝的聚丙烯(PP)。采用化学滴定法、红外光谱法、凝胶色谱法(GPC)和流变等方法表征了接枝产物，并重点应用核磁共振(NMR)技术研究了马来酸酐接枝聚丙烯的分子结构以及MAH的添加量对接枝产物的影响。此外，本文还进行了PP／尼龙6(PA6)共混体系形态形成演变研究。
红外光谱显示，在1700—1900cm~(-1)区域有明显的羰基伸缩振动吸收峰，这说明马来酸酐已经成功地接在聚丙烯链上。化学滴定结果表明产物的接枝率与起始马来酸酐的浓度有关。GPC测试结果表明产物的分子量对起始马来酸酐的浓度有一定的依赖性，马来酸酐的浓度越大，产物的分子量越小，并与流变结果一致。
核磁共振仪对产物的分子结构研究表明：1．接在聚丙烯分子链三级碳上的马来酸酐的信号随MAH浓度的增加而增强，而接在链末端(由聚丙烯链β断裂产生)的MAH信号随MAH浓度的增加强度几乎不变。2．MAH以双键形式接在聚丙烯链末端的信号随MAH浓度的增加显著增强，说明更多的β断裂发生在MAH接枝到PP后，并使聚丙烯分子量随马来酸酐浓度增加而下降。3．MAH的用量对接枝PP链的等规度有很大的影响，主要表现在随MAH浓度增加，PP链的mm序列所占的比例逐渐增大，mr和rr序列所占的比例逐渐减小。
通过PP／PA6共混实验，我们发现：1．在一定的剪切速率(20s~-下，随着剪切时间的增加，尼龙相的粒径减小到一平衡值，随着剪切速率的增加，尼龙粒径达到平衡值所需要的时间逐渐减短。2．剪切时间固定，变化剪切速率，发现随着剪切速率的增加，尼龙相的粒径逐渐减小，3．用接枝后的PP代替纯的PP与尼龙共混，发现尼龙的相区比较模糊，说明相对于PP／PA6体系，PP-g-MAH／PA6体系的相容性更好。
13C-enriched Maleic Anhydride ([2.3-13C2] MAH) grafted isotactic polypropylene (iPP) samples were prepared via solution-grafting. Dicumyl peroxide (DCP) was used as initiator. The grafted rate, molecular weights and molecular structure of MAH grafted PP (PP-g-MAH) were studied by Chemical titration, FTIR spectroscopy, Gel Permeation Chromatography (GPC) and NMR, respectively. In addition, the morphology, formation and evolution of PP/PA6 blending was studied.
The FTIR spectra of PP-g-MAH samples show intense absorption bands at 1700-1900cm-1, indicating that MAH monomers have been grafted onto the chains of the Polypropylene. The results from the chemical titration suggested that the grafted degree increases with increasing initial MAH content. The GPC results showed that the molecular weight decreases with increasing initial MAH content. Similar result was obtained from rheometer measurements.
NMR results showed that: (1) The signals of MAH attached to the tertiary carbons of the iPP chains increased considerably with increasing MAH content, whereas the signals of MAH onto the radical chain ends (with single bond) arising from P scission did not. This result was consistent with the previous simulation study; (2) the signals of MAH onto the radical chain ends with double bonds increased markedly with increasing MAH content, indicating that P scission occurred after MAH attached to the tertiary carbons. As a result, the PP molecular weight decreased with increasing MAH content; (3) the fraction of "mm" construction along PP chains increased with increasing MAH content, whereas the fraction of "mr" and "rr" constructions decreased with increasing MAH content.
According to the experiment of PP/PA6 blending, we believe that (1) keeping the shear rate at 20s-1, the diameter of PA6 particle reduces gradually and becomes constant with the increase of shear time. With the
shear rate increasing, the time becomes short, which the diameter of PA6 particle becomes the constant (2) Keeping the shear time at 80s, the diameter of PA6 particle reduces gradually with the increase of shear rate. (3) The experiment of PP-g-MAH/PA6 blending shows that the compatibility of PP-g-MAH/PA6 is better than PP/PA6.
