TWI445766B - Compositions containing maleimide derivatives, compositions containing maleimide-derived copolymers and films and cells comprising the compositions - Google Patents

Description

Composition containing maleic imine derivative, composition containing maleimide-derived copolymer, and film and battery comprising the same

The present invention relates to a composition, and more particularly to a composition comprising a maleic imide derivative, a composition comprising a maleic imide derived copolymer, and a film and battery comprising the above composition.

Currently, the commercial fuel cell proton conducting membrane is a sulfonic acid group-containing perfluoro-substituted polymer copolymer (PFSA), but the price is very expensive, and the biggest problem in the use of the PEMFC proton conducting membrane is hydrothermal management. When the temperature is close to the boiling point of water, PFSA will reduce the proton conductivity due to water loss, which will reduce the efficiency of PEMFC, which is one of the important reasons for the use of limited PEMFC.

Many non-fluoropolymers are expected to be used in fuel cells, such as sulfonated polystyrene, sulfonating polystyrene using a sulfonating agent or polymerizing a sulfonated monomer (U.S. Patent No. 5,679,482). U.S. Patent No. 6,090,895 discloses a cross-linking process for sulfonated polymers such as sulfonated polyether ketones, sulfonated polyether oximes, sulfonated polystyrenes and the like. However, in the above patent, the sulfonate attached to the benzene ring has a problem of low hydrolysis stability. In addition, generally non-fluoropolymers have the advantage of low cost raw materials, but there are doubts about poor long-term chemical resistance, which also greatly reduces the potential for commercialization.

The Republic of China Patent No. I305214 discloses a polybenzimidazole-polytetrafluoroethylene composite film in which a polybenzimidazole is filled with a pore of a polytetrafluoroethylene pore film by a coupling agent to form an ultrathin ion exchange membrane. However, it must be considered that in the PBI structure, special monomers will become strategic materials in the future, and there are problems that cannot be achieved.

An embodiment of the present invention provides a composition comprising a maleimide derivative, comprising: a fluorine-containing polymer; and a maleimide derivative having the following chemical formula (I) or (II):

Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ , Wherein the weight ratio of the fluorine-containing polymer to the maleimide derivative in the composition is from 5 to 70%.

An embodiment of the present invention provides a composition comprising a maleic imide-derived copolymer, comprising: a fluorine-containing polymer; and a maleimide-derived copolymer having the following chemical formula (III):

Where M is an unsaturated monomer capable of free radical polymerization, m is between 1 and 10,000, n is between 1 and 10,000, and X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide-derived copolymer are The weight ratio in the composition is between 5 and 70%.

An embodiment of the present invention provides a film comprising: a fluorine-containing polymer; and a maleic imine derivative having the following chemical formula (I) or (II) or a male having the following chemical formula (III) Yttrium-derived copolymer:

Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

Where M is an unsaturated monomer capable of free radical polymerization, m is between 1 and 10,000, n is between 1 and 10,000, and X ₁ is , (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide derivative or the horse The weight ratio of the quinoneimine-derived copolymer to the film is between 5 and 70%.

An embodiment of the invention provides a battery comprising: a cathode and an anode; and a film disposed between the cathode and the anode, wherein the film comprises a fluorine-containing polymer and a chemical formula (I) Or a maleic imide derivative of (II) or a maleic imine derivative copolymer having the following chemical formula (III):

Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

Where M is an unsaturated monomer capable of free radical polymerization, m is between 1 and 10,000, n is between 1 and 10,000, and X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide derivative or the horse The weight ratio of the quinoneimine-derived copolymer to the film is between 5 and 70%.

An embodiment of the present invention provides a battery comprising: a cathode and an anode; and a film disposed between the cathode and the anode, wherein the film comprises a fluorine-containing polymer, and the following chemical formula (I) Or a maleic acid imide derivative of (II) or a maleic imide derivative copolymer having the following chemical formula (III) and a lanthanide-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof:

Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

Wherein M is available for free radical polymerization of unsaturated monomers, m is between 1 ~ 10,000, n is between ₁ ~ 10,000, X 1 is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide derivative or the horse The weight ratio of the quinoneimine-derived copolymer to the film is between 5 and 70%.

