石油化工
石油化工
석유화공
PETROCHEMICAL TECHNOLOGY
2015年
1期
42-46
,共5页
丙烯聚合N催化剂%原位核磁共振%环氧氯丙烷%氯化镁%磷酸三丁酯
丙烯聚閤N催化劑%原位覈磁共振%環氧氯丙烷%氯化鎂%燐痠三丁酯
병희취합N최화제%원위핵자공진%배양록병완%록화미%린산삼정지
N-catalyst for propylene polymerization%in situ nuclear magnetic resonance%epichlorohydrin%magnesium chloride%tributyl phosphate
利用原位NMR技术,通过在超声清洗器内超声并加热来模拟实验室的机械搅拌条件,对丙烯聚合N催化剂制备过程中环氧氯丙烷(ECP)所发生的化学反应进行了研究,跟踪表征了不同时刻反应体系的1H NMR谱图和31P NMR谱图,计算出不同反应时刻的ECP转化率,并对体系内的络合情况进行了初步探讨。1H NMR表征结果显示,在N催化剂的制备过程中, MgCl2-ECP-磷酸三丁酯(TBP)体系中ECP发生了化学反应,归属于ECP的H谱峰消失,生成了只有两处H化学位移的新物质ECP·MgCl2;计算结果表明,在反应时间为130 min时,ECP转化率达到90.28%;31P NMR的表征结果显示,TBP与反应产物ECP·MgCl2有更强的络合作用,原有的MgCl2·TBP络合体系解离并生成新的络合物ECP·MgCl2·TBP,导致P的化学位移向高场方向移动。
利用原位NMR技術,通過在超聲清洗器內超聲併加熱來模擬實驗室的機械攪拌條件,對丙烯聚閤N催化劑製備過程中環氧氯丙烷(ECP)所髮生的化學反應進行瞭研究,跟蹤錶徵瞭不同時刻反應體繫的1H NMR譜圖和31P NMR譜圖,計算齣不同反應時刻的ECP轉化率,併對體繫內的絡閤情況進行瞭初步探討。1H NMR錶徵結果顯示,在N催化劑的製備過程中, MgCl2-ECP-燐痠三丁酯(TBP)體繫中ECP髮生瞭化學反應,歸屬于ECP的H譜峰消失,生成瞭隻有兩處H化學位移的新物質ECP·MgCl2;計算結果錶明,在反應時間為130 min時,ECP轉化率達到90.28%;31P NMR的錶徵結果顯示,TBP與反應產物ECP·MgCl2有更彊的絡閤作用,原有的MgCl2·TBP絡閤體繫解離併生成新的絡閤物ECP·MgCl2·TBP,導緻P的化學位移嚮高場方嚮移動。
이용원위NMR기술,통과재초성청세기내초성병가열래모의실험실적궤계교반조건,대병희취합N최화제제비과정중배양록병완(ECP)소발생적화학반응진행료연구,근종표정료불동시각반응체계적1H NMR보도화31P NMR보도,계산출불동반응시각적ECP전화솔,병대체계내적락합정황진행료초보탐토。1H NMR표정결과현시,재N최화제적제비과정중, MgCl2-ECP-린산삼정지(TBP)체계중ECP발생료화학반응,귀속우ECP적H보봉소실,생성료지유량처H화학위이적신물질ECP·MgCl2;계산결과표명,재반응시간위130 min시,ECP전화솔체도90.28%;31P NMR적표정결과현시,TBP여반응산물ECP·MgCl2유경강적락합작용,원유적MgCl2·TBP락합체계해리병생성신적락합물ECP·MgCl2·TBP,도치P적화학위이향고장방향이동。
The chemical reaction of epichlorohydrin(ECP)in the preparation of N-catalyst for propylene polymerization was studied in an ultrasonic cleaner with ultrasonic wave instead of mechanical stirrer by means of in situ NMR technique. The results showed that,there was chemical reaction in the MgCl2-ECP-tributyl phosphate(TBP)system,the1H NMR peak of ECP disappeared and a new product ECP-MgCl2 with only two1H NMR chemical shifts was generated. The chemical reaction was investigated by means of1H NMR and31P NMR in different reaction time. The conversion of ECP in the reaction was obtained by integral area ratio of1H NMR,which reached 90.28% in 130 min. The results of31P NMR indicated that there was strong complexation between TBP and the reaction product(ECP·MgCl2)which led to the disassociation of MgCl2·TBP,the formation of a new complex ECP·MgCl2·TBP,and the movement of the P chemical shift to high field.