One kind coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and its preparation method and application
阅读说明：本技术 一种含锌多面体低聚倍半硅氧烷配位聚合物及其制备方法和应用 (One kind coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and its preparation method and application ) 是由 张文超 张文远 杨荣杰 于 2019-08-29 设计创作，主要内容包括：本发明涉及金属高分子复合材料技术领域,提供了一种含锌多面体低聚倍半硅氧烷配位聚合物及其制备方法和应用。本发明首先在自由基引发剂引发下,使八乙烯基笼型低聚倍半硅氧烷与疏基羧酸化合物发生加成反应,得到八羧基笼型低聚倍半硅氧烷,然后利用配位原理,将其与锌离子进行配位,从而将笼型低聚倍半硅氧烷与锌元素连接起来,得到含锌多面体低聚倍半硅氧烷配位聚合物；并且本发明在配位过程采用乙酸锌与八羧基笼型低聚倍半硅氧烷反应,由于金属乙酸盐的存在,使反应体系对空气不敏感,不需要惰性气体保护,在常温常压下即可进行配位。本发明制备的含锌多面体低聚倍半硅氧烷配位聚合物具有发光性能,且热稳定性好。(The present invention relates to metal-polymer technical field of composite materials, provide one kind coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and its preparation method and application.The present invention is first under radical initiator initiation, make eight ethenyl cage model oligomeric silsesquioxanes and thin carboxylic acid compound that addition reaction occur, obtain eight carboxyl polyhedral oligomeric silsesquioxanes, then coordination principle is utilized, it is coordinated with zinc ion, to connect polyhedral oligomeric silsesquioxane with Zn-ef ficiency, the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc is obtained；And the present invention is reacted using zinc acetate with eight carboxyl polyhedral oligomeric silsesquioxanes in complexation process, due to the presence of metal acetate, is kept reaction system insensitive to air, is not needed inert gas shielding, can be coordinated at normal temperatures and pressures.The coordination polymer of polyhedral oligomeric silsesquioxane containing zinc prepared by the present invention has luminescent properties, and thermal stability is good.)
1. a kind of coordination polymer of polyhedral oligomeric silsesquioxane containing zinc, which is characterized in that have structure shown in Formulas I:
In Formulas I, m=1 or 2, n are positive integer.
2. the preparation method of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc described in claim 1, which is characterized in that packet Include following steps:
Eight ethenyl cage model sesquialter siloxanes, mercaptan carboxylic acid's compound, radical initiator and organic solvent are mixed and added At reaction, eight carboxyl polyhedral oligomeric silsesquioxanes are obtained；
At normal temperatures and pressures, the eight carboxyls polyhedral oligomeric silsesquioxane, alcohols solvent and aqueous zinc acetate solution are mixed into Row complexation reaction obtains the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc.
3. preparation method according to claim 2, which is characterized in that mercaptan carboxylic acid's compound is thioacetic acid or mercapto Base propionic acid.
4. preparation method according to claim 2 or 3, which is characterized in that eight ethenyl cage model sesquialter siloxane with The molar ratio of mercaptan carboxylic acid's compound is 1:8~12.
5. preparation method according to claim 2, which is characterized in that the radical initiator includes azodiisobutyronitrile And/or azobisisoheptonitrile；The gross mass and free radical of eight ethenyl cage model sesquialter siloxane and thin carboxylic acid compound The mass ratio of initiator is 1:0.01~0.02.
6. preparation method according to claim 2, which is characterized in that eight ethenyl cage model sesquialter siloxane and thin base The gross mass of carboxylic acid compound and the volume ratio of organic solvent are 1g:3~4mL.
7. preparation method according to claim 2, which is characterized in that the temperature of the addition reaction is 40~80 DEG C, institute The time for stating addition reaction is 12~36h.
8. preparation method according to claim 2, which is characterized in that the eight carboxyls polyhedral oligomeric silsesquioxane and alcohol The volume ratio of class solvent is 1g:80~100mL；The alcohols solvent is dehydrated alcohol and/or anhydrous methanol.
9. preparation method according to claim 2, which is characterized in that the eight carboxyls polyhedral oligomeric silsesquioxane and second The molar ratio of sour zinc is 1:4.
10. application of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc described in claim 1 as embedded photoluminescent material.
