CN1385464A - Organic compound material containing inorganic nano material, its preparation method and use - Google Patents

Organic compound material containing inorganic nano material, its preparation method and use Download PDF

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CN1385464A
CN1385464A CN01112861A CN01112861A CN1385464A CN 1385464 A CN1385464 A CN 1385464A CN 01112861 A CN01112861 A CN 01112861A CN 01112861 A CN01112861 A CN 01112861A CN 1385464 A CN1385464 A CN 1385464A
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CN1137192C (en
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崔蔚
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

The present invention relates to an organic composite material containing inorganic nano material. According to the application requirements the correspondent inorganic material and organic material can be selected. One kind of composite material is characterized by that the inorganic macromolecular material is dispersed in a specific polymer in the form of nano granules, and another kind of composite material is characterized by that the inorganic macromolecular material is filled into the porous network polymer material. Said invention utilizes the mutual cross-linkage of inorganic macromolecular material and mutual entanglement of inorganic macromolecular material and porous network polymer material to form entanglement type network structure material containing open micropores. Said invention also relates to its preparation method and application in low-temp. fuel cell, secondary cell, lithium cell and other fields.

Description

Organic composite material containing inorganic nano material, preparation method and application thereof
The invention relates to an organic composite material containing inorganic nano-materials, in particular to an organic composite membrane containing inorganic nano-materials, a preparation method thereof and application thereof in fuel cells, secondary batteries and lithium batteries.
The development of high performance, high efficiency batteries (e.g., lithium batteries, fuel cells, etc.) is one of the top technologies in this century. The fuel cell has great significance for solving the environmental pollution as a new clean energy source. The fuel cell can be used as a power source to be applied to the aspects of spaceflight, motor vehicles, submarines, power stations and the like. The significance of using fuel cells in motor vehicles is the reduction of environmental pollution and the elimination of exhaust emissions. The manufacturing technology of the fuel cell is overcome at present. But one of the biggest reasons for hindering the industrialization and commercialization of the battery is that the cost of the battery is too high. Therefore, the development of cheap high-performance materials is of great significance.
The low-temperature fuel cell comprises the following components: current shunts, gas shunts, electrodes and proton exchange membranes as solid dielectrics. Proton exchange membranes are one of the cores of fuel cells and have high technical requirements, such as high chemical, thermal and mechanical stability, and proton conductivity. In addition, its manufacturing cost and material cost must be much lower than the current level to meet the requirements of fuel cell industrialization and commercialization.
Currently, only a few membrane materials are available worldwide for use in fuel cells, such as perfluorosulfonated membranes (trade name Nafion (r)) manufactured by dupont®Hereinafter, abbreviated as fluorine film) are known for their excellent chemical, mechanical and thermal stability as well as high conductivity at lower temperatures. However, the fluorine film has the following problems in application: 1) the production technology of the fluorine film is complex, and the manufacturing cost is very high (about 800 dollars per square meter at present); 2) the water content of the fluorine film is greatly influenced by the environment due to the hydrophilicity of the material, so the electric conductivity is also greatly influenced by the environment; 3) the fluorine membrane has high methanol permeability, and when the fluorine membrane is applied to a direct methanol fuel cell, the energy conversion efficiency is low; 4) the recovery of fluorine membranes is also a big problem at present.
For the above reasons, the necessity and urgency of developing a new membrane material to replace the fluorine membrane are more pronounced. Since the early nineties, a great deal of research work has been carried out to develop non-fluorine membranes. Firstly, the functionalization of high-temperature-resistant high-strength engineering plastics with main chains containing aromatic rings is worth mentioning. Such materials are the best performing class of polymers other than fluoropolymers. These polymers are now commercially available and therefore inexpensive and can be functionalized by relatively simple processes. Such as the sulfonation of Polyetheretherketone (PEEK). The sulfonation method is that polyether-ether-ketone is dissolved in concentrated sulfuric acid, and sulfonic group (-SO) is substituted through electrophilic substitution3H) To adjacent ether bonding sitesOn the aromatic ring. The degree of sulfonation varies with temperature and time. The sulfonated polyether-ether-ketone can be made into cation exchange membrane. Helmer-Metzmann, F., Ledjeff, K., and Nolte,r. in EP0574791a2 it is indicated that Sulfonated Polyetheretherketone (SPEEK) membranes have excellent chemical stability, thermal stability and good application properties as measured in fuel cells. However, when the sulfonation degree is increased for improving the proton conductivity of the membrane, the swelling degree of the SPEEK membrane is high. Thus, while the conductivity of such membranes can meet the requirements of fuel cells, the mechanical stability of the membranes in fuel cells is poor, thereby shortening the useful life of the membranes in the cells.
To reduce the swelling degree of such films, blended crosslinked films were developed. The acidic polymer or the basic polymer is blended into a film by means of physical crosslinking such as hydrogen bonding or salt formation, for example. One recent study is Kerres, J., Ullrich, A., Hein, M., Gogel, V., and Jorissen, J. published at the 17 th Stuttgart plastics workshop (Stuttgart Plastic Coloquium) on 3, 14-15.2001. The research work is that a cross-linking agent is added into a blending system containing different functional polymers, and the physical cross-linking between functional groups leads the structure of a blending film to be stable and the swelling degree of the film to be reduced through the chemical cross-linking of the functional groups and the cross-linking agent. For example in polyethersulfone (PSU-SO) containing lithium sulfonate salts3Li), lithium sulfenate polyethersulfone (PSU-SO)2Li) and amino polyether sulfone with di-iodo alkyl hydrocarbon
Figure A0111286100071
The following crosslinking reaction is formed in the blending system:
although the polymer blend membrane with the coexistence of chemical crosslinking and physical crosslinking improves the stability of the membrane and reduces the swelling degree, the problem of the chemical stability of the membrane is generated. The hydrocarbon chain (-CH) in this material2-CH2-CH2-) are easily decomposed by oxygen for a long time, which would have an effect on the life of the membrane in the fuel cell.
