1.上海交通大学
2.上海科技大学
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王铭钧, 董良昶, 杜, 等. 活性齐聚物电子束固化的理论研究[J]. 辐射研究与辐射工艺学报, 1984,2(4):20-28.
Wang Mingjun, Dong Liaongchang, Du Cong, et al. THEORETICAL STUDY ON ELECTRON BEAM CURING OF ACTIVE OLIGOMER[J]. Journal of Radiation Research and Radiation Processing, 1984,2(4):20-28.
本文研究了聚醚丙烯酸异氰酸酯齐聚物的电子束固化。将这类齐聚物归纳为A,a,型分子,A官能团相互反应,并推导了总反应程度P,A,、溶胶中反应程度P,A(S),及凝胶中反应程度P,A(g),在凝胶点后分别与溶胶分数S,A,之间函数关系式。当S,A,→1时,取极限值可得凝胶化临界条件为,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648200&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648202&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648201&type=,从而可知固化过程的规律为:凝胶点前(S,A,=1):P,A,=P,A(S),并逐渐增加,P,A(g),=0。凝胶点时(S,A,=1):,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648203&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648206&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648204&type=,,,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648208&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648190&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648209&type=,。凝胶点后,凝胶与溶胶共存(0,<,S,A,<,1):P,A(g),>, P,A,>, P,A(S),但P,A,与P,A(g),单调上升,P,A(S),单调下降。全为凝胶时(S,A,=0):P,A,=P,A,(,g,)=1,P,A(S),=0。通过红外光谱测定了不冋剂量的双键特征峰1415 cm,-1,峰高的变化,可求出双键的消失率(即P,A,),并同时测定各剂量的凝胶含量,由P,A,~S,A,的关系式计算P,A,值,两者较吻合,说明这类齐聚物的电子束固化是在双键之间进行的
This paper is concerned with the theory on electron beam curing of polyether acrylic isocyanate oligomers, which belong to the terminal acrylic type with the structure expressed as follows:,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648215&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648224&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648223&type=,As each double bond is a bifunctional group, these oligomers can be considered as the A,a, type molecule in the theoretical treatment. In the present work, the respective relationships among P,A, P,A(S), P,A(g), and S,A, were derived, these parameters are the total reacted extent of group A, the reacted extent of group A in sol, the reacted extent of group A in gel and sol fraction respectively. when S,A,→1, the critical values ofP,A, P,A(S), and P,A(g), are given with following formulae.,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648225&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648227&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648226&type=,Hence, the regularity about the curing process can be described as follows.,Before gel point (S,A,=1), value of P,A, or P,A(S), increases successively since P,A,=P,A(S),and P,A(g),=0;,At gel point (S,A,=1):,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648228&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648230&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648229&type=,After gel point (0,<,S,A,<,1): sol and gel coexist,P,A(g),>,P,A,>,P,A(s), and P,A, and P,A(g), increase monotonously but P,A(S), decreases.,Without sol in system S,A,=0;,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648218&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648222&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42648219&type=,The height of the absorption plak in oligomer was measured from I. R. spectra at different total dose. The disappearance rate of double bond can be characterized with the rate of the height reduction, which is approximately equal to the P,A, value calculated from the equation of P,A, vs. S,A,.
齐聚物电子束固化理论处理凝胶点红外光谱临界条件
OligomerElectron beam curingTheoretical treatmentGel pointI. R. spectrumCritical condition
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