Technical field
The present invention relates to metal-polymer technical field of composite materials, in particular to a kind of sesquialter silicon of polyhedral oligomeric containing zinc Oxygen alkane coordination polymer and its preparation method and application.
Background technique
Metal organic complex, which transmits energy by the UV absorption and intramolecular of organic ligand, makes material launch metal After forming complex fluorescent quenching phenomenon occurs for the characteristic fluorescence of ion, still, part metals ion and ligand, only some Metal ion can retain original fluorescence phenomenon after forming complex, so choosing suitable metal ion could be by fluorescence phenomenon Retain, and the thermal stability of metal organic complex is poor, limits its application field and range.
Polyhedron polyhedral oligomeric silsesquioxane (POSS) be one kind possess be keyed by Si-O-Si made of it is inorganic in Core is connected to the hybrid inorganic-organic materials of apex angle by organic group, and on the one hand this material inherits inorganic matter excellent On the other hand thermostabilization has the possibility of modified with functional group, with hybrid inorganic-organic ligand generation due to the organic group of apex angle For organic ligand, the metallic composite obtained in this way can improve thermal stability.In recent years, the complex of metal and POSS There is relevant report, but preparation method is generally more complex, the complexation process of ligand and metal ion needs to heat and inert gas Protection, the tenor of product is lower, and photoluminescence performance is poor.
Summary of the invention
It is an object of that present invention to provide a kind of coordination polymers of polyhedral oligomeric silsesquioxane containing zinc and preparation method thereof And application.The coordination polymer of polyhedral oligomeric silsesquioxane containing zinc provided by the invention has photoluminescence performance, thermostabilization Property is good, tenor is high, and preparation method is simple, at low cost.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of coordination polymer of polyhedral oligomeric silsesquioxane containing zinc, has structure shown in Formulas I:
In Formulas I, m=1 or 2, n are positive integer.
The present invention provides the preparation method of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc described in above scheme, The following steps are included:
Eight ethenyl cage model sesquialter siloxanes, mercaptan carboxylic acid's compound, radical initiator and organic solvent are mixed into Row addition reaction obtains eight carboxyl polyhedral oligomeric silsesquioxanes；
At normal temperatures and pressures, the eight carboxyls polyhedral oligomeric silsesquioxane, alcohols solvent and aqueous zinc acetate solution are mixed It closes and carries out complexation reaction, obtain the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc.
Preferably, mercaptan carboxylic acid's compound is thioacetic acid or mercaptopropionic acid.
Preferably, the molar ratio of eight ethenyl cage model sesquialter siloxane and mercaptan carboxylic acid's compound is 1:8~12.
Preferably, the radical initiator includes azodiisobutyronitrile and/or azobisisoheptonitrile；Eight vinyl The mass ratio of the gross mass and radical initiator of cage-type silsesquioxane and thin carboxylic acid compound is 1:0.01~0.02.
Preferably, the gross mass and organic solvent of eight ethenyl cage model sesquialter siloxane and thin carboxylic acid compound Volume ratio is 1g:3~4mL.
Preferably, the temperature of the addition reaction is 40~80 DEG C, and the time of the addition reaction is 12~36h.
Preferably, the volume ratio of the eight carboxyls polyhedral oligomeric silsesquioxane and alcohols solvent is 1g:80~100mL； The alcohols solvent is dehydrated alcohol and/or anhydrous methanol.
Preferably, the molar ratio of the eight carboxyls polyhedral oligomeric silsesquioxane and zinc acetate is 1:4.
The present invention provides the coordination polymers of polyhedral oligomeric silsesquioxane containing zinc described in above scheme as photic hair The application of luminescent material.
The present invention mentions a kind of coordination polymer of polyhedral oligomeric silsesquioxane containing zinc, has structure shown in Formulas I, the present invention The coordination polymer of polyhedral oligomeric silsesquioxane containing zinc provided has excellent photoluminescence performance and thermal stability；Implement Example the result shows that, the temperature of initial decomposition of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc provided by the invention can reach To 241.2 DEG C.