A recent literature reports a new series of research efforts on the development of composite inorganic and organic films with the aim of increasing the electrical conductivity and also the mechanical strength of the film. For example, Tazi, B, and Savadouo, O. published in the meeting of the 13th International conference on New Materials for Electrochemical Systems (13th International Symposium on New Materials for Electrochemical Systems), held 7 months 1999, by Tazi, B, and Savadouo, O. by Canada, by copolymerization of thiophene and silicotungstic acid in water-soluble sulfonated perfluoropolymers. The conductivity of the fluoropolymer thus produced is greatly improved. Staiti, P, Freni, S. and Hocevar, S. published in the Journal of Electrical resources (Journal of Power Sources)2000, 90 th research work on blending silica modified with phosphotungstic acid with Polybenzimidazole (PBI) to form organic and inorganic composite membranes. The film has excellent mechanical stability and thermal stability, but poor conductivity. To date, no testing of such composite membranes in fuel cells has been reported.
In high-efficiency lithium batteries which have been widely used in recent years, polypropylene/polyethylene (PP/PE) microporous films are used. The PP/PE film plays a role of assisting Li+Separating the cathode and anode regions. But PP/PE films are not conductive by themselves. Thus, Li+Is transmitted only by its own transition. Development of polymer thin film with ion conductivity for reducing Li+The steric hindrance encountered during the transport process to increase the efficiency of the cell has a high economic benefit.
The invention aims to provide an organic composite material containing inorganic nano-materials, which has strong chemical and thermal stability, low swelling degree and high electric conductivity.
Another object of the present invention is to provide a method for preparing the above organic composite material containing inorganic nano-materials.
It is also an object of the present invention to provide the use of the above organic composite material containing inorganic nanomaterial.
The general concept of the present invention is to develop organic composites containing inorganic nanomaterials. According to the application requirements, particularly the high requirements of the fuel cell on membrane materials, corresponding inorganic materials and corresponding organic materials can be selected, and the application requirements can be met by integrating the respective excellent properties of the inorganic materials and the organic materials.
A first aspect of the present invention provides a first class of organic composites containing inorganic nanomaterials, the composites comprising two of:
(1) an organic polymer (A) selected from:
(A1) polymers containing one or more acidic or basic functional groups selected from the group consisting of sulfonic acid groups, nitro groups, amino groups, pyridyl groups, -H2PO4-COOH and dialkylamino, the polymer matrix being selected from aromatic based polymers consisting of structural units (i) and (ii):
(i) selected from the following aromatic groups:
Figure A0111286100081
(ii) a linking group selected from: -CF2-；-O-；
Figure A0111286100082
(A2) Polybenzimidazole (PBI) and polyimide;
(A3) perfluoro or fluorine-containing sulfonated polymer, (2) inorganic high molecular material (B) selected from:
(B1) a polymer of a hetero-metal,
Figure A0111286100091
m is selected from Si, Ti, Sn, W and P;
(B2) highly branched polyalkoxysiloxanes
(B3) Block copolymerized heterometallic polymers
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
(B4) inorganic polymer materials obtained by modifying the substances in (B1), (B2) and (B3) by heteropoly acid;
the inorganic polymer material (B) is dispersed in the organic polymer (a) in the form of nanoparticles.
In the first type of organic composite material containing inorganic nanomaterial of the present invention, the organic polymer (a) is preferably sulfonated polyether ether ketone (SPEEK), sulfonated polyether ketone (SPEK), sulfonated polyether ether ketone (SPEEKK), or sulfonated polyether ether ketone (SPEEKK)Sulfonated Polyether Ether Sulfone (SPES), sulfonated polyphenylene ether (SPPO), Sulfonated Polyether Sulfone (SPSU), sulfonated nitrated polyether ether ketone, sulfonated aminated polyether ether ketone, Polybenzimidazole (PBI), perfluorinated or fluorinated sulfonated polymers, such as perfluorinated sulfonated polymer Nafion, have the following structural formula:
Figure A0111286100093
the inorganic high-molecular material (B) is preferably a hetero-metallic polymer (B1) in which M is Ti or Si,Highly branched polyethoxysiloxane (B2), and M1And M2A block copolymerized heterometallic polymer of Ti and Si, respectively (B3). The heteropoly acid in (B4) is preferably silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, more preferably silicotungstic acid and phosphotungstic acid.
A second aspect of the present invention is to provide a second class of organic composites containing inorganic nanomaterials, the composites comprising two of:
(1) a porous reticulated polymer material (C) chosen from Polyethylene (PE), polypropylene (PP), Polytetrafluoroethylene (PTFE), Polyetheretherketone (PEEK), Polyetherethersulfone (PES), polyamide, polyimide, and these polymers containing one or more acidic or basic functional groups chosen from-SO3H、-NO2，-NH2and-H2PO4；
(2) An inorganic polymeric material (B) selected from:
(B1) a polymer of a hetero-metal,
Figure A0111286100101
m is selected from Si, Ti, Sn, W and P;
(B2) highly branched polyalkoxysiloxanes
(B3) Block copolymerized heterometallic polymers
Figure A0111286100102
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
the inorganic polymer material (B) is filled in the porous reticular polymer material (C), and the inorganic polymer material (B) is crosslinked with each other and is intertwined with the porous reticular polymer material (C) to form an intertwined network structure material containing open micropores.
In the second type of inorganic nanomaterial-containing organic composite material of the present invention, the open micropores in the entangled network structure of the inorganic polymer material and the porous network polymer material are further functionalized, preferably with a heteropoly acid, a metal alkoxide, or phosphoric acid. The heteropoly acid is preferably silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, and is more preferably silicotungstic acid and phosphotungstic acid; the metal alkoxide is preferably titanium tetrabutylate alkoxide (Ti (OBt)4) Tetrabutyltin alkoxide (Sn (OBt))4) Zirconium tetrabutylate (Zr (OBt))4) It is most preferable thatTitanium tetrabutylate (Ti (OBt)4)。
In the second type of organic composite material containing inorganic nanomaterial of the present invention, the porous reticulated polymer material (C) may be in the form of a film, a foam, a porous particulate material, preferably a film. The polymers are preferably polyethylene, polytetrafluoroethylene, polyetheretherketone and polyetherethersulfone, and also those containing sulfonic acid, nitro or amino groups. The inorganic high molecular material (B) is preferably a hetero metal polymer (B1) in which M is Ti or Si, a highly branched polyethoxysiloxane (B2), and M1And M2A block copolymerized heterometallic polymer of Ti and Si, respectively (B3).