The present invention provides a maleimide-based polymer having an ionic functional group or an ionizable group, which is compatible with a fluorine-containing polymer (for example, PVDF), thereby improving its properties (including: improving conductivity and inhibiting methanol penetration). Degree, enhance antioxidant capacity, etc.). The above composite material can be applied to a fuel cell, and provides a fluorine-based proton exchange membrane with low cost, chemical resistance and high proton conductivity as a key material of the fuel cell.

The copolymerized polymer of the present invention is characterized in that it utilizes a melaimide bond which is chemically stable and which can overcome the hydrolysis problem, and has at least one or more in addition to having an ionic group in the side chain reaction. The side chain or crosslinked melaimide structure is thereby compatible with the blended PVDF to form melaimide-derived polymer/PVDF blending membranes having a heat resistant structure. The invention prepares a series of cross-linked and linear fluorinated proton conductive membranes which are compatible with PVDF and contain ionic groups; or form a Si-O-Si bond by condensation reaction via an amine functional group, A fluorine-containing novel fluorinated novel quinone crosslinked organic/inorganic proton conducting composite membrane containing an ionic group.

The macromolecular structure of the present invention which is compatible with PVDF and has an ionic group can prepare a proton conductive membrane or a composite fluorine-containing proton exchange membrane having low impedance, low film thickness (130 to 100 μm) and high chemical resistance. Different from the shortcomings of the polyimide ionomers thin film technology adopted by most of the existing ones, for example, it is necessary to use high purity, difficult to obtain a large amount of diamine and dianhydride monomer and high molecular weight synthesis conditions and the like, and the characteristics of the present invention are: 1. The polymer structure design can effectively introduce PVDF into the mixed mode, and effectively improve the chemical resistance and physical properties of the polymer film; 2. It can be prepared without good physical properties and high chemical resistance without strict synthesis conditions. The fluorinated proton conductive material avoids complex, time consuming, energy consuming processes such as radiation-grafted membranes.

The above described objects, features and advantages of the present invention will become more apparent and understood.

According to an embodiment of the present invention, there is provided a composition comprising a maleic imide derivative, comprising: a fluorine-containing polymer; and a maleimine derivative having the following chemical formula (I) or (II).

In the chemical formulas (I) and (II), X ₁ may be (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, and B may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

The ionic or ionizable groups possessed on the polymers of the present invention include sulfonated, phosphorylated, carboxylated groups or sulfonyl groups. The ionizable group is a group capable of forming an ionic group such as a thiol, a sulfide, a phosphine, an ester, a cyclic sulfonate, a sultone, an acid anhydride or the like. The ionic group or ionizable group which is present on the polymer of the present invention may be formed by addition reaction of an acid anhydride on a styrene-quinone imide copolymer or a quinone imine polymer with a monomer. The compound is an amine compound such as sodium sulfonate alkylamine, sodium sulfonate aniline, sodium sulfonate phenylalkylamine, sodium sulfonate benzene polyamine, sodium alkylsulfonate aniline, thiol alkylamine, thiol aniline and the like.

In the above composition, the weight ratio of the fluorine-containing polymer to the maleimide derivative is from 5 to 70%, preferably from 5 to 10%.

The above fluorine-containing polymer may include polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE), preferably PVDF.

The above aromatic compounds may include

The above composition further comprises a ruthenium-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof, preferably a ruthenium-based polymer. The lanthanide-containing polymer may include a side-chain branched aminopropyl polydimethylsiloxane or a bis-aminopropyl polydimethylsiloxane in a crosslinked structure. The inorganic oxide may include silica, montmorillonit or laponite. The inorganic acid may include zirconium phosphate or sulfonated silica.

The lanthanide-containing monomer or polymer added to the composition of the present invention can be prepared by a sol-gel method. Its structural feature is a three-dimensional oxane cross-linking structure.

