TW201136953A - Maleimide derivatives, maleimide-derived copolymers and compositions, films and cells comprising the derivatives or copolymers - Google Patents

Abstract

A maleimide derivative of Formula (I) or (II) is provided. In Formula (I), X1 is, (R1 and R2 are -H, -CH3 or -F, p is 1-20, q is 1-100, a is 1-6), aromatic compounds or polysiloxane, and A is -SO3H, -SO2H, -SO3H2, -PO3H2, -PO4H2 or -COOH. In Formula (II), X1 is, (R1 and R2 are -H, -CH3 or -F, p is 1-20, q is 1-100, a is 1-6), aromatic compounds or polysiloxane, and B is -SO3H, -SO2H, -SO3H2, -PO3H2, -PO4H2, -COOH, -H, -CH3, or. A maleimide-derived copolymer of Formula (III) is provided. In Formula (III), M is an unstaturated monomer capable of radical polymerization, m is 1-10000, n is 1-10000, X1 is, (R1 and R2 are -H, -CH3 or -F, p is 1-20, q is 1-100, a is 1-6), aromatic compounds or polysiloxane, and A is -SO3H, -SO2H, -SO3H2, -PO3H2, -PO4H2 or -COOH. The invention also provides a composition, film and cell including the maleimide derivative or the maleimide-derived copolymer.

Description

201136953 VI. Description of the Invention: [Technical Field] The present invention relates to a copolymer, in particular to a maleic imide derivative, a maleimide-derived copolymer, and a derivative or copolymer thereof Composition, film and battery. [Prior Art] Solid polymer proton conducting membranes are widely used in various electrochemical components such as fuel cells, lithium ion secondary batteries, sensors, etc., among them, Polymer Electrolyte Membrane Fuel Cell (PEMFC) Recently, it has received much attention because it is a conversion system for renewable energy. The macromolecular proton conducting membrane is an acidic solid electrolyte. The main function is to prevent the direct contact between the two poles and cause the short circuit. In addition to the direct contact between the two poles, the anode reacts to generate a proton through the cathode to combine with oxygen to complete the reaction. , so that the electrons pass by the external line. At present, the most practical fuel cell proton conducting membrane is a perfluoro-substituted polymer copolymer (PFSA) containing a repeating acid group. Its proton conductivity is 0.01 S/Sm, but the current price is still very expensive and hinders. Large-scale application of products. At present, the biggest problem with the use of proton conductive membranes in PEMFC is water management. Hydrogen ions are 〆 naked protons. Because of their lack of charge to shield the nucleus, protons easily interact with their surrounding nucleophilic substances (such as water), forming a cluster, allowing protons to proceed in the channels formed by water. = Transfer, therefore, when the temperature is close to the boiling point of water, PEVI will lose water: Proton conductivity is reduced, which reduces the efficiency of p£MFc, which is one of the important reasons for the use of water. However, the material characteristics of PFSA still have the disadvantages of 9085-A51585-TW η 201136953: (1) When the temperature exceeds 15〇〇c, the toxicity and corrosion caused by the gas generated by cracking must be considered; (7) The properties of PFSA film are lowered due to high temperature. For example, when the proton conductivity is reduced to 1/10 at 60 °C at 8 °C, the mechanical strong sound is sharply reduced; (7) due to the high temperature and easy water loss characteristics, it is necessary to scale the extra equipment during the jump operation. Such as humidification systems, etc., and increase the considerable cost;, (4) the cost of this material is too high and only a few suppliers,% Μ (10), A coffee Chemical and other companies. Because of the company, it is expected to be used in fuel cellization or in the production of proton conductivity. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Sulfonated polystyrene;:: = 2 = National Patent No. 13 (10) No. 4 - Polyphenylene: Ion :::, the components are made of impregnated, mixed dosing to make a composite material, ^ Conducting the southern molecule or using inorganic acid Proton conduction water content M59, 943, 45th to 6,716, state number, the first object to the eighth; &amp; 4,, 唬). However, this method is still difficult, because the helmet heat color is limited, The polymer is only used as a matrix: angle, slightly. TW. There is a sub-thermal bond between the polymers, so the polymer still has the problem of 201136953 in high temperature environment. There are many methods that have been proposed to overcome these difficulties, such as the use of U Honma Various hydrolyzable a] k〇xyaikyhiiane and solid, ready-time oxygen cross-linked structure · Qian F sub-materials (US Patent No. 6,680, No. 38), although this material has good proton transfer at high temperatures', but after the film is formed, cracks are easily generated and it is difficult to make a test, and when the water content is When there is a high temperature, there will be a problem of dissolution. ... Therefore, 'development--a low cost can be applied to the chaotic system in the fuel cell, the conductive film, and the introduction of inorganic substances to form an organic-inorganic composite material, which is a technology in this field. [Effect of the Invention] - An embodiment of the present invention provides a horse (tetra)imine derivative having the following chemical formula (I) or (n): /,