The first and second inorganic nanomaterial-containing organic composite materials of the present invention may be formed into various physical forms such as films, plates, blocks, strips, powders, etc., according to the use. A particularly preferred form is a composite membrane.
The invention also provides a preparation method of the first type of organic composite material containing the inorganic nano material, which comprises the following steps: preparing a solution (I) containing the inorganic high molecular material (B) selected from the above-mentioned (B1), (B2), (B3) or (B4); preparing a solution (II) containing said organic polymer (A) in a polar organic solvent; and (3) uniformly mixing the solution (I) and the solution (II), and removing the solvent to form the composite material.
The invention also provides a preparation method of the second type of organic composite material containing inorganic nano-materials, which comprises the following steps: preparing a solution (I) containing an inorganic high molecular material (B) selected from the above-mentioned (B1), (B2) or (B3); filling the solution (I) into the pores of the porous reticulated polymer material (C); and (3) crosslinking the inorganic high polymer material (B) in the solution (I) to form a loose net structure, and mutually intertwining the inorganic high polymer material (B) with the porous net polymer material to obtain the composite material containing the open micropores.
The above method may optionally further comprise the step of further functionalizing the open micropores of the resulting composite. The functionalization can be carried out with heteropolyacids, metal alkoxides or phosphoric acids. The heteropoly acid is preferably silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, more preferably silicotungstic acid and phosphotungstic acid, and the metal alkoxide is preferably titanium tetrabutylate alkoxide (Ti (OBt)4) Tetrabutyltin alkoxide (Sn (OBt))4) Zirconium tetrabutylate (Zr (OBt))4) Most preferred is titanium tetrabutylate (Ti (OBt))4)。
In addition, the invention also provides application of the organic composite material containing the inorganic nano material. The first and second organic composite materials containing inorganic nano materials can be used as ion conductive membranes to manufacture membrane electrode units for low-temperature fuel cells, secondary batteries and lithium batteries, and membrane separation engineering such as filtration, gas separation, electrodialysis and reverse osmosis.
The organic composite materials containing inorganic nano materials of the first class and the second class, especially the organic composite membranes containing inorganic nano materials have the function of selective ion permeation, and have good chemical, mechanical and thermal stability and high conductivity. This makes them well-suited for use in low-temperature fuel cells, secondary batteries, and lithium batteries, where they function to isolate the anode and cathode regions and transport ions.
The preparation method of the organic composite material containing the inorganic nano material can well prepare the required composite material, has lower production cost and is suitable for industrial production.
The present invention will be described in further detail with reference to the attached drawings, but the description is only for the understanding of the present invention and is not to be construed as limiting.
FIG. 1 is a schematic representation of a modeled membrane structure of one embodiment of a first class of inorganic nanomaterial-containing organic composite materials of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of a polyethylene film preferably used as the porous reticulated polymer material.
Fig. 3 is a scanning electron microscope photograph of a sulfonated nitro polyether ether ketone composite membrane containing 11.2 wt.% (all percentages below refer to wt.%) of highly branched polyethoxysiloxane.
FIG. 4 is an X-ray diffraction pattern of the highly branched polyethoxysiloxane modified with phosphotungstic acid from example 3.
FIG. 5 is a scanning electron microscope photomicrograph of the sulfonated polyetheretherketone composite membrane of example 3 containing 40 wt.% of highly branched polyethoxysiloxane modified with phosphotungstic acid.
FIG. 6 is an electron diffraction analysis spectrum of the sulfonated polyetheretherketone composite membrane containing phosphotungstic acid modified highly branched polyethoxysiloxane in example 3.
FIG. 7 is a scanning electron micrograph and a transmission electron micrograph of a composite film made of a polyethylene film and highly branched polyethoxysiloxane in example 5.
In a preferred embodiment of the first type of inorganic nanomaterial-containing organic composite material of the present invention, the polymer (a1) having one or more acidic or basic functional groups is a sulfonic acid group-containing, or sulfonic acid group-and nitro group-containing, or sulfonic acid group-and amino group-containing, aromatic base polymer composed of structural unit (i) and structural unit (ii):
(i) selected from the following aromatic groups:
(ii) a thermally stable linking group selected from: -CF2-；-O-；
Methods for the sulfonation of such aromatic-based polymers are known, for example the sulfonation of polyetheretherketones with 98% sulfuric acid, see European patent EP0574791A2 by Helmer-Metzmann, F., Ledjeff, K., and Nolte, R. In addition, Sulfonated Polyetheretherketone (SPEEK) can also be treated to contain nitro or amino groups by techniques known to those skilled in the art, see German patent PCT/DE99/00929 to Cui, W. and Kerres, J.
The inventors of the present invention have conducted a great deal of research and experiments, and selected the following inorganic polymer materials as the inorganic polymer material (B) used in the composite material of the present invention from among a plurality of inorganic polymer materials.
(B1) A polymer of a hetero-metal,
m is selected from Si, Ti, Sn, W and P.
The heterometal polymers can be prepared from metal alkoxides by polycondensation, the preparation of which is known to those skilled in the art. The mixed composite material of the heterometal polymer and other polymers is widely used as an optical material. Because of the hydrophilicity, non-swelling property and good mechanical property of the hetero-metal polymer, the hetero-metal polymer plays roles in ventilation, hydrophilicity, material mechanical stability enhancement and the like in the composite material.
