CN110358069B - 一种主链含硒聚酯及其制备方法 - Google Patents
一种主链含硒聚酯及其制备方法 Download PDFInfo
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- CN110358069B CN110358069B CN201910643717.0A CN201910643717A CN110358069B CN 110358069 B CN110358069 B CN 110358069B CN 201910643717 A CN201910643717 A CN 201910643717A CN 110358069 B CN110358069 B CN 110358069B
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- selenium
- main chain
- polyester
- seleno
- butyrolactone
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- BAYKBDMKYMFICN-UHFFFAOYSA-N [Se]=C1CCCO1 Chemical compound [Se]=C1CCCO1 BAYKBDMKYMFICN-UHFFFAOYSA-N 0.000 claims abstract description 56
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- 150000007527 lewis bases Chemical class 0.000 claims abstract description 37
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
技术领域
本发明涉及高分子材料的技术领域,尤其涉及一种主链含硒聚酯及其制备方法。
背景技术
含硒高分子材料具有低毒性、易加工成型等优点,受到研究者的青睐。目前的研究表明,在聚合物中引入含硒功能团后,可以实现多种功能性材料的构建。典型的例子有以下几类:硒化合物的独特电子结构使其可以作为有效的光电功能材料的构筑基元;含硒聚合物由于其具有多重刺激响应性,经适当的结构设计,与靶向功能基团结合后,该类聚合物可以实现在特定的外界刺激条件下,如氧化、还原、pH、不同波段的光源照射、酶等,进行靶向定位和包裹药物的可控释放;聚合物中的含硒官能团也可以用于构建模拟酶,与类似结构、相同硒含量和质量浓度的小分子类似物相比,其催化活性大大提高;同时,由于硒原子拥有较硫原子大的摩尔体积分数,将硒功能团引入聚合物结构中还可以实现高折光指数材料的构建。结合硒原子所具有的光电性能,为其在光学和光电材料的应用奠定了基础。
目前,对含硒聚合物的合成与制备方法的研究较少。
如申请公开号为CN109593154A的中国专利文献中公开了一种含硒马来酰亚胺聚合物及其制备方法和应用,其技术路线是将马来酰亚胺单体与苯乙烯类单体(两种单体中至少一种单体中含有硒醚键)以不同摩尔比例进行活性自由基聚合,得到多种折光指数的含硒马来酰亚胺聚合物。但首先,该制备工艺中的原料单体(SePMI或PhSeSt)的制备较为复杂,且最终制备的聚合物的主链重复单元中不含硒。
申请公布号为CN 107383348 A的中国专利文献中公开了一种单硒醚聚合物及其制备方法,制备方法包括将硒内酯、不饱和一元醇在催化剂的作用下,在40~70℃下发生反应,得到烯酯二硒醚;将烯酯二硒醚溶于有机溶剂,在-20~-10℃下向其中加入磺酰氯进行反应,然后升温进一步反应,得到单硒醚聚合物。但由于该技术方案采用了逐步聚合的方法,制备的单硒醚聚合物结构复杂,且具有宽的分子量分布,较小的分子量。
发明内容
针对现有技术中存在的上述问题,本发明公开了一种主链含硒聚酯及其制备方法,该主链含硒聚酯具备明确的结构、较高的分子质量,较窄的分子量分布,主链重复单元具有酯和硒醚的完全交替结构。
具体技术方案如下:
一种主链含硒聚酯,主链为全交替结构,结构通式如下式(Ⅰ)或下式(Ⅱ)所示:
式中,n=10~5000;
R1选自H,R2选自H、C1~C20的烷基、C8H16C(=O)OCH3、CH2OCH2CH=CH2、CH2Cl、(CH3)2、CH2O(C=O)C(=CH2)CH3或C6H5;
或者,R1与R2成环,选自C4H8、C3H6或CH2CH(CH=CH2)CH2CH2;
R3选自H,R4选自H、Br或OCH2CHCH2;
或者,R3选自CH3,R4选自CH3、CH2Cl、CH2OCH2C6H5或CH2OH。
优选地,所述主链含硒聚酯具有如下结构式:
所述主链含硒聚酯的制备方法:
以1,4-硒代丁内酯和含氧单体为原料,以路易斯碱作为催化剂,在引发剂存在的条件下,经本体聚合或溶液聚合在-40~120℃于自生压力下制备得到。