A (I) where X is the ten r1rV card ci2HVaj "(R, and ^ TT and is: CH3 or -F, P is between 1 and 20, q is between 1 and 1 〇., a is between 1 and 6) , an aromatic compound or polyoxyalkylene; and A is, s〇3H, __s〇, h, _SC&gt; 3H2, 4〇3H2, -P〇4H2 or -COOH.

9085-A51585-TW 9 201136953

(Π) -fCR1R2)- f 〒2Ht〇1i~ where X] is P, R (R1 and R2 are -H, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a 1 to 6), aromatic compound or polyoxo-oxygen; and B is -SO3H, -SO2H, uu

In one embodiment of the present invention, there is provided a maleimide-derived copolymer having the following chemical formula (III): 9085-A51585-TW 10 (III) 201136953

A wherein M is a non-planar monomer capable of radical polymerization; m is between 1 and 10000; η is between iqoooo; &amp; is -fCR1R2·)^- -ChH-〇. (R and R are ·Η, - CH3 or -F, p between 1 and 20 at 1 to 100, a between 1 and 6), aromatic or polyoxo, and A is _Sq3H, _s〇2H, 初, 1, or - COOH. 4h2 - An embodiment of the present invention provides a composition of the following formula (1) or (8), which is derived from a maleimine derivative, a formula (I is a maleimide-derived copolymer; and - an inorganic oxidation) , inorganic acid or a mixture thereof. ', person', u

9085-A51585-TW

II 201136953 —fCR1R2)—where X; is P ,

Is -Η, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxyalkylene; and A is -S03H, -S02H, -S03H2, -Ρ03Η2, -P〇4H2 or -COOH. 〇

OH

HijJ where X; is

B (II) -fCR1R2^-, -ch4-o-

R 2 a q

(R1 and IT are -H, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxane; and B is -S03H , -S〇2H,

-S03H2, -P03H2, -P04H2, -COOH, -Η, _CH3,

OH HN o or 9085-A51585-TW 12 201136953

A (III) wherein M is free radical polymerization and monomer; m is between -fCR1R2Ji-

1~10 0 0 0 ; η between CH

10000 ; X! is R (R4 R2 is -H, -CH3 or _F, p is between '~20: q between woo' a between"), aromatic compound or poly-stone oxy- ing and Α -SO3H, -SO2H, p or -COOH. 2 °3^2 ' -P〇4H2

According to an embodiment of the present invention, there is provided a hafnium imine derivative of the formula (1) or (n): a maleimide-derived copolymer having the following formula (III). 2 one has the following chemistry

9085-A51585-TW 13 201136953 -fCR1R2V, CH- I &gt;2 'a 〇- where X] is ' , FT (R1 and R' are -H, -CH3 or -F, p is between 1 and 20, q Between 1 and 100, a between 1 and 6), an aromatic compound or polyoxyalkylene; and A is -S〇3H, -S02H, -S〇3H2, -P03H2, -Ρ04Η2 or -COOH.