(B2) Highly branched polyalkoxysiloxanes
Hyperbranched polymers emerging in recent years have attracted the interest of numerous researchers due to their unique properties. The highly branched polymer has high branching degree, loose structure and low density, thus having good solubility and being easy to dissolve in various organic solvents. Secondly, due to the open nature of the structure, hyperbranched polymers are susceptible to reaction with other molecular functional groups. It is particularly noteworthy that the highly branched inorganic polymers also have good solubility. For example, highly branched polyalkoxysiloxanes are readily soluble in various organic solvents such as tetrahydrofuran, toluene and the like, while having good compatibility.
The structure of the highly branched polyalkoxysiloxanes is given in the following examples, where the alkoxy group is an ethoxy group,
[ formula I ]
(highly branched polyethoxysiloxane (hPSOet))
(B3) Block copolymerized heterometallic polymers
Figure A0111286100142
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
the polymers can be prepared by copolymerization methods known to those skilled in the art.
(B4) The inorganic polymer material obtained by modifying the end groups of the substances in (B1), (B2) and (B3) by heteropoly acid takes phosphotungstic acid as an example, and the reaction mechanism is as follows:
the inventor of the present invention has made studies and selected a solution method to prepare the first class of organic composite materials containing inorganic nanomaterials of the present invention, wherein the inorganic macromolecules form dispersed phase regions with uniform size in the organic polymer material, and the size of the phase regions is in the nanoscale range. The specific mechanism is as follows: because the inorganic high molecular materials (B) all contain hydroxyl, when the inorganic high molecular materials (B) are mixed with the functional polymer (A) in solution, the hydroxyl is subjected to crosslinking reaction to form a nano microphase region with the following structure:
in addition, when heteropoly acid is added into the inorganic high molecular polymer to form microgel, and then the microgel is mixed with the functional high molecular (A), and when the solvent is volatilized, the microgel is aggregated to form nano particles. Fig. 1 shows a schematic view of a modeled membrane structure.
Because the functional group of the selected functionalized polymer (A) interacts with the hydroxyl on the surface of the inorganic high molecular material, the particles formed by the inorganic material can be well dispersed in the organic polymer, the interface combination of the phase region is firm, and the compatibility of the inorganic material and the organic material is greatly improved. Wherein the inorganic nanoparticles act as physical cross-linking sites. The mechanical properties of the film, i.e. the robustness and flexibility of the film, are thus greatly improved. And through-CH2-CH2-……-CH2The composite membranes of the invention show superior chemical stability compared to membranes crosslinked to improve mechanical properties. In addition, since both the inorganic nanoparticles and the organic polymer are conductive materials, their combination forms a specific ion transport channel (as shown in fig. 1), so that the conductivity of the film is greatly improved.
The first kind of organic composite material containing inorganic nanometer material is ion conducting material and ion conducting film containing sulfonated nitro polyether ether ketone (SNPEEK) and high branched polyethoxy siloxane (hPSiEt), and the content of hPSiEt is 0.1-70 wt.%. Preferred composites of the first type also contain Sulfonated Polyetheretherketone (SPEEK) and phosphotungstic acid (H)3PW12O40) An ion conductive composite membrane of modified hPSOIT. H3PW12O40The content in hPSiEt is 0.1-90 wt.%, based on H3PW12O40The content of the modified hPSiOEt in the composite material and the composite film is 0.1 to 70 wt.%, based on the total weight of the polymer (a) and the inorganic polymer material (B).
The second type of organic composite material containing inorganic nano material is prepared by filling inorganic high molecular material into porous reticular organic polymer material, crosslinking inorganic high molecular material around porous reticular organic polymer fiber to form loose reticular structure of inorganic high molecular material, and intertwining the loose reticular structure and porous reticular organic polymer material to obtain composite material containing open micropores. The composite material contains open micropores uniformly distributed, and the conductivity of the film can be purposefully improved by further functionalizing the surface walls of the micropores. These matters will be further described in the embodiments with reference to the drawings.
In the second type of inorganic nanomaterial-containing organic composite material of the present invention, the porous network polymer material (C) is preferably a polymer material having excellent properties in various respects, such as a polyethylene film, a polytetrafluoroethylene film, a polyetheretherketone film, and a polyetherethersulfone film. For example, the porosity of the polyethylene film shown in FIG. 2 is about 85%. What is needed isThe inorganic polymer material (B) used is, as described for the first type of inorganic nanomaterial-containing organic composite material, preferably a highly branched polyalkoxysiloxane, particularly preferably a highly branched polyethoxysiloxane (hPSOt). In the film-making process, the reaction mechanism is as follows:
Figure A0111286100161
[ formula II ]
The inorganic polymer contained in the prepared composite membrane can reach 85 wt.%. The cross-linked inorganic high molecules form nano particles in a polymer porous network, the particles are mutually overlapped, the structure is loose, and the membrane contains open micropores, so that the membrane has good flexibility. The inner surface of the micropores contains acidic groups. In such composite membranes, the inorganic polymeric network acts as a binder. The inorganic polymer entangled on the organic polymer fiber after cross-linking increases the solidity of the membrane, and the composite membrane prepared therefrom has good mechanical properties, chemical stability and ionic conductivity. Also, the thermal stability of the composite film is improved, and thus the use temperature is increased. Because the content ratio of the inorganic polymer in the composite membrane is very high, the membrane hardly deforms in aqueous solution, thereby ensuring that the membrane keeps long-term stability in a use environment.
A second class of inorganic nanomaterial-containing organic composite materials preferred in the present invention is hPSiOEt-containing polyethylene composite membranes, wherein the content of inorganic polymeric material can be as high as 90 wt.%. Preferred composites also containThe content of the titanium heterometal and the hPSOET can reach 90wt percent. Preferred composites also contain phosphotungstic acid (H)3PW12O40) Polyethylene composite membrane of modified hPSiEt, in which phosphotungstic acid (H)3PW12O40) The content of the modified hPSiOEt may be up to 90 wt.%, based on the total weight of the inorganic polymeric material (B) and the porous network polymeric material (C).
