1.上海交通大学,上海
2.上海科技大学,上海
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王铭钧, 刘钰铭. 聚合物辐射交联过程中凝胶生成的动力学研究[J]. 辐射研究与辐射工艺学报, 1988,6(1):11-16.
Wang Mingjun, Liu Yuming. STUDY ON THE KINETICS OF GEL FORMATION IN THE RADIATION CROSSLINKING REACTION[J]. Journal of Radiation Research and Radiation Processing, 1988,6(1):11-16.
本文研究所推导的凝胶生成动力学方程,可清楚地理解凝胶生成的机理如下:(1)当交联度q,<,q,g,时,体系全为溶胶,交联仅发生在溶胶分子之间(q,g,为凝胶点)。(2)当q=q,g,时,这是凝胶与溶胶共存的起始点,体系仍然全为溶胶,交联仍在溶胶分子之间进行。(3)当q,>,q,g,时,交联越过了凝胶点,体系中凝胶与溶胶共存。从动力学方程中可清楚地知道,溶胶转变成凝胶是溶胶分子中未交联的链单位(对重均链长而言)与凝胶分子中未交联单位之间的相互作用,溶胶分子被逐渐带入凝胶,导致溶胶分数的减少,而溶胶中每有,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648842&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648837&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648843&type=,与凝胶产生交联,则会造成体系中溶胶减少dS。,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648845&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648847&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648846&type=,为辐照剂量R的减函数,S为溶胶分数)。单位剂量的交联度q,0,是剂量的减函数,可以公式,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648856&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648858&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648857&type=,计算各剂量的q,0,值,从而可知q,0,~R关系。在已知,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648860&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648865&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648862&type=,和q,0,~R关系后,由,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648869&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648871&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648870&type=,关系式可讨论交联过程中凝胶的分配。
From the kinetic equation of gel formation obtained by this study, the mechanism of gel formation may be interpreted clearly as follows:,(1) When the degree of crosslinking q,<,q,g, the system is sol and the crosslinking reaction is only carried out between the sol molecules. (q,g, is the gel point).,(2) when q=q,g, there exists a beginning point where the gel is coexisted with the sol, and the system is still sol, and the crosslinking reaction is still carried out between the sol molecules.,(3) When q,>,q,g, the crosslinking reaction exceeds the gel point and the gel is coexisted with the sol. The kinetic equation shows clearly that the transformation from sol into gel is caused by crosslinking reaction of the uncrosslinked chain units between the sol and gel molecules. As a result the sol molecules are transformed into the gel molecules gradually, and the sol fraction is reduced. When the chain units ,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648872&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648874&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648873&type=, in sol are crosslinked with gel, the sol fraction in the system are reduced ds (where ,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648875&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648884&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648876&type=, is a function of the radiation dose and S is sol fraction.),The degree of crasslinking per unit dose (q,0,) is reduced function of dose (R), so its value for every irradiation dose may be calculated by following equation,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648879&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648881&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648885&type=,therefore, the relationship between q,0, and R will be known. After knowing the correlation between ,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648882&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648890&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648889&type=, vs R and q,0, vs R, the distribution of gel and sol in the process of radiation crosslinking can be discussed according to the equation ,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648900&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648893&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648901&type=, dR as well.
溶胶分数凝胶分数凝胶点交联度裂解度溶胶与凝胶的分配凝胶形成动力学
Sol fractionGel fractionGel pointDegree of crosslinkingDegree of degradationkinetics of gel formationAssignment of sol and gel
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