(II) where Xi is —(-CR1R2)^- -ch-H-o-

R 2 aq (R1 and R' are -H, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or polyoxyalkylene; B is -S〇3H, -S02H, -so3h2, -po3h2, -po4h2

9085-A51585-TW 14 201136953

A (III)

Wherein] Vi 1~10000 fCH-^ is a free-spinning unsaturated monomer 'a n between 〇-40000; X] is —(:CR1R2

At 19 9 and R is 屯, _CH3 or -F, ρ8 1~2〇, q is between 1 and 1 p, p is 帛p. ; 丨1~6), aromatic compound is reduced, and Α is _S〇3H, _s〇h ϋ石夕 or -COOH. 2 s〇3h2 ^po3h2 ^p〇4H2

According to still another embodiment of the present invention, there is provided a film comprising: a composition comprising a maleimide derivative having the following chemical formula (1) or (9) or a horse having the following chemical formula (m) The quinone imine-derived copolymer is combined with a 5-fold polymer, an inorganic oxide, an inorganic acid or a mixture thereof.

A (I) 9085-A5I585-TW 15 201136953 where: &gt;&lt;〇 is -cr1rV heart CH-f-0- aq (R1 and R' are -Η, -CH3 or -F, p is between 1 and 20 , q is between 1 and 100, a is between 1 and 6), an aromatic compound or polyoxyalkylene; and A is -S03H, -S02H, -so3h2, -po3h2, -po4h2 or -COOH.

(II) -fCR1R2)^ -CHH—O- &gt;2 'aq where X is , 'P , (R1 and R2 are -H, -CH3 or -F, p is between 1 and 20, q is between 1 ~100, a between 6), aromatic compounds or polyoxyalkylene; and B is -S03H, -S02H, uu

-so3h2, -po3h2, -po4h2 / Η Η \

OH HN or o 9085-A51585-TW 16 (III) 201136953

/, 4 can be free radical polymerization of unsaturated monomers; m between 1 ~ 10000; n between L00; χ] is a fCR1R2 ^ _ - 10 9 〇 -, know aq (R and R are - Η, -CH3 or, p is between ^20, q is between 1 and 100, a is between 1 and 6), aromatic or polyoxyalkylene; and A is -S03H, -S02H, -S03H2, -P〇3h2 , ·Ρ〇4Η2 or -CO〇H. 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 Malayan having the following chemical formula (1) or (11) An imine derivative or a maleidene-derived copolymer having the following chemical formula (III).

A (I) 9085-A51585-TW 17 201136953 where χ is -fCR1R2^-, -ch4—〇· aq (R1 and R: are -H, -CH3 or -F, p is between 1 and 20, q 1 to 100, a between 1 and 6), an aromatic compound or polyoxyalkylene; and A is -S03H, -S02H, -S03H2, _Ρ03Η2, -Ρ04Η2 or -COOH.

(Π) -^CR1R2^^ -CH-VO- &gt;2 fa q where X is, 'p, R&quot; (R1 and R' are -H, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), an aromatic compound or polyoxyalkylene; and B is -S03H, -S02H,

-S〇3H2, -P03H2, -P04H2, -COOH, -Η, -CH3, or

OH HN o 9085-A51585-TW 18 (III) 201136953

1~10000; η is between 1~10〇〇〇r2 (r1 and R2 are -Η, γη { ·ρ 2 垸; " and Α is -S〇3H, ·%Η, .s〇3H2, pg II 2 or -COOH. 'ΌαΚ An embodiment of the present invention provides a battery comprising: - an anode; and - a film disposed between the cathode and the anode, the composition comprising the composition comprising The following chemical or (in) horse (iv) imine derivatives or - an imine-derived copolymer having the following chemical formula (IV) and - containing a Schiffy polymer, an inorganic oxide acid or a mixture thereof.

201136953 Its (4), temporary 〇 - (R) and R / is -Η, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), aromatic compounds or Polyoxyalkylene; and A is -S03H, -S02H, -so3h2, -po3h2, -po4h2 or -COOH.

