CN1030571C - 利用脉冲激光制备含卤聚合物的方法 - Google Patents
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Abstract
本发明涉及一种激光在光聚合反应中的应用,提出了用脉冲激光解离某些过渡金属羰基化合物,使其失掉一个或几个配位体,并与反应体系中同时存在的有机卤化物相互作用,生成含有卤素的活泼中间体,引发某些烯类单体快速聚合,生成含卤聚合物的方法该发明提出的这种用脉冲激光直接合成含卤聚合物的方法,能在常温、常压下进行,其单体转化率高于95%,聚合反应速率按每分钟的单体转化率计算,接近5%/分,聚合物粘均分子量达105量级,方法简便。
Description
本发明涉及一种激光在光聚合反应中的应用,提出了用脉冲激光解离某些过渡金属羰基化合物,使其失掉一个或几个配位体,并与反应体系中同时存在的有机卤化物相互作用,生成含有卤素的活泼中间体,由这种活泼中间体引发某些有机单体快速聚合,生成含卤聚合物的方法。
当前把含有不饱和键的有机单体合成聚合物的方法有若干种,例如热化学法、电化学法、r-射线辐照法、电子轰击法、等离子体法、光化学法和激光化学等。很早以前就有人用光化学方法研究聚合物的合成,特别是以英国C.H.Bamford为代表的有关学者,他们从六十年代以来,系统地研究了一系列过渡金属羰基化合物在光引发聚合反应中的应用,他们的方法特点是使用高压汞灯之类普通光源,照射某些过渡金属化合物和有机卤化物,使它们发生反应生成含有卤素的自由基,在一定温度下引发某些单体聚合。他们的方法虽然与本发明有相似之处,例如他们也同时使用过渡金属羰基化合物和有机卤化物作引发剂,但是,在他们大量的工作中未见研究乙烯咔唑体系,尤其是他们没有使用脉冲激光作照射光源。普通光源的强度,单色性,相干性,方向性远不如激光。本发明采用激光,特别是紫外脉冲激光作照射光源,不但加快了聚合反应的速度,而且引发了不同的反应通道,例如他们的研究认为羰基化合物和有机卤化物在普通光照射下是产生自由基引发单体聚合的,而我们用脉冲激光照射过渡金属羰基化合物和有机卤化物,产生的不仅是自由基引发一种过程,同时还有其他引发过程(例如离子引发过程)存在,因此,所用光源类型的不同,反应体系的不同和反应通道的不同是本发明与C.H.Bamford等人工作的区别,参考文献:
[1]C.H.Bamford,In“Reactivity Mechanism and Structure in Polymer Chemistry”(Ed A.D.Jenkins and A.Ledwity),Wiley,N.Y.1974,Chpt3
上述这些光化学和激光化学制备聚合物的方法,基本上都是光引发自由基聚合过程。我们使用短脉冲、高功率的紫外激光使分子激发到高电子激发态,产生基态分子所没有的反应通道,具有特殊的反应选择性,见文献:N.J.Turro,Privatc Commnication(1979)
本发明与我们发明的88108240.6号专利“激光增强催化制备聚合物的方法”不同,在88108240.6号专利中,反应体系不含有机卤化物,而本发明的反应体系中同时使用过渡金属羰基化合物和有机卤化物。有机卤化物的加入不但提高了聚合反应速度,而且使反应生成物中含有卤素,这对于某些需要进行卤素掺杂而进行改性的聚合物来说,是一种能把聚合过程和掺杂过程合为一种过程的好办法。这是本发明与88108240.6号专利不同的地方。
本发明的目的在于克服上述方法的不足,提供用短脉冲,高功率的激光解离某些过渡金属羰基化
合物,并与在反应体系内加入的有机卤化物相互作用,提高聚合反应速度和使聚合反应生成物中含有卤素。
本发明不同于其他已有技术,它是这样来实现用脉冲激光直接合成含卤聚合物的,即采用脉冲激光照射含有Cr(CO)6,W(CO)6,Mo(CO)6,Fe(CO)5,Fe2(CO)9,Fe3(CO)12,Ni(CO)4,Co2(CO)8,Mn2(CO)10,Re2(CO)10,Os3(CO)12,Rh4(CO)12,Rh6(CO)16,Ru3(CO)12,Co(NO)(CO)3,C6H5Cr(CO)3等过渡金属羰基化合物和CCl4,CBr4,CHBr3,CHI3,CHCl3等有机卤化物的单体溶液,选择相应于M-CO键能的光子(即合适的波长),打断金属与羰基的键,使M(CO)m失去部分配位体,生成具有不饱和配位体的中间活泼体M(CO)n(其中n<m),这种中间活泼体本身是一种活性很高的催化剂,它一方面促进化学反应的进行,同时它与体系中存在的有机卤化物相互作用,生成含有卤素的自由基,从而快速引发自由基聚合反应;此外,体系中存在的有机卤化物,在激光照射下还能与某些单体形成电荷转移络合物,这种络合物因溶剂作用发生解离后产生离子性活泼中间体,也能引发离子性聚合反应,以上两种引发过程可表示如下:
Ⅰ.自由基引发过程
