CN106975516B - 磁性棒状耐高温鎓盐相转移催化剂的制备方法 - Google Patents
磁性棒状耐高温鎓盐相转移催化剂的制备方法 Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及一种磁性棒状耐高温鎓盐相转移催化剂的制备方法,在磁场诱导作用下,将含有烷基或烷氧基长碳链间隔臂的苯乙烯衍生物单体在交联剂、引发剂存在条件下包覆在磁性纳米棒表面,并用溶剂清洗棒状复合物,除去未反应单体和交联剂后再与有机胺或有机膦反应以鎓盐化,制得磁性棒状耐高温鎓盐相转移催化剂。得到的每一个棒状相转移催化剂,以独立的磁子在体系中自行旋转,大大增加了两相的接触概率,因此具有较高的催化活性,而且具有高度的化学稳定性,耐温性好,能够催化温度较高的反应,该相转移催化剂很容易从反应体系中分离,只需外加磁场就可实现相转移催化剂的回收再利用。
Description
技术领域
本发明属于高分子催化剂的制备方法,涉及一种磁性棒状耐高温鎓盐相转移催化剂的制备方法,具体涉及在磁场诱导作用下以含有烷基或烷氧基长碳链间隔臂的苯乙烯衍生物为单体通过聚合包覆磁性粒子,形成棒状复合物,再经过季铵化或季鏻化制得的磁性棒状鎓盐相转移催化剂。
背景技术
相转移催化剂的作用主要是在两相反应系统中将反应物与催化剂形成的离子对转移到非质子溶剂中,避免由于使用质子溶剂造成的反应物的溶剂化,从而加速反应的进行。采用相转移催化剂可以改变离子的溶剂化程度、增大离子的反应活性、加快反应速度、简化处理手续,进而提高反应效率。
鎓盐类相转移催化剂使用范围较为广泛。但是小分子催化剂在反应完成后难以除去,严重影响产物的纯度以及性能,催化剂难以回收再利用,增加了催化剂使用的成本,造成极大地浪费。为克服以上缺点,近年来出现了负载型相转移催化剂,主要是树脂负载型相转移催化剂。该类催化剂的使用,提高了催化剂的回收效率,降低了贵重相转移催化剂的使用成本,而且环境友好,但是一般树脂基相转移催化剂耐热性较差,只能催化温度较低的反应,在催化高温反应方面应用受到限制,该类相转移催化剂的分离主要是依靠过滤、重力沉降和离心等方法进行,这种去除方法耗能费时。使相转移催化剂赋予磁性能和耐高温性,得到的磁性耐高温相转移催化剂将具有以下优点:从反应体系中去除的过程简单,只需外加磁场就可将其分离出来,而且不会破坏催化剂的结构,不影响其催化效率,可以很方便高效的回收再利用,节能快捷;在磁性纳米棒表面包覆耐高温聚合物壳层并将其鎓盐化,得到的每一个棒状相转移催化剂,可作为一个独立的磁子,在体系中自行旋转,大大增加了两相的接触概率。磁性棒状相转移催化剂不仅具有较高的催化活性,而且具有高度的化学稳定性,耐温性。磁性棒状耐高温鎓盐相转移催化剂因其优异的耐高温性、较高的催化性能以及易分离性将具有广泛的应用空间。
负载型相转移催化剂因其以上优异特性而成为近年来的研究热点,但目前尚未出现磁性棒状耐高温鎓盐相转移催化剂及其制备方法的报道。
发明内容
要解决的技术问题
为了避免现有技术的不足之处,本发明提出一种磁性棒状耐高温鎓盐相转移催化剂的制备方法。
技术方案
一种磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于步骤如下:
步骤1:将硅烷偶联剂、磁性纳米粒子、酸或碱与溶剂以质量比为1~40:1~3:1~15:1000~5000混合,在温度25~80℃下反应8~24小时;使硅烷偶联剂对磁性纳米粒子进行表面功能化修饰,使其表面带上双键;
步骤2:将单体、交联剂和修饰后的磁性纳米粒子在溶剂中超声混合均匀,距离混合容器1~10cm处放一块磁铁,再加入引发剂;将体系加热至30~90℃静置,聚合反应0.5~12小时,得到包覆有耐高温聚合物的磁性纳米棒;
用溶剂清洗产物,除去未反应的单体和交联剂;
所述单体、交联剂、引发剂、磁性纳米粒子质量比为30~70:1~15:0.1~15:2~10;
所述磁铁为5000Gs;