(II) ('Cr'r2·)— 12 aq where X] is P, R (R1 is -H, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 to 6), an aromatic compound or polyoxyalkylene; and B is -S03H, -S〇2H,

-S03H2, -P03H2, -P04H2, -COOH, -Η,

9085-A51585-TW 20 201136953

(III)

1~10000 fCH- two°" unsaturated monomer for radical polymerization, flat limb, m between 11] between 1 and 10000; X is for; a Ό q (R1 and R2 are -Η, -CH3 or _F, 1~20, q between 1~Ρ between di, 3 between 1 and 6), aromatic compound ^ milk system, and ΑS_3〇, -s〇2H, _ commit 2 or Ju Shi Xi or -COOH.汨2, -Ρ〇4Η2

In order to achieve the above object of the present invention, only the following description of the preferred embodiments will be described as follows: Features and advantages can be more apparent and can be combined with the drawings, and the details are made.

An embodiment of the present invention provides a maleic imine derivative having the following chemical formula (I) or (II). 9085-A51585-TW 21 201136953

A (I) ~(-CR^R2·)— In the chemical formula (1), X〗 can be p ,

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. A can be -S03H, -S02H, -S03H2, -P〇3H2, -Ρ04Η2 or -COOH.

(II) —(-CR1R2·)— In the chemical formula (π), x can be p ,

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. B can be -S03H, -S02H, -S03H2, -Ρ03Η2, -Ρ04Η2, 9085-A51585-TW 22 201136953

According to an embodiment of the present invention, there is provided a method of derivatization of a mixture of the following formula (III).

(III) In the chemical formula (III), hydrazine may be an unsaturated monomer which can undergo radical polymerization. m is between 1 and 10,000. η is between ΚΚΚΚΚ). Χι can be -CH4-0- 'a -fCR1R2-)- ^ PR (R1 and R2 can be -H, -CH3 or -F, P is between 1 and 20, q is between i~1〇〇, a A, an aromatic compound or a polyoxyalkylene. A may be -S〇3H, _s〇2H, _s〇3H2, _P〇3il2, -P〇4h2 or -COOH.

The above aromatic compound may include or.

The present invention provides a maleic imine polymer having at least an ionic group or an ionizable group (for example, a sulfonic acid group) (for example, styrene·Malay 9085-A51585-TW 23 201136953 imine::two Or a maleidinide polymer) as a polymer electrolyte. ^], the ionizable group of the present invention

Also includes thiol, larva k F; IL, phosphine, ester, ring sulfonate, sulfonate liver, d 'utilization of styrene-based maleic anhydride copolymer on the reaction To form a styrene maleimide copolymer having at least an ionic group or a conventional ionized group of the present invention. ^In the case of 'utilization—anhydride group on a maleic anhydride polymer

The reaction is carried out to form a maleimide polymer of the invention having at least an ionic or ionizable group. / In the examples, the styrene-maleic anhydride copolymer and the maleic acid 5 may be copolymers, terpolymers or ruthenium polymers. An embodiment of the present invention provides a combination of a maleic imide derivative of the formula (1)_) or a maleic amine-derived copolymer of the following formula: = 匕 = organic acid or a mixture thereof. The above-mentioned cleavage polymerization "the organic compound, the inorganic acid or a mixture thereof is preferably selected as a cleavage polymer =

9085-A5J585-TW 24 201136953 —fCR1R2^— In chemical formula (I), X! can be P,

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. A can be -S03H, -S02H, -S〇3H2, -Ρ03Η2, -Ρ04Η2 or -COOH.

(Π) -fCR1R2·^ In the chemical formula (π), x] can be ρ ,

R (R) and R2 may be -Η, -CH3 or -F, ρ is from 1 to 20, q is from 丨 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. B can be -S03H, -S02H, -S03H2, -Ρ03Η2, -Ρ04Η2, -C〇OH, -H, -CH3,

9085-A51585-TW 25

(Ill) In the chemical formula (m), M may be a monomer which can be subjected to radical polymerization and a monomer. m is between 1 and 10,000. η is between 1 and 10,000. X] can be (R1 and R2 can be -H, -CH. -(&quot;CR1R2)^, or -F, p is between 1 and 20, q is between 1 and 100 'a between 1 and 6), An aromatic compound or polyoxyalkylene. A can be -S03H, -S02H, -Ρ03Η2, -P〇4H2 or -COOH.