In the above composition, the weight ratio of the maleimide derivative to the ruthenium-containing polymer, the inorganic oxide, the inorganic acid or a mixture thereof is from 1/3 to 1/20.

According to an embodiment of the present invention, there is provided a composition comprising a maleimide-derived copolymer comprising: a fluorine-containing polymer; and a maleimide-derived copolymer having the following chemical formula (III).

In the chemical formula (III), M is an unsaturated monomer which can undergo radical polymerization, m is from 1 to 10,000, n is from 1 to 10,000, and X ₁ is (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH.

In the above composition, the weight ratio of the fluorine-containing polymer to the maleimide-derived copolymer is from 5 to 70%, preferably from 5 to 10%.

The above fluorine-containing polymer may include polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE), preferably PVDF.

The above aromatic compounds may include

The above composition further comprises a ruthenium-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof, preferably a ruthenium-based polymer. The lanthanide-containing polymer may include a side-chain branched aminopropyl polydimethylsiloxane or a bis-aminopropyl polydimethylsiloxane in a crosslinked structure. The inorganic oxide may include silica, montmorillonit or laponite. The inorganic acid may include zirconium phosphate or sulfonated silica.

In the above composition, the weight ratio of the maleimide-derived copolymer to the ruthenium-containing polymer, the inorganic oxide, the inorganic acid or a mixture thereof is from 1/3 to 1/20.

An embodiment of the present invention provides a film comprising: a fluorine-containing polymer; and a maleic imine derivative having the following chemical formula (I) or (II) or a male having the following chemical formula (III) A quinone imine derived copolymer.

In the chemical formulas (I) and (II), X ₁ may be (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, and B may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

In the chemical formula (III), M is an unsaturated monomer which can undergo radical polymerization, m is from 1 to 10,000, n is from 1 to 10,000, and X ₁ is (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH.

In the above film, the weight ratio of the fluorine-containing polymer to the maleimide derivative or the maleimide-derived copolymer is from 5 to 70%, preferably from 5 to 10%.

The above fluorine-containing polymer may include polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE), preferably PVDF.

The above aromatic compounds may include

The above film further comprises a ruthenium-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof, preferably a ruthenium-based polymer. The lanthanide-containing polymer may include a side-chain branched aminopropyl polydimethylsiloxane or a bis-aminopropyl polydimethylsiloxane in a crosslinked structure. The inorganic oxide may include silica, montmorillonit or laponite. The inorganic acid may include zirconium phosphate or sulfonated silica.

In the above film, the weight ratio of the maleimide derivative or the maleimide-derived copolymer to the ruthenium-containing polymer, the inorganic oxide, the inorganic acid or a mixture thereof is from 1/3 to 1/20.

An embodiment of the invention provides a battery comprising: a cathode and an anode; and a film disposed between the cathode and the anode. The above film comprises a fluorine-containing polymer and a maleidinide derivative having the following chemical formula (I) or (II) or a maleic imide derivative copolymer having the following chemical formula (III).

In the chemical formulas (I) and (II), X ₁ may be (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, and B may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

In the chemical formula (III), M is an unsaturated monomer which can undergo radical polymerization, m is from 1 to 10,000, n is from 1 to 10,000, and X ₁ is (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH.

In the above film, the weight ratio of the fluorine-containing polymer to the maleimide derivative or the maleimide-derived copolymer is from 5 to 70%, preferably from 5 to 10%.

The above fluorine-containing polymer may include polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE), preferably PVDF.

The above aromatic compounds may include

The battery may be a fuel cell, and the fuel may be hydrogen or methanol.

An embodiment of the invention provides a battery comprising: a cathode and an anode; and a film disposed between the cathode and the anode. The above film comprises a fluorine-containing polymer, a maleic imine derivative having the following chemical formula (I) or (II) or a maleic imine derivative copolymer having the following chemical formula (III) and a lanthanide-containing copolymer The polymer, inorganic oxide, inorganic acid or a mixture thereof is preferably a ruthenium-based polymer.