The present invention will be further illustrated by the following examples, which are provided for illustrative purposes only and are not intended to limit the scope and spirit of the present invention.
The characterization method of the membranes in the examples is as follows: structural characterization: scanning Electron Microscope (SEM), electron Transmission Electron Microscope (TEM), elemental identification: electron diffraction analysis (EDX), measurement parameters 20KV thermal stability test: thermal gravimetric method (TGA), measurement parameters are 10K/min, 2K/min, O2/N2Conductivity detection: the impedance spectrometer has the measurement parameters of 100mHz-500KHz and 25 ℃, and the membrane is treated in water in advance before the test. Process conditions for membrane treatment: soaked in 0.2N sulfuric acid at different temperatures for 24 hours and then rinsed in water. Membrane porosity and pore size distribution: the specific surface area of the features was calculated by the BET method and the pore size distribution was calculated by the B.J.H method. Swelling degree measurement: the weight of the film before and after swelling was determined by weight method, and then the degree of swelling was calculated
Example 1
Examples organic composite materials containing inorganic nano-materials according to the first category of the present invention were prepared using organic polymer (a) and inorganic polymer material (B) and their amounts shown in table 1.
The preparation method of the organic composite material containing the inorganic nano material comprises the following steps: an inorganic polymer material (B) was dissolved in an organic solvent shown in table 1, a solution of the polymer (a) in the same organic solvent was added thereto, and the mixture was stirred and mixed to polycondense the inorganic polymer material (B), and dried at 120 ℃ to evaporate the solvent, thereby forming a nano-scale microphase region. The hydroxyl groups contained on the surface of the inorganic nanoparticles interact with functional groups (such as sulfonic acid groups or nitro groups) contained in the polymer (a), ensuring good compatibility between the inorganic phase and the organic continuous phase. The amounts of the inorganic high molecular material (B) used in Table 1 are given in weight percent based on the total weight of the polymer (A) and the inorganic high molecular material (B).
TABLE 1
Film sample Numbering Polymer (A) Inorganic polymer material (B) Inorganic polymer material (B) The dosage is wt% Organic solvent
1a SNPEEK hPSiOEt 24.3 NMP
1b SPEEK hPSiOEt 3.2 NMP
1c SPEEK hPSiOEt 10.0 NMP
1d SPEEK hPSiOEt 30.5 NMP
1e SPEK PTiO 8.3 DMAC
1f SAPEEK PTiO 15.1 DMSO
1g SPES PSiO 10.2 DMAC
1h SPPES PSiO 15.2 DMAC
1i SPPO PTiSiO 18.8 DMSO
1j SPSU hPSiOEt 25.9 DMAC
1k PBI PSiO 8.3 DMAC
1l PSU-H2PO4 PSnO 5.3 DMAC
1m PSU-COOH PTiSiO 4.2 DMSO
1n Nafion hPSiOEt 39.6 NMP
1o Nafion hPSiOEt 72.3 NMP
Note: SNPEEK represents sulfonated nitro polyether ether ketone, SPEEK represents sulfonated polyether ether ketone, SPEK represents sulfonated polyether ketone, SAPEEK represents sulfonated amino polyether ether ketone, SPES represents sulfonated polyether ether sulfone, SPPES represents sulfonated poly biphenyl polyether sulfone, SPPO represents sulfonated polyphenyl ether, SPSU represents sulfonated polyether sulfone, PBI represents polybenzimidazole, PSU-H2PO4Represents containing-H2PO4Polyether sulfone of the group, PSU-COOH represents polyether sulfone containing-COOH group, Nafion represents perfluorinated sulfonated polymer; hPSOEt represents a highly branched polyethoxysiloxane, PTiO represents a heterometal titanium polymer (i.e., M is Ti (B1)), PSiO represents a heterometal silicon polymer (i.e., M is Si (B1)), PSnO represents a heterometal tin polymer (i.e., M is Sn (B1)), and PTiSiO represents a block copolymerized heterometal titanium silicon polymer (i.e., M is Sn1And M2Block copolymerized heterometallic polymers of Ti and Si, respectively); NMP is N-methylpyrrolidone, DMAC represents N, N' -dimethylacetamide; DMSO denotes dimethyl sulfoxide.
Example 2
A composite membrane of sulfonated nitro polyether ether ketone (SNPEEK) containing highly branched polyethoxysiloxane (hPSOET) was prepared according to the preparation method given in example 1, wherein the mixing ratios of the materials used are shown in Table 2.
TABLE 2
Film sample Numbering Polymer (A) Inorganic polymer material (B) Inorganic polymer material (B) The dosage is wt% Organic solvent
2a SNPEEK hPSiOEt 0.5 NMP
2b SNPEEK hPSiOEt 11.2 NMP
2c SNPEEK hPSiOEt 20.5 NMP
2d SNPEEK hPSiOEt 24.3 NMP
2e SNPEEK hPSiOEt 39.2 NMP
2f SNPEEK hPSiOEt 56.8 NMP
2g SNPEEK hPSiOEt 68.4 NMP
The composite film obtained as above was characterized, and it was found that the inorganic high molecular material (hPSiOEt) was dispersed in the form of nanoparticles in the polymer (snepeek). For example, fig. 3 shows a scanning electron microscope photograph of a sulfonated nitro polyetheretherketone composite membrane containing 11.2 wt.% highly branched polyethoxysiloxane. As can be seen, the nanoparticles are uniformly distributed in the sulfonated nitro polyether ether ketone in the inorganic phase formed by the polycondensation of hPSiEt with water.
Soaking the composite film in water, and measuring the conductivity at 25 deg.C to be 1.5 × 10-4To 1.0X 10-2S/cm. The swelling degree of the film is less than 40%.
Example 3
An organic composite membrane containing inorganic nano-materials is prepared by using sulfonated polyether ether ketone (SPEEK) and highly branched polyethoxy siloxane (hPSOIT) modified by heteropoly acid.