步骤3:向磁性纳米棒复合物中加入胺类有机物或膦类有机物和分散介质,加热至20~90℃进行鎓盐化,反应持续8~24小时;所述磁性粒子、有机胺或膦类有机物、分散介质的质量比为1~5:5~100:100~800;
步骤4:用溶剂充分清洗产物,除去未反应的原料,得到磁性棒状耐高温鎓盐相转移催化剂。
所述硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷或乙烯基三乙氧基硅烷。
所述磁性粒子为四氧化三铁、三氧化二铁、钡铁氧体或镍铁氧体。
所述单体为4-氯甲基苯乙烯、4-(3-氯丙基)苯乙烯、4-(3-溴丙基)苯乙烯、4-(4-氯丁基)苯乙烯、4-(4-溴丁基)苯乙烯、4-(5-氯戊基)苯乙烯、4-(5-溴戊基)苯乙烯、4-(6-氯己基)苯乙烯、4-(6-溴己基)苯乙烯、4-((2-氯乙氧基)甲基)苯乙烯、4-((2-溴乙氧基)甲基)苯乙烯、4-((3-氯丙氧基)甲基)苯乙烯、4-((3-溴丙氧基)甲基)苯乙烯、4-((4-氯丁氧基)甲基)苯乙烯或4-((4-溴丁氧基)甲基)苯乙烯。
所述交联剂为二乙烯基苯、双甲基丙烯酸乙二醇酯、二丙烯基苯、二乙烯基苯基甲烷或N-N-亚甲基双丙烯酰胺。
所述引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化月桂酰或异丙苯过氧化氢。
所述有机胺为三甲胺、三甲胺盐酸盐、三乙胺、三乙胺盐酸盐、三丁胺、二甲基乙醇胺、甲基二乙醇胺、二辛基乙醇胺或吡啶。
所述膦类有机物为三丁基膦、三辛基膦、三苯基膦或三乙基膦。
所述分散介质为1,2-二氯乙烷、1,4-二氧六环、丙酮、水或乙醇。
所述溶剂为乙腈、水或乙醇。
有益效果
本发明提出的一种磁性棒状耐高温鎓盐相转移催化剂的制备方法,在磁场诱导作用下,将含有烷基或烷氧基长碳链间隔臂的苯乙烯衍生物单体在交联剂、引发剂存在条件下包覆在磁性纳米棒表面,并用溶剂清洗棒状复合物,除去未反应单体和交联剂后再与有机胺或有机膦反应以鎓盐化,制得磁性棒状耐高温鎓盐相转移催化剂。得到的每一个棒状相转移催化剂,可作为一个独立的磁子,在体系中自行旋转,大大增加了两相的接触概率,因此具有较高的催化活性,而且具有高度的化学稳定性,耐温性好,能够催化温度较高的反应,该相转移催化剂很容易从反应体系中分离,只需外加磁场就可实现相转移催化剂的回收再利用。磁性棒状耐高温鎓盐相转移催化剂因其优异的耐高温性以及易分离性将在许多化学反应中具有应用价值。
本发明方法将磁性纳米粒子及含有烷基和烷氧基长碳链间隔臂的苯乙烯衍生物单体在交联剂、引发剂存在条件下依靠磁场诱导作用制备棒状复合物,再与有机胺或有机膦反应以鎓盐化,制得磁性棒状耐高温鎓盐相转移催化剂。
附图说明
图1:磁性棒状耐高温鎓盐相转移催化剂的透射电镜照片
图2:磁性棒状耐高温鎓盐相转移催化剂制备示意图
具体实施方式
现结合实施例、附图对本发明作进一步描述:
实施例1:含有丁基间隔臂的磁性棒状耐高温季铵型相转移催化剂的制备
将4g 4-(4-溴丁基)苯乙烯、1g二乙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶4cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至70℃,反应10h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-(4-溴丁基)苯乙烯和二乙烯基苯,将溶剂置换成水之后冷冻干燥得聚(4-(4-溴丁基)苯乙烯-co-二乙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的1,2-二氯乙烷中,加入10g三甲胺水溶液,80℃下反应24小时。反应结束后用乙醇充分清洗,得到含有丁基间隔臂的磁性棒状耐高温季铵型相转移催化剂。
实施例2:含有丁基间隔臂的磁性棒状耐高温季鏻型相转移催化剂的制备