CBr3→自由基聚合反应 (4)
Ⅱ.离子引发过程
D+→阳离子引发聚合反应
A-→阴离子引发聚合反应
其中D是给电子性单体分子,A是吸电子
性配合剂分子,例如CCl4,CHCl3,CBr4,CHBr3,CHI3,Cl2,SO2等都是)
可以看出,本发明使用的反应体系,在激光照射下不但产生活性很高的催化剂,而且可以同时产生几种引发过程,所以聚合反应能在常温、常压下比只加羰基化合物的体系更快速进行。
本发明适用的单体有乙烯、卤化乙烯、丙烯、卤代丙烯、丁烯、卤代丁烯、戍烯、卤代戍烯、丁二烯-1,3;苯乙烯、α-甲基苯乙烯、乙烯酯、丙烯酸酯、甲基丙烯酸酯、丙烯腈、甲基丙烯腈、丙烯酰胺、甲基丙烯酰胺、N-乙烯基咔唑,N-乙烯基吡咯烷酮。根据不同的反应体系选择不同的激光波长范围。激光输出能量至少需要1毫焦耳/脉冲,一般使用1-2毫焦耳/脉冲,所用激光器可以是Nd:YAG泵染料调频激光器,氮分子激光器,准分子激光器等。
下面用具体的实施例子和制备过程的附图来详细说明:
取500克工业纯乙烯咔唑单体,用甲醇重结晶法进行提纯,于真空干燥箱内降压干燥,测其熔点为64.5℃-65℃,备用。称量140.8mgW(CO)6(美国Aofa公司产品)和132.8mgCBr4(上海试剂供应站产品),放进200ml防光性磨口三角并内,加入20mlC6H6(分析纯,北京化工厂产品),经搅拌全部溶解后,再加入1.54g乙烯咔唑,继续搅拌至溶解,然后将三角并放在调好的光路中,如图1所示,[1]是Na:YAG激光器,[2]是染料激光器,[3]是半反透镜。本发明主要使用Na:YAG激光器的三倍频激光355nm辐照样品,光斑直径为10mm,光强为2毫焦耳/脉冲,脉冲频率为10Hz,[4]为激光功率计,[5]是光学多道分析仪,用来监测反应过程中体系吸收特性的变化,[6]是透镜,[9]高压钨灯,作探测光源。反应物[7]在照射过程中一直用电磁搅拌器[8]进行搅拌,照射20分钟后,将过量的甲醇加入反应溶液(甲醇是沉淀剂),立刻有絮状沉淀物析出,为灰白色,经干燥后称其重量得1.49克聚合物,经计算得单体转化率为98%。把这种反应生成物用溶解再沉淀法进行三次提纯后,测得其粘均分子量为6×105-Mn,该样品的红外光谱分析和元素分析证明,所得聚合物为溴代聚乙烯咔唑。溴代聚乙烯咔唑是一种改进型有机光敏半导体材料,它比聚乙烯咔唑本身具有更宽的光谱相应范围,如果用恶英翁染料进行再增感,可以制得高灵敏度、透明性有机光敏半导体材料。
本发明的优点是能够利用激光,特别是紫外脉冲激光在室温、常压下制备含卤素的聚合物材料,
而且把单体的聚合过程和聚合物的掺杂改性过程合为一步进行,反应的速度快,效率高、节省能量,还可以用调节各种激光参数(例如波长、光强、重复频率、辐照时间等)的方法,在室温下制备不同分子量的聚合物,十分方便。
Claims (4)
1、一种利用脉冲激光制备含卤聚合物的方法,其特征在于:在常温、常压下用波长260nm-700nm的脉冲激光照射含有W(CO)6,Mo(CO)6过渡金属羰基化合物和CCl4或CBr4有机卤化物的单体溶液,照射时间为15-30分钟,其过渡金属羰基化合物的浓度为10-2-10-3克分子/升,有机卤化物的浓度为10-2-10-4克分子/升,单体浓度为1-3克分子/升。
2、按权利要求1.所述用脉冲激光制备含卤聚合物的方法,其特征在于:所使用的过渡金属羰基化合物是Cr(CO)6,MO(CO)6,W(CO)6,Fe(CO)5,Fe2(CO)9,CoFe2(CO)4,Co2(CO)8,Co(No)(CO)3,Ni(CO)4,Mn2(CO)10,Re2(CO)10,Rh4(CO)12,Rh6(CO)10,Ru3(CO)12,C6H5Cr(CO)3。
3、按权利要求1.所述的用脉冲激光制备含卤聚合物的方法,其特征在于:使用Nd:YAG泵染料高频激光器的二倍频、三倍频、四倍频激光;使用N2分子激光;使用准分子激光作照射源。所选用的激光波长与所用的羰基化合物和有机卤化合物的吸收波长相匹配。
4、按权利要求1.所述的用脉冲激光制备含卤聚合物的方法,其特征在于使用的单体是乙烯、卤代乙烯、丙烯、卤代丙烯、丁烯、戍烯、卤代戍烯、丁二烯-1,3、苯乙烯、α-甲基苯乙烯、丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯腈、甲基丙烯腈、丙烯酸胺、甲基丙烯酰胺、N-乙烯基咔唑、N-乙烯基吡咯烷酮。
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CN1317431C (zh) * | 2002-08-26 | 2007-05-23 | 财团法人大阪产业振兴机构 | 结晶核的制造方法及结晶条件的筛选方法 |
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