The structural formula of the sulfonated polyether ether ketone is as follows:
the sulfonation degree is 40-50%.
The structure of the highly branched polyethoxysiloxane is shown in formula [ I ] above. The terminal-OEt group of the highly branched inorganic polymer can be hydrolyzed to-OH, which can be further functionalized with a heteropoly acid (e.g., phosphotungstic acid), the reaction equation of which is shown in the above formula [ II ].
The preparation method of the membrane comprises the following steps: highly branched polyethoxysiloxane (hPSiEt) was dissolved in ethanol, and then a heteropoly acid (HPWA: phosphotungstic acid, or HSiWA: silicotungstic acid) of the kind and amount shown in Table 3 was added and stirred at room temperature. Taking 3d in Table 3 as an example, 31.3 wt.% phosphotungstic acid was added (this value is based on the total amount of phosphotungstic acid and highly branched polyethoxysiloxane). In addition, SPEEK is dissolved in N-methylpyrrolidone (NMP) to prepare a SPEEK-NMP solution. Then, the HPWA/hPSOIT ethanol solution prepared above is added to the SPEEK-NMP solution with stirring. Removing solvent ethanol and NMP, and drying at 120 deg.C under vacuum condition to obtain composite membrane.
TABLE 3 formulation of hPSOIT modified with heteropolyacid
Numbering Heteropolyacids The content of heteropoly acid is wt%
3a HPWA 5.0
3b HPWA 14.7
3c HPWA 26.7
3d HPWA 31.3
3e HPWA 47.6
3f HPWA 64.5
3g HPWA 84.5
3h HSiWA 0.5
3i HSiWA 5.9
3j HSiWA 20.2
3k HSiWA 40.4
3l HSiWA 70.5
3m HSiWA 85.2
The resulting composite membranes are shown in table 4. Wherein the content of the heteropoly acid (HPWA and HSiWA) is the weight percentage of the heteropoly acid in the inorganic high molecular material (B), and the weight percentage of the inorganic high molecular material (B) is based on the total weight of the inorganic high molecular material (B) and the polymer (A).
TABLE 4
Film sample Numbering Polymer (A) Inorganic polymer material (B) Inorganic polymer material (B) The dosage is wt% Organic solvent
4a SPEEK HPWA/hPSiOEt (31.3wt.％HPWA) 10.0 ethanol/NMP
4b SPEEK HPWA/hPSiOEt (31.3wt.％HPWA) 31.3 ethanol/NMP
4c SPEEK HPWA/hPSiOEt (31.3wt.％HPWA) 40.0 ethanol/NMP
4d SPEEK HPWA/hPSiOEt (31.3wt.％HPWA) 64.5 ethanol/NMP
4e SPEEK HSiWA/hPSiOEt (40.4wt.％HSiWA) 5.0 ethanol/NMP
4f SPEEK HSiWA/hPSiOEt (40.4wt.％HSiWA) 24.5 ethanol/NMP
FIG. 4 is an X-ray diffraction pattern of hPSiEt modified with phosphotungstic acid. Phosphotungstic acid is crystalline in the solid state, and the structure thereof is changed into an amorphous state, namely an amorphous state after the reaction with hPSOIT. However, it can be seen from the figure that as the content of phosphotungstic acid increases, the sample gradually transits from amorphous to crystalline, which indicates that part of phosphotungstic acid has not reacted with hPSOIT.
The structure of the composite membrane prepared in this example and the mechanism of proton transfer in the membrane are shown in fig. 1.
In the film prepared as above, the hPSiOEt nanoparticles modified with heteropoly acid are uniformly distributed in the sulfonated polyetheretherketone matrix, and for example, fig. 5 shows a scanning electron micrograph of the 4c film in table 4.
Using thermogravimetric analysis (2K/min, O)2TGA) were measured: physically adsorbed water in the resulting film is volatilized at a temperature in the range of 0 ℃ to 300 ℃. From 350 ℃ the sulfonic acid groups are cleaved from the polymer chain. When the temperature is higher than 450 deg.C, HPWA or HSiWA starts to decompose, the residue remained at 745 deg.C is inorganic polymer, and residue P of HPWA2O5Or residues SiO of HSiWA2. This indicates that the composite film is stable in an oxygen atmosphere at a temperature range of 0 to 350 ℃.
A composite membrane prepared from phosphotungstic acid modified hyperbranched polyethoxysiloxane is treated in a 0.2N sulfuric acid solution at 80 ℃ for 1 hour. Then, the plate was rinsed with clean water and detected by EDX. As shown in fig. 6, the film contains elements such as W, S, P, Si, O, etc., and thus it can be seen that the composite film is very stable in an acidic solution. Similarly, composite membranes made from silicotungstic acid modified hyperbranched polyethoxysiloxane also have similar properties.
The conductivity of the composite film changes with the proportion of the organic material and the inorganic material in the composite film. When the film contains 10-60 wt.% of heteropolyacid, its conductivity at 25 deg.C is 2.6 × 10-3To 1.4X 10-2S/cm.
Example 4
In this example, a second type of organic composite membrane containing inorganic nano-materials according to the present invention was prepared, and the inorganic polymer material (B) and the porous network polymer material (C) used are shown in table 5. The composite membrane is prepared by filling an inorganic high molecular material into a porous network polymer membrane.
Firstly, dissolving an inorganic high molecular material in an organic solvent shown in table 5, pouring the obtained solution into a porous polymer film, and after the solvent is volatilized, carrying out hydrolytic condensation on the inorganic high molecular material to enable the inorganic high molecular material to be crosslinked around polyethylene fiber yarns and attached to the polyethylene fiber yarns so as to form an intertwined network. Composite membranes containing different weight percentages can be prepared according to different concentrations of the inorganic high molecular material in the solution. The weight percentage of the inorganic high molecular material in the composite membrane can be up to 85 wt%, based on the total weight of the inorganic high molecular material (B) and the porous reticular polymer material (C).