红外光谱显示，在1700—1900cm~(-1)区域有明显的羰基伸缩振动吸收峰，这说明马来酸酐已经成功地接在聚丙烯链上。化学滴定结果表明产物的接枝率与起始马来酸酐的浓度有关。GPC测试结果表明产物的分子量对起始马来酸酐的浓度有一定的依赖性，马来酸酐的浓度越大，产物的分子量越小，并与流变结果一致。
核磁共振仪对产物的分子结构研究表明：1．接在聚丙烯分子链三级碳上的马来酸酐的信号随MAH浓度的增加而增强，而接在链末端(由聚丙烯链β断裂产生)的MAH信号随MAH浓度的增加强度几乎不变。2．MAH以双键形式接在聚丙烯链末端的信号随MAH浓度的增加显著增强，说明更多的β断裂发生在MAH接枝到PP后，并使聚丙烯分子量随马来酸酐浓度增加而下降。3．MAH的用量对接枝PP链的等规度有很大的影响，主要表现在随MAH浓度增加，PP链的mm序列所占的比例逐渐增大，mr和rr序列所占的比例逐渐减小。
通过PP／PA6共混实验，我们发现：1．在一定的剪切速率(20s~-下，随着剪切时间的增加，尼龙相的粒径减小到一平衡值，随着剪切速率的增加，尼龙粒径达到平衡值所需要的时间逐渐减短。2．剪切时间固定，变化剪切速率，发现随着剪切速率的增加，尼龙相的粒径逐渐减小，3．用接枝后的PP代替纯的PP与尼龙共混，发现尼龙的相区比较模糊，说明相对于PP／PA6体系，PP-g-MAH／PA6体系的相容性更好。
13C-enriched Maleic Anhydride ([2.3-13C2] MAH) grafted isotactic polypropylene (iPP) samples were prepared via solution-grafting. Dicumyl peroxide (DCP) was used as initiator. The grafted rate, molecular weights and molecular structure of MAH grafted PP (PP-g-MAH) were studied by Chemical titration, FTIR spectroscopy, Gel Permeation Chromatography (GPC) and NMR, respectively. In addition, the morphology, formation and evolution of PP/PA6 blending was studied.
The FTIR spectra of PP-g-MAH samples show intense absorption bands at 1700-1900cm-1, indicating that MAH monomers have been grafted onto the chains of the Polypropylene. The results from the chemical titration suggested that the grafted degree increases with increasing initial MAH content. The GPC results showed that the molecular weight decreases with increasing initial MAH content. Similar result was obtained from rheometer measurements.
NMR results showed that: (1) The signals of MAH attached to the tertiary carbons of the iPP chains increased considerably with increasing MAH content, whereas the signals of MAH onto the radical chain ends (with single bond) arising from P scission did not. This result was consistent with the previous simulation study; (2) the signals of MAH onto the radical chain ends with double bonds increased markedly with increasing MAH content, indicating that P scission occurred after MAH attached to the tertiary carbons. As a result, the PP molecular weight decreased with increasing MAH content; (3) the fraction of "mm" construction along PP chains increased with increasing MAH content, whereas the fraction of "mr" and "rr" constructions decreased with increasing MAH content.
According to the experiment of PP/PA6 blending, we believe that (1) keeping the shear rate at 20s-1, the diameter of PA6 particle reduces gradually and becomes constant with the increase of shear time. With the
shear rate increasing, the time becomes short, which the diameter of PA6 particle becomes the constant (2) Keeping the shear time at 80s, the diameter of PA6 particle reduces gradually with the increase of shear rate. (3) The experiment of PP-g-MAH/PA6 blending shows that the compatibility of PP-g-MAH/PA6 is better than PP/PA6.
引文
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