The above aromatic compounds may include

The above ruthenium-containing polymer may include aminopropy 1 polydimethylsiloxane or a bis-aminopropyl poly decyl oxime in a crosslinked structure (bis_amin〇pr〇) State polydimethylsiloxane). The above inorganic oxide may include silica, montmorillonit or pyrophene. The above inorganic acid may include zirconium phosphate or sulfonated silica.

The ratio of the upper lanthanide-containing polymer, the inorganic oxide, the inorganic acid or a mixture thereof to the maleidinide derivative or the maleic imide-derived copolymer may be eight 9085-A515S5-TW 26 201136953 in 1/3~ 1/20 (weight ratio). The above-described maleic imine derivative or maleimide-derived copolymer may be physically or with a monomer containing a lanthanoid polymer, an inorganic oxide, an inorganic acid or a mixture thereof or a functional group having any form compatible therewith Chemically attaching, for example, an addition reaction with an anhydride group on a styrene-maleic anhydride copolymer or a maleic anhydride polymer to form a chemical bond with a lanthanide-containing polymer or monomer, for example, with an alkane An amine, an alkanediamine, a polyetheretheramine, a polyetheretheramine, an aniline, an alkylaniline, a benzoquinoneamine, a polyamidamine, a polyphenylenediamine, or an amine group containing a broken hydrocarbon amine such as aminopropyltriethoxysilane The compound forms a chemical bond. The above-mentioned monomer attached to the maleidinide derivative or the maleic imide-derived copolymer may be an amine-based compound such as sodium nitrite, sodium sulfonate, sodium phenyl sulfonate, sulfonate. Sodium phenylpolyamine, sodium alkyl sulfonate aniline, thiol alkylamine or thiol aniline. By appropriately adjusting the proportion of the crosslinked structure formed after the attachment, the mechanical properties and hydraulic properties of the copolymer as a whole can be improved. The above-mentioned maleimide-derived copolymer containing a lanthanoid monomer or polymer can be prepared by a sol-gel method, and the structure is characterized by a crosslinked structure of a decane having a three-dimensional space. According to an embodiment of the present invention, there is provided a film comprising a maleic imine derivative having the following formula (I) or (II) or a maleic amine-derived copolymer having the following formula (III).

9085-A51585-TW (i) 201136953

—fCR1R2|— In chemical formula (I), X! can be P,

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. A can be -S03H, -S02H, -S03H2, -Ρ03Η2, -Ρ04Η2 or -COOH.

(II) —(-CR1R2}-

In chemical formula (II), X can be P

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from -1 to 100, a is from 1 to 6), an aromatic compound or polyoxyalkylene. B can be -S〇3H, -S02H, -S〇3H2, -P〇3H2, -Ρ04Η2, 9085-A51585-TW 28 201136953

-COOH -Η, -CH-

monomer. =::: can be (III) - fCR1R2^ - q ^ v (R and r2 can be -H, -CH3" 'P'i is between 1 and 20, q is between Hoo'a and oxygen. A can be __, 曰, -p〇3H2, _p〇4H2 or _C00H. S〇3il2 Taishufang 族族1 can include cH2 points, heart. 〇_ f \Ming Tao version can be used as a proton A conductive membrane (proton transfe), which is used in, for example, a fuel cell battery cell. In one embodiment of the present invention, an i scoop is provided to a single species, including a composition, a _&gt; VIII have the following formula (1) or 1) of the maleidin derivative or

90S5-A5I585-TW 29 201136953

- Malay-derived copolymerized polymer having the following chemical formula, no money, inorganic IW. 〃 W

R2 H (R) and R2 can be ^^ ^ 1~20, q between 1~1〇〇, &amp; 八~马Ή, &lt;Η3 or _F,p is in the oxygen hospital. A can be like 3H , a_== aromatic compound or poly-stone or -COOH. 3H2, 4&gt; 〇3H2, _p〇4H2

In the chemical formula (Π), Xl can be ten RlRf

9085-A51585-TW 30 201136953

(R) and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. B can be -S03H, -S〇2H, -S〇3H2, -Ρ03Η2, -Ρ04Η2

-COOH, -Η, -CH3,

(HI) In the chemical formula (III), M may be an unsaturated monomer which can undergo radical polymerization. m is between 1 and 10,000. η is between 1 and 10,000. X] can be ^CR1R2f- P, R (R) and R2 can be _H, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6 and aromatic. a compound or polyoxyalkylene. A can be -S03H, -S02H, -S03H2, -P〇3H2, -P〇4H2 or -COOH.