TABLE 5
Film sample Numbering Porous net shape Polymer material (C) Inorganic polymer material (B) Inorganic polymer material (B) The dosage of the composition is wt% Organic solvent
5a PE film hPSiOEt 69.8 Xylene
5b PTFE film hPSiOEt 25.5 Xylene
5c PTFE film hPSiOEt 65.6 Xylene
5d PTFE film hPSiOEt 76.5 Xylene
5e PEEK film PTiO 35.3 NMP
5f SPEEK membrane PSiO 70.6 THF
5g SNPEEK film PSnO 60.1 THF
5h PES film PSiO 45.8 THF
5i PP film PTiSiO 75.2 NMP
Note: PE is polyethylene, PTFE is polytetrafluoroethylene, PEEK is polyether-ether-ketone, SPEEK is sulfonated polyether-ether-ketone, SNPEEK is sulfonated nitro polyether-ether-ketone, PES is polyether-ether-sulfone, PP is polypropylene; THF is tetrahydrofuran. The meanings of the other abbreviations are noted later in Table 1.
Example 5
As shown in example 4, highly branched polyethoxysiloxane (hPSiEt) was first dissolved in xylene, the resulting solution was poured into a porous PE film, and after evaporation of the solvent, the inorganic polymeric material was subjected to hydrolytic condensation to crosslink around and attach to the polyethylene filaments, forming an intertwined network. Composite membranes containing different weight percentages were prepared depending on the concentration of hPSOIT in the solution (Table 6). The weight percentage of the inorganic high molecular material in the composite membrane can reach 90 wt%, which is calculated by the total weight of the inorganic high molecular material (B) and the porous reticular polymer material (C).
TABLE 6
Film sample Numbering Porous net shape Polymer material (C) Inorganic polymer material (B) Inorganic polymer material (B) The dosage is wt%
6a PE film hPSiOEt 5.2
6b PE film hPSiOEt 20.1
6c PE film hPSiOEt 48.5
6d PE film hPSiOEt 69.8
6e PE film hPSiOEt 80.0
6f PE film hPSiOEt 86.5
The composite film obtained above was characterized by a scanning electron microscope and a transmission electron microscope, and it was found that the composite film had a layered structure containing inorganic polymer particles having a diameter of about 50 nm in the layer. The particles are in a loose and mutually overlapped structure (see figure 7).
The PE composite membrane prepared by the BET method and containing 80 wt.% of hPSiEt has a porosity of about 55% and a pore size distribution in the range of 1.5-10 nm, most of which is in the range of 1.5-3 nm. Specific surface area of 582 m2A density of 2.6 g/cm3。
Example 6
The pore walls of the composite membrane prepared in example 5 contain hydroxyl groups, and thus may be further surface-modified. For example, the conductivity of the porous composite membrane can be increased and the porosity can be decreased by introducing an acidic group.
Example 6a preparation of a hybrid film of a hetero-metal containing polymer PTiO.
The hPSOET-PE composite membrane prepared in example 5 was treated with a solution containing titanium tetrabutylate (Ti (OBt))4) Is immersed in the xylene solution for 2 hours. Taking out the composite membrane from the solution to obtain the membrane made of Ti (OBt) adsorbed in the membrane4And (3) a polymerized heterometal titanium polymer. The solvent was then removed and the composite membrane was post-treated in a 1N sulfuric acid solution. The composite membrane thus obtained was characterized.
The reaction equation occurring in the above process is：
Figure A0111286100241
According to Ti (OBt)4The composite film containing different concentrations of the hetero-metal titanium polymer can be prepared by the concentration in the solution and the aperture size of the composite film. The film has a decomposition temperature of 270 deg.C or higher (TGA, 10K/min, O) in an oxygen atmosphere2). The content of the heterometallic titanium polymer in the film is in the range of 10-35 wt.%, and its corresponding conductivity is 7.8 x 10-4S/cm to 1.74X 10-3S/cm.
In example 6b and example 6c, Sn (OBt) was used4And Zr (OBt)4Instead of Ti (OBt) in example 6a4Otherwise, the procedure is as described in example 6a, with the same results as in example 6 a.
Example 7
This example prepares a composite membrane containing a heteropoly acid.
In example 7a, the hPSOET-PE composite membrane prepared in example 5 was immersed in an ethanol solution of phosphotungstic acid for 3 hours, then the ethanol solvent was removed at 25 ℃, and the temperature was raised to 50 ℃ and dried in vacuum at 25 mbar for 5 hours. The resulting composite membrane was then characterized.
The concentration of the phosphotungstic acid can be determined according to the ethanol solution of the phosphotungstic acid used in the preparation process and the aperture size of the composite membrane. Can be measured by a weighing method (namely measuring the weight difference of the composite membrane before and after the reaction with the phosphotungstic acid). In the composite membranes containing phosphotungstic acid prepared in this example, the content of phosphotungstic acid was in the range of 5 to 25 wt.%, and the decomposition temperature of these composite membranes in an oxygen atmosphere was 300 ℃ or higher (TGA, 2K/min, O)2). Conductivity at 25 ℃ (10% H)2O) at 2.0X 10-3To 9.6X 10-3S/cm. The conductivity of the film at 95 ℃ is 1.28X 10-2To 2.54X 10-2S/cm.
In examples 7b, 7c and 7d, tests were carried out using silicotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, respectively, in place of phosphotungstic acid, and the composite membranes obtained were subjected to the same tests as in example 7a, with similar results.

Claims (10)

1. An organic composite material comprising inorganic nanomaterials, the composite material comprising two of:
(1) an organic polymer (A) selected from:
(A1) polymers containing one or more acidic or basic functional groups selected from the group consisting of sulfonic acid groups, nitro groups, amino groups, pyridyl groups, -H2PO4-COOH and dialkylamino, the polymer matrix being selected from aromatic based polymers consisting of structural units (i) and (ii):
(i) selected from the following aromatic groups:
Figure A0111286100021
(ii) a linking group selected from: -CF2-；-O-；
(A2) Polybenzimidazole (PBI) and polyimide;
(A3) perfluorinated or fluorinated sulfonated polymers;
(2) an inorganic polymeric material (B) selected from:
(B1) a polymer of a hetero-metal,
m is selected from Si, Ti, Sn, W and P;
(B2) highly branched polyalkoxysiloxanes
(B3) Block copolymerized heterometallic polymers
Figure A0111286100024
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
(B4) inorganic polymer materials obtained by modifying the substances in (B1), (B2) and (B3) by heteropoly acid;
the inorganic polymer material (B) is dispersed in the organic polymer (a) in the form of nanoparticles.
