Synthesis Of Bottlebrush Copolymers And Organic Nanotubes For Their Catalytic Application

Bottlebrush copolymers have attracted much attention due to the advantage of the densely grafted polymeric side chains,multiple synthesis method and the size in nano scale.In the past decades,bottlebrush copolymers have widely applied in constructing organic nanotube,stimuli-responsive materials,bio-pharmaceutical,self-assembly in solution and organic/inorganic hybrid nanostructures.This thesis is based on the perspective of the functionality of bottlebrush copolymers,and further engineers the nanostructures of bottlebrush materials.The goal of this thesis is to develop new strategy for preparing nanostructured bottlebrush copolymers,invent novel nanostructured bottlebrush materials and further explore the practical applications of these materials in the field of catalysis.In the chapter two,we synthesized two kinds of intramolecular crosslinking of bottlebrush copolymers that can conduct "one-pot" cascade reactions when added together(CCBCl and CCBC2).One was supported sulfonic acid(PTSA)which can act as acid catalyst(CCBC1),the other was supported N-methyl-N-(2-((4-vinylbenzyl)oxy)ethyl)pyridine-4-amine(VEMAP)which can act as base catalyst(CCBC2).The grafting number of monomer phenyl 4-vinylbenzene sulfonate(PVBS)is 23,4-(3-butenyl)styrene(BS)is 10 and the N-isopropylacrylamide(NIPAAm)is 220 in the side chain of acid bottlebrush copolymer(CCBCl).The grafting number of monomer VEMAP is 10,BS is 4,styrene is 4,NIPAAm is 260 in the side chain of base bottlebrush copolymer(CCBC2).After the "one-pot" cascade experiment,we conclude that the small molecules such as PTSA or DMAP could freely diffuse into the core of the bottlebrush copolymer and deactivate the acidic or basic groups through acid-base neutralization reactions and the presence of cross-linking in the core layer of bottlebrush copolymer appears to be essential for producing site isolation effects for"one-pot" cascade reactions.Moreover,this is the first time that bottlebrush copolymers were applied in catalyze "one-pot" cascade reaction and expand the application of bottlebrush copolymers.In the chapter three,we report a method to construct organic nanotubes through a bottlebtush soft template.We synthesized three kinds of nanotubes including:Acid-nanotube,Base-nanotube and Pd-nanotube.The nanotube can be applied to catalyze the Knoevenagel reaction in water,"one-pot" cascade reaction and Suzuki-Miyaura coupling reaction.The conversion of Knoevenagel reaction in water is 95%when used Base-nanotube as catalyst.The conversion of(dimethoxymethyl)benzene and yield of final product is 100%in the "one-pot"cascade reaction when used Acid-nanotube and Base-nanotube as catalyst.The conversion of 4-iodoanisole in the Suzuki-Miyaura coupling reaction is 97%when used Pd-nanotube as catalyst.The organic nanotube catalyst can be recycled 5 times and the catalytic activity have no obvious decrease.From the result,we can conclude that the organic nanotube supported catalyst have much more potential application in industry than the intramolecular crosslinking bottlebrush copolymers and created a new multifunctional bottlebrush nanomaterial.In the chapter four,we report an amphiphilic bifunctional acid and base organic nanotube used in catalyze "one-pot" cascade reaction(Acid-Base-nanotube).The bifunctional organic nanotube was constructed through a soft template method and imidazole was supported in the core as base site and sulfonic acid on the shell as acid site.We demonstrated that the cavity microenvironment of the amphiphilic bifunctional nanotubes is similar to dichloromethane through the fluorescence experiment.The conversion of(dimethoxymethyl)benzene and yield of final product is 100%in the "one-pot" cascade reaction conducted in H2O when used Acid-Base-nanotube as catalyst.We can separate the product from the reaction mixture through adding ethyl ether into the reaction bottle.The bifunctional organic nanotube catalyst can be recycled 6 times and the catalytic activity have no obvious decrease.The develop of this new bifunctional organic nanotube open a new method to construct bifunctional catalyst.In the chapter five,we synthesized a hyper crosslinked microporous organic nanotube supported amine via intermolecular hyper crosslinking(Amine-MNNs).One part the Amine-MNNs then turned to supported tungstate through an easy ion exchange and catalysis the selective oxidation of sulfides(TMNNs).The conversion and selective can achieve to 99%at mild conditions.The tungstate supported hyper crosslinked microporous organic nanotube can be recycled 8 times and the catalytic activity have no obvious decrease.The other part the amino-groups in the Amine-MNNs were fractional reacted with an environment friendly acid catalyst phosphotungstic acid and formed an acid-base bifunctional hyper crosslinked microporous organic nanotube(PTA-MNNs).The conversion of(dimethoxymethyl)benzene is 100%and the yield of final product is 99%in the"one-pot" cascade reaction conducted in malononitrile when used PTA-MNNs as catalyst.The PTA-MNNs catalyst can be recycled 8 times and the catalytic activity have no obvious decrease.We open a new method for the development of nanomaterials in catalyze the selective oxidation of sulfides and "one-pot" cascade reaction.