The above aromatic compounds may include

9085-A51585-TW 31 201136953 The upper yttrium-containing polymer may comprise an aminopropyl polycJimethylsiloxane or a bis-aminopropyl polydiphenyl group in a crosslinked structure. BiS-aminopropyi polydimethylsiloxane. The above inorganic oxide may include silica, montmorillonit or iaponite. The above inorganic acid may include zirconium ph〇sphate or sulfonated silica. The ratio of the above ruthenium-containing polymer, inorganic oxide, inorganic acid or a mixture thereof to a maleidinide derivative or a maleimide-derived copolymer may be from 1/3 to 1/20 (by weight). The film of the present invention can be applied to a battery element such as a fuel cell as a proton conductive film (such as a known membrane). The polymer material selected for the proton conducting membrane of the present invention is inexpensive, and is easier to manufacture and use than the conventional perfluoropolymer. In an embodiment of the invention, a battery is provided comprising a cathode disk and an anode, and a film disposed between the cathode and the anode. The above film comprises a maleic imine derivative having the following chemical formula (I) or (II) or a maleic imide derivative copolymer having the following chemical formula (III). ’,

A (I)

9085-A51585-TW 201136953 -(&quot;CR1R2-) - In the chemical formula (I), X] can be p,

(R1 and R2 may be -Η, -CH3 or -F, p is from 1 to 20, q is from 1 to 100, a is from 1 to 6), an aromatic compound or a polyoxyalkylene. A can be -S03H, -S02H, -S03H2, -Ρ03Η2, -Ρ04Η2 or -COOH.

In the chemical formula (π), X can be -^r1r2)T,

(R) and R2 may be -Η, -CH3 or -F, p is -COOH, 1~2 0, q is between 1 and 10 0, a is between 1 and 6), aromatic compound or polylithic Oxytomane. B can be -S03H, -S02H, -S03H2, -Ρ03Η2, -Ρ04Η2, H, -CH3

9085-A51585-TW 33 (III) 201136953

In the chemical formula (III), M may be an unsaturated monomer which can undergo radical polymerization. m is between 丨~1〇〇〇〇°η! ~1_. &amp; can be -fCR1R2^ - 'a 〇Η+-〇-, (R1 and R2 can be -H, -CH3 or: ' Ρ between 1~20 ' q between 1~10〇, a between 1 ~6), aromatized or poly-stone. A can be anything else, %%, _s〇, -P03H2, -P〇4h2 or _c〇〇H. The aryl fluoride compound may include a mernt Γ film which can be applied to a battery element such as a fuel cell as a -f sub-conductor. alcohol. The present invention may be a fuel cell, which may use hydrogen or a ruthenium anode, as an embodiment, providing a battery comprising a cathode and a film disposed between the cathode and the anode. Derivatives or - have the following: a heart: a corpse) and a "manganese-derived copolymer", an imine-derived copolymerization σ, an oxime emulsion, an inorganic acid or a mixture thereof.

9085-A51585-TW 201136953

—fCR1R2- In Chemical Formula (1), Xi can be 'aq R (R1 and R2 can be -Η, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, and a is between 1 and 6) , an aromatic compound or polyoxetane. A can be -S〇3H, _S02H, -S03H2, -Ρ03Η2, -P〇4H2 or -COOH.

〇 Hrsi

B (II) —(-CR1R2- In the chemical formula (II), Xi can be R (R) and R2 can be -H, -CH3 or -F, p is between 1 and 2 0, and q is between 1 and 1. 0 0, a between 1 and 6), aromatic compound or polylithic 9085-A51585-TW 35 201136953 oxane. B can be _s〇3H, -S〇2h

-COOH -H, -CH3, -S〇3H2, _P〇3H2, -P〇4h

In the chemical formula (III), M can be an unsaturated precursor which can promote the radical polymerization of ή丄 j. Hey! It’s between 1-1000. The median [ n ) is between 1 and 10,000. X] can be

R 2 3 —fCR1R2-)—(R) and R2 may be _H, -ch3 or -F, P is between (4), q is between (10), &amp; is between (a), aromatic or polyoxyalkylene A can be _s〇3H, _s〇2H, _s〇3^, '-Ρ03Η2, -P〇4h2 or -COOH.