2. The inorganic nanomaterial-containing organic composite material of claim 1, wherein:
the organic polymer (a) is selected from sulfonated polyether ether ketone (SPEEK), sulfonated polyether ketone (SPEK), sulfonated polyether ether ketone (SPEEKK), Sulfonated Polyether Ether Sulfone (SPES), sulfonated polyphenylene ether (SPPO), Sulfonated Polyether Sulfone (SPSU), sulfonated nitrated polyether ether ketone, sulfonated aminated polyether ether ketone, Polybenzimidazole (PBI), perfluorinated or fluorinated sulfonated polymers, such as perfluorinated sulfonated polymer Nafion, having the following structural formula:
Figure A0111286100031
the inorganic high molecular material (B) is selected from a hetero metal polymer (B1) in which M is Ti or Si, a highly branched polyethoxysiloxane (B2), and M1And M2Block copolymerized heterometallic polymer of Ti and Si, respectively (B3), the heteropolyacid in (B4) being silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, preferably silicotungstic acid and phosphotungstic acid.
3. An organic composite material comprising inorganic nanomaterials, the composite material comprising two of:
(1) a porous reticulated polymer material (C) chosen from Polyethylene (PE), polypropylene (PP), Polytetrafluoroethylene (PTFE), Polyetheretherketone (PEEK), Polyetherethersulfone (PES), polyamide, polyimide, and these polymers containing one or more acidic or basic functional groups chosen from-SO3H、-NO2、-NH2and-H2PO4；
(2) An inorganic polymeric material (B) selected from:
(B1) a polymer of a hetero-metal,
Figure A0111286100032
m is selected from Si, Ti, Sn, W and P;
(B2) highly branched polyalkoxysiloxanes
(B3) Block copolymerized heterometallic polymers
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
the inorganic polymer material (B) is filled in the porous reticular polymer material (C), and the inorganic polymer material (B) is crosslinked with each other and is intertwined with the porous reticular polymer material (C) to form an intertwined network structure material containing open micropores.
4. The organic composite material containing inorganic nanomaterial as claimed in claim 3, wherein the open micropores in the entangled network structure of the inorganic polymeric material and the porous network polymeric material are further functionalized, preferably with heteropolyacids, preferably silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, more preferably silicotungstic acid and phosphotungstic acid, metal alkoxides, preferably titanium tetrabutylate (Ti (OBt))4) Tetrabutyltin alkoxide (Sn (OBt))4) Zirconium tetrabutylate (Zr (OBt))4) Most preferred is titanium tetrabutylate (Ti (OBt))4)。
5. The organic composite material containing inorganic nanomaterial of claim 3 or 4, wherein the porous reticulated polymer material (C) is in the form of a film, a foam, a porous particulate material, preferably a film.
6. The organic composite material containing inorganic nanomaterial of claim 3 or 4, the polymers being polyethylene, polytetrafluoroethylene, polyetheretherketone and polyetherethersulfone, and those containing sulfonic acid groups, nitro groups or amino groups, the inorganic macromolecular material (B) being selected from the group consisting of a heterometal polymer (B1) in which M is Ti or Si, a highly branched polyethoxysiloxane (B2), and M1And M2A block copolymerized heterometallic polymer of Ti and Si, respectively (B3).
7. The inorganic nanomaterial-containing organic composite material of claim 1 or claim 3, which is in the physical form of a film, a sheet, a block, a strip, a powder, preferably a composite film.
8. A method for preparing an organic composite material containing inorganic nanomaterials, the method comprising the steps of:
preparing a solution (I) containing an inorganic polymer material (B) selected from the group consisting of:
(B1) a polymer of a hetero-metal,
Figure A0111286100042
m is selected from Si, Ti, Sn, W and P;
(B2) highly branched polyalkoxysiloxanes
(B3) Block copolymerized heterometallic polymers
M1、M2Are respectively selected from Si, Ti, Sn, W and P;
filling the pores of the porous reticulated polymer material (C) with a solution (I), said polymer being chosen from Polyethylene (PE), polypropylene (PP), Polytetrafluoroethylene (PTFE), Polyetheretherketone (PEEK), Polyetherethersulfone (PES), polyamide, polyimide, and these polymers containing one or more acidic or basic functional groups chosen from-SO3H、-NO2、-NH2and-H2PO4；
Crosslinking the inorganic high molecular material (B) in the solution (I) to form a loose net structure, and mutually intertwining the inorganic high molecular material (B) with the porous net polymer material to obtain a composite material containing open micropores;
optionally, the open pores of the resulting composite are further functionalized.
9. A process as claimed in claim 8, wherein the functionalization is carried out with a heteropolyacid, preferably silicotungstic acid, phosphotungstic acid, silicomolybdic acid and molybdenum phosphotungstic acid, more preferably silicotungstic acid and phosphotungstic acid, a metal alkoxide, preferably titanium tetrabutylate alkoxide (Ti (OBt)4) Tetrabutyltin alkoxide (Sn (OBt))4) Zirconium tetrabutylate (Zr (OBt))4) Most preferred is titanium tetrabutylate (Ti (OBt))4)。
10. Use of the inorganic nanomaterial-containing organic composite material of claims 1 to 7 as an ion-conducting membrane for the fabrication of membrane electrode units for low temperature fuel cells, for secondary batteries, lithium batteries, in membrane separation processes such as filtration, gas separation, electrodialysis, reverse osmosis.
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