In the chemical formulas (I) and (II), X ₁ may be (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, and B may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ ,

In the chemical formula (III), M is an unsaturated monomer which can undergo radical polymerization, m is from 1 to 10,000, n is from 1 to 10,000, and X ₁ is (R ¹ and R ² may be -H, -CH ₃ or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), aromatic compound or polyoxane, A It may be -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH.

In the above film, the weight ratio of the fluorine-containing polymer to the maleimide derivative or the maleimide-derived copolymer is from 5 to 70%, preferably from 5 to 10%.

The above fluorine-containing polymer may include polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE), preferably PVDF.

The above aromatic compounds may include

The above ruthenium-containing polymer may include an aminopropyl polydimethylsiloxane or a bis-aminopropyl polydimethylsiloxane in a crosslinked structure. . The inorganic oxide may include silica, montmorillonit or laponite. The inorganic acid may include zirconium phosphate or sulfonated silica.

In the above film, the weight ratio of the maleimide derivative or the maleimide-derived copolymer to the ruthenium-containing polymer, the inorganic oxide, the inorganic acid or a mixture thereof is from 1/3 to 1/20.

The battery may be a fuel cell, and the fuel may be hydrogen or methanol.

The present invention provides a maleimide-based polymer having an ionic functional group or an ionizable group, which is compatible with a fluorine-containing polymer (for example, PVDF), thereby improving its properties (including: improving conductivity and inhibiting methanol penetration). Degree, enhance antioxidant capacity, etc.). The above composite material can be applied to a fuel cell, and provides a fluorine-based proton exchange membrane with low cost, chemical resistance and high proton conductivity as a key material of the fuel cell.

The copolymerized polymer of the present invention is characterized in that it utilizes a melaimide bond which is chemically stable and which can overcome the hydrolysis problem, and has at least one or more in addition to having an ionic group in the side chain reaction. The side chain or crosslinked melaimide structure is thereby compatible with the blended PVDF to form melaimide-derived polymer/PVDF blending membranes having a heat resistant structure. The invention prepares a series of cross-linked and linear fluorinated proton conductive membranes which are compatible with PVDF and contain ionic groups; or form a Si-O-Si bond by condensation reaction via an amine functional group, A fluorine-containing novel fluorinated novel quinone crosslinked organic/inorganic proton conducting composite membrane containing an ionic group.

The macromolecular structure of the present invention which is compatible with PVDF and has an ionic group can prepare a proton conductive membrane or a composite fluorine-containing proton exchange membrane having low impedance, low film thickness (130 to 100 μm) and high chemical resistance. Different from the shortcomings of the polyimide ionomers thin film technology adopted by most of the existing ones, for example, it is necessary to use high purity, difficult to obtain a large amount of diamine and dianhydride monomer and high molecular weight synthesis conditions and the like, and the characteristics of the present invention are: 1. The polymer structure design can effectively introduce PVDF into the mixed mode, and effectively improve the chemical resistance and physical properties of the polymer film; 2. It can be prepared without good physical properties and high chemical resistance without strict synthesis conditions. The fluorinated proton conductive material avoids complex, time consuming, energy consuming processes such as radiation-grafted membranes.

[Examples] [Example 1]

In a single-necked reaction flask, 4 g of sodium hydroxide was dissolved in 20 ml of water, and 12.49 g of 2-aminoethanesulfonic acid (AESA) was added thereto, and the mixture was reacted at 60 ° C for 3 hours. Most of the water was removed by a rotary evaporator, and dried in a vacuum oven at 80 ° C for 24 hours to obtain a sodium 2-aminoethanesulfonate (SAES) powder.