发明人在深入研究含氧单体与其他单体共聚的基础上,开发出了1,4-硒代丁内酯和含氧单体的交替共聚。其中,1,4-硒代丁内酯的直接开环聚合非常困难,而含氧单体具有较大的环张力,在热力学上为此共聚反应提供了可能。从而,形成了本发明。
进一步地,在制备主链含硒聚酯时,含硒单体的选择具有唯一性,经过发明人前期的大量研究发现,若以四、六、或者七元环硒代内酯替代1,4-硒代丁内酯时,将无法获得具有酯和硒醚完全交替结构的主链含硒聚酯。
上述制备方法中:
所述含氧单体选自环氧化合物、氧杂环丁烷、3-取代氧杂环丁烷中的至少一种;
所述环氧化合物选自环氧乙烷、环氧丙烷、1,2-环氧丁烷、C5~C20的α-氧化烯、环氧十一烯酸甲酯、烯丙基缩水甘油醚、环氧氯丙烷、环氧异丁烷、环氧环己烷、4-乙烯基环氧环己烷、甲基丙烯酸缩水甘油酯、环氧环戊烷、氧化苯乙烯中的至少一种;
所述3-取代氧杂环丁烷选自3,3-二甲基氧杂环丁烷,3-甲基-3-苄氧基甲基氧杂环丁烷、3-氯甲基-3-甲基氧杂环丁烷、3-甲基-3-氧杂环丁烷甲醇、3-(烯丙氧基)氧杂环丁烷、3-溴氧杂环丁烷中的至少一种。
优选地,所述含氧单体选自环氧乙烷、环氧丙烷、苯基缩水甘油醚、苄基缩水甘油醚、3-氯甲基-3-甲基氧杂环丁烷中的至少一种。上述优选的含氧单体均为便宜易得的工业产品,且储运方便;尤其重要的是优选的含氧单体与1,4-硒代丁内酯具有很好的反应性和优异的效果。
所述路易斯碱选自季铵盐、季鏻盐、有机碱、碱金属醇盐中的至少一种;
所述季铵盐选自双(三苯基正膦基)氯化铵、十六烷基三甲基卤化铵、四丁基氢氧化铵、十二烷基三甲基卤化铵、十烷基三甲基卤化铵、苄基三乙基卤化铵、苄基三丙基卤化铵、苄基三丁基卤化铵、苄基三乙基醋酸铵、苄基三丙基醋酸铵、苄基三丁基醋酸铵、四乙基醋酸铵、四丁基碘化铵、四丁基硝酸铵、四丙基醋酸铵中的至少一种;
所述季鏻盐选自四苯基氯化鏻、四苯基溴化鏻、四烷基卤化鏻盐、苄基三苯基溴化膦、丁基三苯基碘化膦、丙基三苯基溴化膦中的至少一种;
所述有机碱选自1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)、1,8-二氮杂双环[5.4.0]十一-7-碳烯、7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、1,5,7-二氮杂双环[5.4.0]十一-7-碳烯中的至少一种;
所述碱金属醇盐选自甲醇钠、甲醇钾、甲醇锂、乙醇钠、乙醇钾、乙醇锂、叔丁醇钾、叔丁醇锂、叔丁醇钠中的至少一种。
优选地,所述路易斯碱选自双(三苯基正膦基)氯化铵([PPN]Cl,结构式记为1)、四苯基氯化鏻(PPh4Cl,结构式记为2)、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)(结构式记为3)、甲醇钠(CH3ONa,记为4),上述优选的路易斯碱便宜易得且具有较高的催化活性。
所述引发剂选自具有活泼氢的化合物,如水、醇、有机羧酸、端羟基聚醚、端羧基聚醚中的至少一种。
所述醇可以选自1,4-苯二甲醇、苯甲醇、C1~C20的醇;
所述有机羧酸可以选自苯甲酸、C1~C20的酸;
所述端羟基聚醚可以选自PEG、聚氧化丙烯、聚四氢呋喃、聚苯乙烯、聚丙烯酸酯;
所述端羧基聚醚可以选自PEG、聚氧化丙烯、聚四氢呋喃、聚苯乙烯、聚丙烯酸酯。
优选地,所述引发剂选自水、1,4-苯二甲醇、乙酸、PEG中的至少一种。
若选自PEG,则进一步优选PEG-2000。
优选地:
所述1,4-硒代丁内酯和含氧单体的摩尔比为0.1~10:1;进一步优选为0.5~2,在上述进一步优选范围内,能同时保证这两种单体的转化率和利用率较高,节约成本。
所述路易斯碱与含氧单体的摩尔比为1:10~5000;进一步优选为1:50~500,在优选范围内,聚合反应时间较短且催化剂用量合适。
所述引发剂与含氧单体的摩尔比为1:10~5000;进一步优选为1:50~500,在优选范围内,聚合反应所需时间较短,且聚合产物分子量较大。
如果采用溶液聚合的方式制备所述含硒聚酯,则采用的溶剂选自二氯甲烷、氯仿、四氢呋喃、甲苯、三氯苯、邻二氯苯、间二氯苯、对二氯苯、二甲基甲酰胺中的至少一种;进一步优选为二氯甲烷、四氢呋喃、甲苯。
再优选:
所述含氧单体选自环氧乙烷、环氧丙烷、苯基缩水甘油醚、苄基缩水甘油醚或3-氯甲基-3-甲基氧杂环丁烷;
所述路易斯碱选自[PPN]Cl、PPh4Cl、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)或甲醇钠;
所述引发剂选自水、1,4-苯二甲醇、乙酸或PEG-2000;
所述1,4-硒代丁内酯和含氧单体的摩尔比为0.5~2;
所述路易斯碱与含氧单体的摩尔比为1:50~500;
所述引发剂与含氧单体的摩尔比为1:50~500;
所述聚合反应为溶液聚合,以二氯甲烷、四氢呋喃或甲苯为溶剂,在-40~120℃于自生压力下反应0.1~12h。
经试验发现,优选的原料与工艺条件下制备到的主链含硒聚酯的数均分子量可以在1~100kg/mol范围内进行调节,分子量分布可以在1.1~2.0的范围内进行调节。
再进一步优选:
所述含氧单体选自环氧乙烷,所述路易斯碱选自[PPN]Cl或1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),所述引发剂选自1,4-苯二甲醇;
所述1,4-硒代丁内酯和含氧单体的摩尔比为0.5~2,路易斯碱与含氧单体的摩尔比为1:50~500,引发剂与含氧单体的摩尔比为1:200。经试验发现,采用上述进一步优选的原料与工艺条件下制备到的主链含硒聚酯兼具较高的数均分子量与较窄的分子量分布。
与现有技术相比,本发明具有如下优点:
(1)本发明是在大量实验研究的基础上,首次实现了1,4-硒代丁内酯和含氧单体的完全交替共聚合,1,4-硒代丁内酯容易制备且含氧单体便宜易得,因此该共聚反应的实用价值较大;
(2)本发明中采用的催化体系,商业上便宜易得,得到了结构明确,无金属残留且无色的主链重复单元含硒聚酯,无需繁琐的后处理纯化步骤;
(3)本发明制备得到的主链重复单元含硒聚酯为完全交替结构,主链和端基结构明确,在食品包装,涂料,生物和电子领域有着广泛的应用前景。
附图说明
图1为实施例1制备的共聚聚合产物的1H NMR谱图;
图2为实施例1制备的共聚聚合产物的13C NMR谱图;
图3为实施例11制备的共聚聚合产物的1H NMR谱图;
图4为实施例11制备的共聚聚合产物的13C NMR谱图;
图5为实施例12制备的共聚聚合产物的1H NMR谱图;
图6为实施例12制备的共聚聚合产物的13C NMR谱图。
具体实施方式
为了更为具体地描述本发明,下面结合附图及具体实施方式对本发明的技术方案进行详细说明。
以下实施例中作为原料单体的1,4-硒代丁内酯自制得到,制备步骤如下:
将4-溴丁酰氯溶解在无水甲苯中并缓慢加入NaSeH溶液。在室温下剧烈搅拌该混合物。在氩气下反应6-12小时。用5%NaHCO3水溶液洗涤并干燥后,真空除去甲苯。减压蒸馏所得残余物,得到1,4-硒代丁内酯。
实施例1 1,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),引发剂1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mLTHF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/200/20/1。置于25℃下于自生压力下反应0.1h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
本实施例制备得到的主链含硒聚酯的1H NMR谱图如图1所示,13C NMR谱图如图2所示。观察图1和图2可知,图中未见聚醚链节所对应的峰,说明所得产物为交替链节结构,产物的结构通式如下:
实施例21,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),引发剂1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mLTHF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷,1,4-硒代丁内酯,路易斯碱与引发剂的摩尔比为5000/50000/1/25。置于25℃下于自生压力下反应12h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例3 1,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mLTHF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/400/4/1。置于25℃下于自生压力下反应1h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例41,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/200/1/1。置于25℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例5 1,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱双(三苯基正膦基)氯化铵([PPN]Cl),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mLTHF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为500/250/1/2.5。置于25℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例61,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱四苯基氯化鏻(PPh4Cl),1,4-苯二甲醇(BDM)和1,4-硒代丁内酯(SBL),之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/200/1/20。