将4g 4-(4-溴丁基)苯乙烯、1g二乙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶4cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至70℃,反应10h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-(4-溴丁基)苯乙烯和二乙烯基苯,将溶剂置换成水之后冷冻干燥得聚(4-(4-溴丁基)苯乙烯-co-二乙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的乙醇中,加入9g三丁基膦,75℃下反应24小时。反应结束后用乙醇充分清洗,得到含有丁基间隔臂的磁性棒状耐高温季鏻型相转移催化剂。
实施例3:含有己基间隔臂的磁性棒状耐高温季铵型相转移催化剂的制备
将4g 4-(6-氯己基)苯乙烯、1g二乙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶3cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至60℃,反应12h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-(6-氯己基)苯乙烯和二乙烯基苯,将溶剂置换成水之后冷冻干燥得聚(4-(6-氯己基)苯乙烯-co-二乙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的1,4-二氧六环中,加入8g三正丁胺,80℃下反应24小时。反应结束后用乙醇充分清洗,得到含有己基间隔臂的磁性棒状耐高温季铵型相转移催化剂。
实施例4:含有丙氧基甲基间隔臂的磁性棒状耐高温季铵型相转移催化剂的制备
将4g 4-((3-溴丙氧基)甲基)苯乙烯、1g二丙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶3cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至80℃,反应12h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-((3-溴丙氧基)甲基)苯乙烯和二丙烯基苯,将溶剂置换成水之后冷冻干燥得聚4-((3-溴丙氧基)甲基)苯乙烯-co-二丙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的1,2-二氯乙烷中,加入8g三正丁胺,80℃下反应20小时。反应结束后用乙醇充分清洗,得到含有丙氧基甲基间隔臂的磁性棒状耐高温季铵型相转移催化剂。
实施例5:含有丙氧基甲基间隔臂的磁性棒状耐高温季鏻型相转移催化剂的制备
将4g 4-((3-溴丙氧基)甲基)苯乙烯、1g二丙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶3cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至80℃,反应12h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-((3-溴丙氧基)甲基)苯乙烯和二丙烯基苯,将溶剂置换成水之后冷冻干燥得聚4-((3-溴丙氧基)甲基)苯乙烯-co-二丙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的1,2-二氯乙烷中,加入6g三乙基鏻,80℃下反应24小时。反应结束后用乙醇充分清洗,得到含有丙氧基甲基间隔臂的磁性棒状耐高温季鏻型相转移催化剂。
实施例6:含有丁氧基甲基基间隔臂的磁性棒状耐高温季铵型相转移催化剂的制备
将4g 4-((4-氯丁氧基)甲基)苯乙烯、1g二乙烯基苯、0.5g Fe3O4磁性纳米粒子、600mL乙腈加入到1000mL烧瓶中,超声分散30分钟;距离烧瓶5cm处放置一磁铁(0.50T),将0.2g偶氮二异丁腈分散于200mL乙腈中,快速倒入烧瓶中,体系加热至80℃,反应12h,得到聚合物包覆的磁性纳米棒,先用乙腈清洗产物,再用乙醇充分清洗以除去未反应的4-((4-氯丁氧基)甲基)苯乙烯和二乙烯基苯,将溶剂置换成水之后冷冻干燥得聚4-((4-氯丁氧基)甲基)苯乙烯-co-二乙烯基苯)包覆的Fe3O4磁性纳米棒。