[Comparative Example 1] Preparation of polystyrene-maleic anhydride polymer film

In a two-necked round neck flask, 5 g of dry polystyrene-maleic anhydride polymer (styrene: maleic anhydride = 1:1) and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use) were placed. , dissolved by magnet stirring. Take 1.67 g of SAES and 5.73 g of bis-aminopropyl polydimethylsiloxane (X-22; molecular weight 900), dissolve in 90 ml of dimethyl hydrazine (dehydrated with calcium hydride before use), and warm to 70 ° C. After the magnet was thoroughly stirred to completely dissolve, the solution of the conical flask was poured into a two-necked round neck flask and reacted at a temperature of 80 ° C for 1 hour. The appropriate amount of the solution in the two-necked round neck flask was placed in an aluminum dish at a temperature of 60 ° C for 10 hours in an oven. After the film formation, the film was placed in a vacuum oven at 120 ° C for 12 hours, and then subjected to a thermal ring closure reaction in a vacuum oven at a temperature of 200 ° C for 48 hours to complete the polystyrene-maleic anhydride containing in this example. Preparation of molecular films.

[Example 2] Preparation of Polystyrene-Maleic Anhydride Polymer Film (5% PVDF) of the Invention (1)

In a two-necked round neck flask, 5 g of dry polystyrene-maleic anhydride polymer (styrene: maleic anhydride = 1:1) and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use) were placed. , dissolved by magnet stirring. Take 1.67 g of SAES and 5.73 g of X-22, dissolve in 90 ml of dimethylarylene (dehydrated with calcium hydride before use), and pour into a two-necked round neck flask at a temperature of 80 ° C. 1 hour. After the reaction, a PVDF solution was further added to the two-necked round neck flask, and the blending ratio was adjusted to 5%. Film was formed in an aluminum dish, and the temperature was 60 ° C in an oven. After 10 hours, the film was placed in a vacuum oven at 120 ° C, water was removed for 12 hours, and then subjected to a thermal closed-loop reaction in a vacuum oven at a temperature of 200 ° C for 48 hours. That is, the preparation of the polystyrene-maleic anhydride polymer film of the present embodiment is completed.

[Example 3] Preparation of Polystyrene-Maleic Anhydride Polymer Film (10% PVDF) of the Invention (2)

In a two-necked round neck flask, 5 g of dry polystyrene-maleic anhydride polymer (styrene: maleic anhydride = 1:1) and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use) were placed. , dissolved by magnet stirring. Take 1.67 g of SAES and 5.73 g of X-22, dissolve in 90 ml of dimethylarylene (dehydrated with calcium hydride before use), and pour into a two-necked round neck flask at a temperature of 80 ° C. 1 hour. After the reaction, a PVDF solution was further added to the two-necked round neck flask, and the blending ratio was adjusted to 10%. Film was formed in an aluminum dish, and the temperature was 60 ° C in an oven. After 10 hours, the film was placed in a vacuum oven at 120 ° C, water was removed for 12 hours, and then subjected to a thermal closed-loop reaction in a vacuum oven at a temperature of 200 ° C for 48 hours. That is, the preparation of the polystyrene-maleic anhydride polymer film of the present embodiment is completed.

[Embodiment 4] Preparation of polystyrene-maleic anhydride polymer film (70% PVDF) of the invention (3)

In a two-necked round neck flask, 5 g of dry polystyrene-maleic anhydride polymer (styrene: maleic anhydride = 1:1) and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use) were placed. , dissolved by magnet stirring. Take 1.67 g of SAES and 5.73 g of X-22, dissolve in 90 ml of dimethylarylene (dehydrated with calcium hydride before use), and pour into a two-necked round neck flask at a temperature of 80 ° C. 1 hour. After the reaction, a PVDF solution was further added to a two-necked round neck flask, and the blending ratio was adjusted to 70%. Film was formed in an aluminum dish, and the temperature was 60 ° C in an oven. After 10 hours, the film was placed in a vacuum oven at 120 ° C, water was removed for 12 hours, and then subjected to a thermal closed-loop reaction in a vacuum oven at a temperature of 200 ° C for 48 hours. That is, the preparation of the polystyrene-maleic anhydride polymer film of the present embodiment is completed.

[Embodiment 5] guide Measurement of electricity and water content

After proton exchange, the film was sandwiched between stainless steel electrodes, the electrode length was 3 cm, and the electrodes were fixed by 1 cm. The impedance of the film was measured by an AC impedance analyzer (CH Instrument model 604A), and the film was calculated by the following formula. Proton conductivity:

σ is the proton conductivity (S/cm); l is the electrode distance fixed to 1 cm; R is the impedance value; A is the proton conduction area = film thickness × 3 cm.