The above ruthenium-containing polymer may include aminopropyl po ydimethylsiloxane of a side chain or a bis-aminopropyl bis-aminopropyl of a crosslinked structure. 9085-A515S5-TW 36 201136953 polydimethylsiloxane). The inorganic oxide may include silica, montmorillonit or laponite. The above inorganic acid may include zirconium phosphate or sulfonated silica. The ratio of the above-mentioned ε-based polymer, inorganic oxide, inorganic acid or a mixture thereof to a maleimide derivative or a maleimide-derived copolymer may be between 1/3 and 1/20 (weight ratio) ). The film of the present invention can be applied to a battery element such as a fuel cell as a proton transfer φ membrane. The battery of the present invention may be a fuel cell, and the fuel may use hydrogen or decyl alcohol. [Examples] [Example 1] A single-necked reaction flask was charged with 4 g of sodium hydroxide dissolved in 20 ml of water, and 12.49 g of 2-aminoetlianesulfonic acid (AESA) was added thereto, and Φ was reacted at 60 ° C for 3 hours. Most of the water was removed using a rotary evaporator and placed in a vacuum oven at 80oC, and sodium salt was added to the sodium 2-aminoethanesulfonate (SAES) powder for 24 hours. [Example 2] Preparation of Copolymer (1) 5 g of dry polystyrene-maleic anhydride trowel, ping: maleic anhydride = 1:1), and 60 ml were placed in a round bottle. Tetrahydrofuran (used