置于25℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例7 1,4-硒代丁内酯/EO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-10℃的环氧乙烷(EO)。环氧乙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为5000/500/25/1。置于25℃下于自生压力下反应10h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例8 1,4-硒代丁内酯/PO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱四苯基氯化鏻(PPh4Cl),引发剂水,1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-10℃的环氧丙烷(PO)。环氧丙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/200/1/4。置于25℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
经核磁氢谱与核磁碳谱测试可知,制备得到的产物未见聚醚链节所对应的峰,说明所得产物为交替链节结构,产物的结构通式如下:
实施例9 1,4-硒代丁内酯/PO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-10℃的环氧丙烷(PO)。环氧丙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为500/500/2.5/1。置于25℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例10 1,4-硒代丁内酯/PO交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱甲醇钠,引发剂乙酸,1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-40℃的环氧丙烷(PO)。环氧丙烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为500/500/2.5/1。置于-40℃下于自生压力下反应3h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
实施例11 1,4-硒代丁内酯/PGE交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),引发剂PEG-2000,1,4-硒代丁内酯(SBL)和1mL THF,之后加入1mL已经冷却至-10℃的苯基缩水甘油醚(PGE)。苯基缩水甘油醚、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为200/400/1/1。置于120℃下于自生压力下反应2h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
本实施例制备得到的主链含硒聚酯的1H NMR谱图如图3所示,13C NMR谱图如图4所示。观察图3和图4可知,图中未见聚醚链节所对应的峰,说明所得产物为交替链节结构,产物的结构通式如下:
实施例12 1,4-硒代丁内酯/BnGE交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),1,4-苯二甲醇(BDM),1,4-硒代丁内酯(SBL)和1mL TOL,之后加入1mL已经冷却至-10℃的苄基缩水甘油醚(BnGE)。苄基缩水甘油醚、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为500/500/2.5/1。置于60℃下于自生压力下反应4h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
本实施例制备得到的主链含硒聚酯的1H NMR谱图如图5所示,13C NMR谱图如图6所示。观察图3和图4可知,图中未见聚醚链节所对应的峰,说明所得产物为交替链节结构,产物的结构通式如下:
实施例131,4-硒代丁内酯/3-氯甲基-3-甲基氧杂环丁烷交替共聚合成主链重复单元含硒聚酯
聚合反应前先将10mL的史莱克管于110℃下2小时左右除去水分并在干燥器中冷却至室温;依次向反应釜中加入若干质量的路易斯碱甲醇钠,引发剂水,1,4-硒代丁内酯(SBL)和1mL CH2Cl2,之后加入1mL已经冷却至-10℃的3-氯甲基-3-甲基氧杂环丁烷。3-氯甲基-3-甲基氧杂环丁烷、1,4-硒代丁内酯、路易斯碱与引发剂的摩尔比为500/1000/2.5/1。置于120℃下于自生压力下反应3h。反应结束后先用四氢呋喃溶解粗产物,再在100mL甲醇/盐酸的混合物(盐酸摩尔浓度为5%)中沉淀出聚合物,重复洗三次,真空干燥至恒重。通过凝胶色谱测定聚合物的分子量与分子量分布,测试结果见表1。