Moisture content is to soak the film in water, after completely moisturizing, remove the residual water on the surface of the film, measure the weight of the film, and calculate the moisture content = (wet film weight - dry film weight) / wet film Heavy, as shown in Table 1.

[Embodiment 6] Test of chemical resistance and mechanical strength

The oxidative stability test method of the film is as follows: the sample is immersed in Fenton's reagent (2 ppm FeSO ₄ in 3% hydrogen peroxide), heated to 80 ° C, and held for one hour, and the weight change of the sample before and after the reaction is measured, and the residual amount is high. The film has better chemical resistance. It can be seen from Table 2 that the film blended with PVDF has better oxidation stability than the unblended film.

The film was subjected to mechanical strength test by a tensile tester, and the maximum stress (MPa) and Young Modulus (GPa) data are shown in Table 2.

[Embodiment 7] Direct methanol fuel cell single cell test

The above film was separately fabricated into a membrane electrode unit cell, and the performance of the methanol fuel cell unit was tested at 60 °C. E-TEK PtRu/C (Pt content 20 wt%) was used for the anode, and E-TEK Pt/C catalyst (Pt content 20 wt%) was used for the cathode. The amount of the anion and anode catalyst coating was 2 mg Pt/cm ² , and the area of the catalyst layer was 5 cm ² . The anode feed was a 2.0 M aqueous methanol solution with a feed rate of 2 ml/min. The cathode feed was oxygen at a feed rate of 100 ml/min. Figure 1 is a graph of the test results for a methanol fuel cell single cell, including current density versus potential, and current density versus power density. It can be seen from Fig. 1 that the film properties of Example 3 have the best performance.

[Embodiment 8] Test compatible with PVDF blending

The compatibility of the composite polymer membrane of the present invention with PVDF was tested by XRD (Fig. 2) and DSC (Fig. 3), respectively. It can be seen from Fig. 2 and Fig. 3 that the film of the system and the PVDF can reduce the crystallinity of the PVDF and decrease the endothermic peak of the melting point, which proves that the compatibility is good.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the invention may be modified and retouched without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

1 is a polarization curve and power density of a methanol fuel cell single cell test in accordance with an embodiment of the present invention.

Figure 2 is a graph showing the results of proton conducting polymeric XRD mixed with PVDF according to an embodiment of the present invention.

Figure 3 is a graph showing the results of a proton-conducting polymer DSC blended with PVDF according to an embodiment of the present invention.

Claims (33)