The present invention provides the preparation methods of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc described in above scheme. The invention firstly uses sulfydryl-double bond click chemistry reactions to make oligomeric times of eight ethenyl cage models under radical initiator initiation Addition reaction occurs for half siloxanes and thin carboxylic acid compound, obtains eight carboxyl polyhedral oligomeric silsesquioxanes, then using matching Position principle, it is coordinated with zinc ion, to polyhedral oligomeric silsesquioxane be connected with Zn-ef ficiency, products therefrom With photoluminescent property not available for inorganic metal salt；And the present invention uses zinc acetate and eight carboxyl cages in complexation process The reaction of type oligomeric silsesquioxane, due to the presence of metal acetate, keeps reaction system insensitive to air, does not need indifferent gas Body protection, to temperature without particular/special requirement, does not need to heat, can be coordinated at normal temperatures and pressures.Preparation provided by the invention Method is simple, easy to operate, and reaction condition is mild, reproducible.
Detailed description of the invention
Fig. 1 is the FT-IR spectrogram for the addition product that embodiment 1 obtains；
Fig. 2 is the addition product that embodiment 1 obtains1H NMR spectra；
Fig. 3 is the addition product that embodiment 1 obtains13C NMR spectra；
Fig. 4 is the addition product that embodiment 1 obtains29Si NMR spectra；
Fig. 5 is the polyhedral oligomeric silsesquioxane coordination polymer recombination luminescence material containing Zn-ef ficiency prepared by embodiment 1 The FT-IR spectrogram of material；
Fig. 6 is the XPS spectrum figure of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc prepared by embodiment 1；
Fig. 7 is the TG spectrogram of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc prepared by embodiment 1；
Fig. 8 is the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and eight carboxyl POSS ligands prepared by embodiment 1 Luorescence excitation spectrogram；
Fig. 9 is the polyhedral oligomeric silsesquioxane coordination polymer and eight carboxyls containing Zn-ef ficiency prepared by embodiment 1 The fluorescent emission spectrogram of POSS ligand.
Specific embodiment
The present invention provides a kind of coordination polymers of polyhedral oligomeric silsesquioxane containing zinc, have structure shown in Formulas I:
In Formulas I, m=1 or 2, n are positive integer.
The coordination polymer of polyhedral oligomeric silsesquioxane containing zinc provided by the invention is by eight carboxyl polyhedral oligomeric sesquialter silicon Oxygen alkane (eight carboxyl POSS) is obtained with zinc ion coordination, has eight carboxyls that can be coordinated in eight carboxyl POSS ligand structures, The content of zinc ion is high in the coordination polymer of formation, and then also will be more by zinc ion bring gain effect；And eight Carboxyl POSS has luminescence generated by light phenomenon, and resulting polymers remain on reservation photoluminescence performance after coordination.
The present invention provides the preparation method of the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc described in above scheme, The following steps are included:
Eight ethenyl cage model sesquialter siloxanes, mercaptan carboxylic acid's compound, radical initiator and organic solvent are mixed into Row addition reaction obtains eight carboxyl polyhedral oligomeric silsesquioxanes；
At normal temperatures and pressures, the eight carboxyls polyhedral oligomeric silsesquioxane, alcohols solvent and aqueous zinc acetate solution are mixed It closes and carries out complexation reaction, obtain the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc.
The present invention by eight ethenyl cage model oligomeric silsesquioxanes, dredge carboxylic acid compound, radical initiator and organic Solvent mixing carries out addition reaction, obtains eight carboxyl polyhedral oligomeric silsesquioxanes (eight carboxyl POSS), i.e. addition product.This hair It is bright to be reacted using sulfydryl-double bond click chemistry, carboxyl is introduced into formation hybrid inorganic-organic ligand in octavinyl-POSS, then It is further coordinated with zinc ion and ligand, it is low to obtain excellent heat stability, the polyhedron containing zinc with photoluminescence performance Polysilsesquioxane coordination polymer.
In the present invention, the thin carboxylic acid compound is preferably thioacetic acid or mercaptopropionic acid；The eight vinyl cage The molar ratio of type silsesquioxane and thin carboxylic acid compound are preferably 1:8~12, more preferably 1:9~11.
In the present invention, the radical initiator preferably includes azodiisobutyronitrile and/or azobisisoheptonitrile；It is described The mass ratio of the gross mass and radical initiator of eight ethenyl cage model sesquialter siloxanes and thin carboxylic acid compound is preferably 1: 0.01~0.02, more preferably 1:0.015.