将0.2g上述聚合物包覆的磁性纳米棒分散在300mL的乙醇中,加入10g三乙胺,75℃下反应24小时。反应结束后用乙醇充分清洗,得到含有丁氧基甲基基间隔臂的磁性棒状耐高温季铵型相转移催化剂。
Claims (10)
1.一种磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于步骤如下:
步骤1:将硅烷偶联剂、磁性纳米粒子、酸或碱与溶剂以质量比为1~40:1~3:1~15:1000~5000混合,在温度25~80℃下反应8~24小时;使硅烷偶联剂对磁性纳米粒子进行表面功能化修饰,使其表面带上双键;
步骤2:将单体、交联剂和修饰后的磁性纳米粒子在溶剂中超声混合均匀,距离混合容器1~10cm处放一块磁铁,再加入引发剂;将体系加热至30~90℃静置,聚合反应0.5~12小时,得到包覆有耐高温聚合物的磁性纳米棒;
用溶剂清洗产物,除去未反应的单体和交联剂;
所述单体、交联剂、引发剂、磁性纳米粒子质量比为30~70:1~15:0.1~15:2~10;
所述磁铁为5000Gs;
步骤3:向磁性纳米棒复合物中加入胺类有机物或膦类有机物、以及分散介质;加热至20~90℃进行鎓盐化,反应持续8~24小时;所述磁性纳米棒复合物、胺类有机物或膦类有机物、分散介质的质量比为1~5:5~100:100~800;
步骤4:用溶剂充分清洗产物,除去未反应的原料,得到磁性棒状耐高温鎓盐相转移催化剂。
2.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷或乙烯基三乙氧基硅烷。
3.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述磁性纳米粒子为四氧化三铁、三氧化二铁、钡铁氧体或镍铁氧体。
4.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述单体为4-氯甲基苯乙烯、4-(3-氯丙基)苯乙烯、4-(3-溴丙基)苯乙烯、4-(4-氯丁基)苯乙烯、4-(4-溴丁基)苯乙烯、4-(5-氯戊基)苯乙烯、4-(5-溴戊基)苯乙烯、4-(6-氯己基)苯乙烯、4-(6-溴己基)苯乙烯、4-((2-氯乙氧基)甲基)苯乙烯、4-((2-溴乙氧基)甲基)苯乙烯、4-((3-氯丙氧基)甲基)苯乙烯、4-((3-溴丙氧基)甲基)苯乙烯、4-((4-氯丁氧基)甲基)苯乙烯或4-((4-溴丁氧基)甲基)苯乙烯。
5.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述交联剂为二乙烯基苯、双甲基丙烯酸乙二醇酯、二丙烯基苯、二乙烯基苯基甲烷或N-N-亚甲基双丙烯酰胺。
6.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化月桂酰或异丙苯过氧化氢。
7.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述胺类有机物为三甲胺、三甲胺盐酸盐、三乙胺、三乙胺盐酸盐、三丁胺、二甲基乙醇胺、甲基二乙醇胺、二辛基乙醇胺或吡啶。
8.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述膦类有机物为三丁基膦、三辛基膦、三苯基膦或三乙基膦。
9.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述分散介质为1,2-二氯乙烷、1,4-二氧六环、丙酮、水或乙醇。
10.根据权利要求1所述磁性棒状耐高温鎓盐相转移催化剂的制备方法,其特征在于:所述溶剂为乙腈、水或乙醇。
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