A composition comprising a maleic imine derivative, comprising: a fluorine-containing polymer; and a maleimine derivative having the following chemical formula (I) or (II): Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ , Wherein the weight ratio of the fluorine-containing polymer to the maleimide derivative in the composition is from 5 to 70%. The composition containing the maleic imine derivative according to claim 1, wherein the fluorine-containing polymer comprises polyvinylidene fluoride (PVDF) and perfluorosulfonic acid (PFSA). Or polytetrafluoroethene (PTFE). A composition comprising a maleic imine derivative according to claim 1, wherein the aromatic compound comprises The composition containing the maleic imine derivative according to claim 1, wherein the weight ratio of the fluorine-containing polymer to the maleimide derivative in the composition is between 5 and 10 %. The composition containing the maleic imine derivative as described in claim 1, further comprising a lanthanide-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof. The composition containing a maleic imine derivative according to claim 5, wherein the lanthanoid-containing polymer comprises a side-chain branched aminopropyl polydimethylsiloxane or Bis-aminopropyl polydimethylsiloxane in the structure. A composition comprising a maleic imide derivative according to claim 5, wherein the inorganic oxide comprises silica, montmorillonit or laponite. A composition comprising a maleic imide derivative according to claim 5, wherein the inorganic acid comprises zirconium phosphate or sulfonated silica. The composition containing a maleic imine derivative according to claim 5, wherein the maleimide derivative and the lanthanoid-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof are used in the The weight ratio in the composition is between 1/3 and 1/20. A composition comprising a maleimide-derived copolymer comprising: a fluoropolymer; and a maleimide-derived copolymer having the following chemical formula (III): Where M is an unsaturated monomer capable of free radical polymerization, m is between 1 and 10,000, n is between 1 and 10,000, and X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide-derived copolymer are The weight ratio in the composition is between 5 and 70%. The composition containing the maleic imine-derived copolymer according to claim 10, wherein the fluorine-containing polymer comprises polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA). Or polytetrafluoroethene (PTFE). A composition comprising a maleimide-derived copolymer as described in claim 10, wherein the aromatic compound comprises The composition comprising the maleic imide-derived copolymer according to claim 10, wherein the weight ratio of the fluorine-containing polymer to the maleimide-derived copolymer in the composition is between 5 -10%. A composition comprising a maleic imide-derived copolymer as described in claim 10, further comprising a lanthanide-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof. The composition comprising a maleic imide-derived copolymer according to claim 14, wherein the lanthanide-containing polymer comprises a side-chain branched aminopropyl polydimethylsiloxane or Bis-aminopropyl polydimethylsiloxane in the crosslinked structure. A composition comprising a maleic imide-derived copolymer as described in claim 14, wherein the inorganic oxide comprises silica, montmorillonit or laponite. A composition comprising a maleic imide-derived copolymer as described in claim 14, wherein the inorganic acid comprises zirconium phosphate or sulfonated silica. The composition comprising a maleic imide-derived copolymer according to claim 14, wherein the maleimide-derived copolymer and the ruthenium-containing polymer, inorganic oxide, inorganic acid or a mixture thereof The weight ratio in the composition is between 1/3 and 1/20. A film comprising: a fluorine-containing polymer; and a maleic imine derivative having the following chemical formula (I) or (II) or a maleated imine derivative copolymer having the following chemical formula (III): Where X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, B is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , - PO ₃ H ₂ , -PO ₄ H ₂ , -COOH, -H, -CH ₃ , Where M is an unsaturated monomer capable of free radical polymerization, m is between 1 and 10,000, n is between 1 and 10,000, and X ₁ is (R ¹ and R ² are -H, -CH ₃ or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane, and A Is -SO ₃ H, -SO ₂ H, -SO ₃ H ₂ , -PO ₃ H ₂ , -PO ₄ H ₂ or -COOH, wherein the fluorine-containing polymer and the maleimide derivative or the horse The weight ratio of the quinoneimine-derived copolymer to the film is between 5 and 70%. The film according to claim 19, wherein the fluorine-containing polymer comprises polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA) or polytetrafluoroethene (PTFE). . The film of claim 19, wherein the aromatic compound comprises The film of claim 19, wherein the fluoropolymer and the maleimide derivative or the maleimide-derived copolymer are in a weight ratio of 5-10% in the film. . The film of claim 19, further comprising a lanthanide-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof. The film of claim 23, wherein the lanthanide-containing polymer comprises a side-chain branched aminopropyl polydimethylsiloxane or a cross-linked structure of di-aminopropyl poly Bis-aminopropyl polydimethylsiloxane. The film of claim 23, wherein the inorganic oxide comprises silica, montmorillonit or laponite. The film of claim 23, wherein the inorganic acid comprises zirconium phosphate or sulfonated silica. The film of claim 23, wherein the maleic imide derivative or the maleimide-derived copolymer and the lanthanoid-containing polymer, inorganic oxide, inorganic acid or a mixture thereof are used in the film The weight ratio in the film is between 1/3 and 1/20. A battery comprising: a cathode and an anode; and a film as described in claim 19, disposed between the cathode and the anode. The battery of claim 28, wherein the battery is a fuel cell. The battery of claim 29, wherein the fuel of the fuel cell is hydrogen or methanol. A battery comprising: a cathode and an anode; and a film as described in claim 23, disposed between the cathode and the anode. The battery of claim 31, wherein the battery is a fuel cell. The battery of claim 32, wherein the fuel of the fuel cell is hydrogen or methanol.