In the present invention, the organic solvent is preferably acetone, petroleum ether, acetonitrile, methylene chloride, chloroform, tetrahydro One of furans is a variety of；The gross mass of eight ethenyl cage model sesquialter siloxane and thin carboxylic acid compound with it is organic molten The volume ratio of agent is preferably 1g:3~4mL.
In the present invention, the temperature of the addition reaction is preferably 40~80 DEG C, further preferably 42~60 DEG C, more excellent 45~48 DEG C are selected as, the time of the addition reaction is preferably 12~36h, more preferably 15~for 24 hours.The present invention is preferably first by eight Ethenyl cage model oligomeric silsesquioxane dredges carboxylic acid compound and organic solvent mixing, obtains mixed solution；Then again to institute It states and radical initiator is added in mixed solution, cause addition reaction.
In the present invention, when raw material is to dredge base propionic acid, the structure such as formula of the eight carboxyls polyhedral oligomeric silsesquioxane Shown in II；
After the completion of addition reaction, the present invention preferably by addition product feed liquid liquid separation, then by gained upper layer yellow liquid into Row drying obtains eight carboxyl polyhedral oligomeric silsesquioxanes.The present invention does not have particular/special requirement to the specific method of the liquid separation, makes With method well known to those skilled in the art；The temperature of the drying is preferably 60 DEG C, and the dry time is preferably 8h, is done Gained yellow solid is eight carboxyl polyhedral oligomeric silsesquioxanes after dry.
After obtaining eight carboxyl polyhedral oligomeric silsesquioxanes, the present invention is at normal temperatures and pressures, low by the eight carboxyls cage modle Polysilsesquioxane, alcohols solvent and aqueous zinc acetate solution mixing carry out complexation reaction, obtain the sesquialter silicon of polyhedral oligomeric containing zinc Oxygen alkane coordination polymer.In the present invention, the alcohols solvent is preferably dehydrated alcohol and/or anhydrous methanol；Eight carboxyl The quality of polyhedral oligomeric silsesquioxane and the volume ratio of alcohols solvent are preferably 1g:80~100mL, more preferably 1g:90mL； The aqueous zinc acetate solution is preferably anhydrous zinc acetate aqueous solution, and the mass concentration of the aqueous zinc acetate solution is preferably 0.5~ 0.65%, more preferably 0.6%；The molar ratio of the eight carboxyls polyhedral oligomeric silsesquioxane and zinc acetate is preferably 1:4.This Invention is reacted using zinc acetate with eight carboxyl polyhedral oligomeric silsesquioxanes in complexation process, due to the presence of metal acetate, Keep reaction system insensitive to air, do not need inert gas shielding, to temperature without particular/special requirement, does not need to heat, entirely match Position process is carried out at normal temperatures and pressures.
The present invention preferably first mixes eight carboxyl polyhedral oligomeric silsesquioxanes and alcohols solvent, and it is low to obtain eight carboxyl cage modles Then the alcoholic solution of polysilsesquioxane again mixes the alcoholic solution of eight carboxyl polyhedral oligomeric silsesquioxanes and aqueous zinc acetate solution It closes and carries out complexation reaction；After the alcoholic solution of eight carboxyl polyhedral oligomeric silsesquioxanes and aqueous zinc acetate solution are mixed, mixed liquor In have white solid precipitation, as coordination product；The present invention does not have particular/special requirement to the time of the complexation reaction, reacts to white Color solid is precipitated complete.
In the present invention, the complexation reaction can carry out at normal temperatures and pressures, without carrying out additional heating or cooling, Without additional pressurization；Room temperature of the present invention is specially room temperature, and normal pressure is specially a standard atmospheric pressure.
After the completion of complexation reaction, the present invention preferably filters gained complexation reaction product feed liquid, the solid product that will be obtained It is successively washed and is dried, obtain the coordination polymer of polyhedral oligomeric silsesquioxane containing zinc；In the present invention, the washing Preferably include the deionized water successively carried out washing and dehydrated alcohol washing；The temperature of the drying is preferably 50~110 DEG C, more Preferably 80 DEG C, the dry time is preferably 7~11h, more preferably 10h.
The present invention also provides the coordination polymers of polyhedral oligomeric silsesquioxane containing zinc described in above scheme as photic The application of luminescent material.The coordination polymer of polyhedral oligomeric silsesquioxane containing zinc provided by the invention has Photoluminescence Can, and stability is good.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair The restriction of the scope of the present invention.