经核磁氢谱与核磁碳谱测试可知,制备得到的产物未见聚醚链节所对应的峰,说明所得产物为交替链节结构,产物的结构通式如下:
表1
注:1含氧单体种类:EO为环氧乙烷、PO为环氧丙烷、PGE为苯基缩水甘油醚、BnGE为苄基缩水甘油醚。2引发剂种类:水,BDM为1,4-苯二甲醇,乙酸以及PEG-2000。3路易斯碱种类:1为双(三苯基正膦基)氯化铵([PPN]Cl),2为四苯基氯化鏻(PPh4Cl),3为1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物),4为甲醇钠。4路易斯碱与含氧单体的摩尔比。5引发剂与含氧单体的摩尔比;61,4-硒代丁内酯与含氧单体的摩尔比;7溶剂种类:THF:四氢呋喃,CH2Cl2:二氯甲烷,TOL:甲苯;8Mn:数均分子量,由凝胶渗透色谱法测定;9PDI:分子量分布,由凝胶渗透色谱法测定。
实施例1~13为有机路易斯碱催化1,4-硒代丁内酯与含氧单体共聚结果,可以看出此类无金属引发体系具有优异的催化活性以及普适性。
以上所述仅为本发明的若干个具体实施方式,应当指出,对于本领域的普通技术人员来说,还可以做出许多变型和改进,所有未超出权利要求所述的变型或改进均应视为本发明的保护范围。
Claims (9)
2.根据权利要求1所述的主链含硒聚酯,其特征在于,所述主链含硒聚酯的数均分子量为1~100kg/mol,分子量分布为1.1~2.0。
3.根据权利要求1或2所述的主链含硒聚酯的制备方法,其特征在于:
以1,4-硒代丁内酯和含氧单体为原料,以路易斯碱作为催化剂,在引发剂存在的条件下,经本体聚合或溶液聚合在-40~120℃于自生压力下制备得到;
所述含氧单体选自环氧化合物、氧杂环丁烷、3-取代氧杂环丁烷中的至少一种;
所述路易斯碱选自季铵盐、季鏻盐、有机碱、碱金属醇盐中的至少一种;
所述引发剂选自具有活泼氢的化合物。
4.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于:
所述环氧化合物选自环氧乙烷、环氧丙烷、1,2-环氧丁烷、C5~C20的α-氧化烯、环氧十一烯酸甲酯、烯丙基缩水甘油醚、环氧氯丙烷、环氧异丁烷、环氧环己烷、4-乙烯基环氧环己烷、甲基丙烯酸缩水甘油酯、环氧环戊烷、氧化苯乙烯中的至少一种;
所述3-取代氧杂环丁烷选自3,3-二甲基氧杂环丁烷,3-甲基-3-苄氧基甲基氧杂环丁烷、3-氯甲基-3-甲基氧杂环丁烷、3-甲基-3-氧杂环丁烷甲醇、3-(烯丙氧基)氧杂环丁烷、3-溴氧杂环丁烷中的至少一种。
5.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于:
所述季铵盐选自双(三苯基正膦基)氯化铵、十六烷基三甲基卤化铵、四丁基氢氧化铵、十二烷基三甲基卤化铵、十烷基三甲基卤化铵、苄基三乙基卤化铵、苄基三丙基卤化铵、苄基三丁基卤化铵、苄基三乙基醋酸铵、苄基三丙基醋酸铵、苄基三丁基醋酸铵、四乙基醋酸铵、四丁基碘化铵、四丁基硝酸铵、四丙基醋酸铵中的至少一种;
所述季鏻盐选自四苯基氯化鏻、四苯基溴化鏻、四烷基卤化鏻盐、苄基三苯基溴化膦、丁基三苯基碘化膦、丙基三苯基溴化膦中的至少一种;
所述有机碱选自1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)、1,8-二氮杂双环[5.4.0]十一-7-碳烯、7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、1,5,7-二氮杂双环[5.4.0]十一-7-碳烯中的至少一种;
所述碱金属醇盐选自甲醇钠、甲醇钾、甲醇锂、乙醇钠、乙醇钾、乙醇锂、叔丁醇钾、叔丁醇锂、叔丁醇钠中的至少一种。
6.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于,所述引发剂选自水、醇、有机羧酸、端羟基聚醚、端羧基聚醚中的至少一种。
7.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于:
所述1,4-硒代丁内酯和含氧单体的摩尔比为0.1~10:1;
所述路易斯碱与含氧单体的摩尔比为1:10~5000;
所述引发剂与含氧单体的摩尔比为1:10~5000。
8.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于,所述溶液聚合采用的溶剂选自二氯甲烷、氯仿、四氢呋喃、甲苯、三氯苯、邻二氯苯、间二氯苯、对二氯苯、二甲基甲酰胺中的至少一种。
9.根据权利要求3所述的主链含硒聚酯的制备方法,其特征在于,所述本体聚合或溶液聚合的时间为0.1~12h。
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