9085-A51585-TW 37 201136953 Before using calcium hydride to remove water, it is dissolved by magnet stirring. Take 1_82 g of SAES and 90 ml of dimercaptopurine (use water to remove water before use). In a conical flask, warm to 70 ° C. After the magnet is fully stirred to completely dissolve, the solution of the conical flask is obtained. Pour into a two-necked round neck flask and react at a temperature of 80 ° C for 1 hour. The amount of SAES used can vary depending on the ion exchange equivalent required. 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 DC 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 styrene·maleimide copolymerization of the present example. Preparation of the substance (1). [Example 3] Preparation of styrene-maleimide copolymer (2) 5 g of dry polystyrene-maleic anhydride polymer (styrene: maleic anhydride) was placed in a two-necked round neck flask. = 1:1), and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use), dissolved by stirring with a magnet. Take 1.82 g of SAES and 90 ml of dimercaptopurine (use calcium hydride to remove water before use). In a conical flask, warm to 70 ° C. After the magnet is fully stirred to completely dissolve, pour the solution of the conical flask. The mixture was placed in a two-necked round neck flask and reacted at a temperature of 80 ° C for 1 hour. The amount of SAES used can vary depending on the ion exchange equivalent required. After the reaction, 2.74 g of aminopropyltriethoxysilane was placed in a two-necked round neck flask and reacted at a temperature of 80 DC for 2 hours. Further, 5 ml of distilled water was placed in a two-necked round neck flask to carry out a hydrolysis condensation reaction of ethoxy decane at a temperature of 80 ° C for 3 hours. The appropriate amount of the solution in the two-necked round neck flask was placed in an aluminum melon 9085-A51585-TW 38 201136953 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, water was removed 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 styrene-malay enamel of the present example. Preparation of the imine copolymer (2). [Example 4] Preparation of styrene-maleimide copolymer (3) 5 g of dry polystyrene-maleic anhydride φ polymer (styrene: Malay) was placed in a two-necked round neck flask. Anhydride = 1:1), and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use), dissolved by stirring with a magnet. Take 1.43 g of SAES and 90 ml of dimercaptopurine (use calcium hydride to remove water before use). In a conical flask, warm up to 80 ° C. After the magnet is fully stirred to completely dissolve, pour the solution of the conical flask. Into a two-necked round neck flask, the temperature was 80 ° C for 1 hour. After the reaction, another 2.47 g of polypropylene melamine diamine (Jaffamine XTJ-502, Huntsman) was placed in a two-necked round neck flask and reacted at 80 ° C for 2 hours. 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 a baking box. 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 styrene-Malaysia of the present example. Preparation of the amine copolymer (3). The amount of SAES and polypropylene ether polyvinyl ether diamine can be varied depending on the ion exchange equivalent required to achieve the purpose of controlling the ion exchange equivalent and mechanical properties of the high molecular conductivity membrane. [Example 5] 9085-A51585-TW 39 201136953 Preparation of styrene-maleimide copolymer (4) 5 g of dry polystyrene-maleic anhydride polymer was placed in a two-necked round neck flask ( Stupid ethylene: maleic anhydride = 1:1), and 60 ml of tetrahydrofuran (dehydrated with calcium hydride before use), dissolved by stirring with a magnet. Take 1.43 g of SAES and 90 ml of dimercaptopurine (use calcium hydride to remove water before use). In a conical flask, heat up to 80DC. After the magnet is fully stirred to completely dissolve, pour the solution of the conical flask. In a two-necked round neck flask, the reaction was carried out at a temperature of 80 ° C for 1 hour. After the reaction, 2.47 g of polyetheneamine (Jaffamine XTJ-506, Huntsman) was placed in a two-necked round neck flask and reacted at 80 ° C for 2 hours. 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 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 2 Torr. (:, 48 hours, the preparation of the styrene-maleimide copolymer (4) of this example was completed. The amount of SAES and polyetheramine used can be changed according to the required ion exchange equivalent, The purpose of controlling the ion exchange equivalent and mechanical properties of the polymer conductive membrane is achieved. [Example 6] Preparation of styrene·maleimide copolymer (5) 5 g of dry poly in a two-necked round neck flask was placed. Styrene-maleic anhydride polymer (styrene: maleic anhydride = 1:1), and 6 ml of tetrahydrofuran (dehydrated with calcium hydride before use), dissolved by magnet stirring. Take 143 g of SAES and 9 〇 Mm dimercapto is hard (use chlorinated material to remove water before use). In a conical flask, heat up to 8 °c with the magnet fully stirred to completely dissolve.

9085-A51585-TW 40 201136953 The solution of the conical flask was poured into a two-necked round neck flask and reacted at 80 ° C for 1 hour. After the reaction, 4.12 g of polypropylene triamine (Jaffamine T-5000s, Huntsman) was placed in a two-necked round neck flask and reacted at 80 ° C for 2 hours. The appropriate amount of the solution in the two-necked round neck flask was placed in an aluminum sub-system 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 styrene-Malayiya of the present example. Preparation of the amine copolymer (5). The amount of SAES and polytriamine used can be varied according to the ion exchange equivalent of φ required to achieve the purpose of controlling the ion exchange equivalent and mechanical properties of the polymer conductive membrane. [Example 7] Conductivity and moisture content measurement The film was sandwiched between stainless steel electrodes, the electrode length was 3 cm, and the electrodes were fixed by 1 cm, and the film was measured by an AC impedance analyzer (CH Instrument model 604A). Impedance value, the following formula calculates the proton conduction of the film • Degree:

RxA σ is the proton conductivity (S/cm); / is the electrode distance fixed to 1 cm; R is the impedance value, A is the proton conduction area = film thickness x 3 cm. Moisture content is to soak the film in water, so that after completely moisturizing, remove the residual water on the surface of the film and measure the weight of the film, which is calculated by the following formula, as shown in Table 9085-A5.1585-TW 41 201136953 0 Moisture content = (wet film weight - dry film weight) / wet film weight meter - sample film thickness water content ion exchange equivalent proton conductivity (μιη) (wt%) (meq / g) C7 (S / cm ^ Example 3 250 39 1.10 〇 057 Example 4 200 70 1.25 0 033 Example 5 210 82 0.97 〇 041 Example 6 190 31 1.18 0 025 Nafion-11 7 180 24 0.91 0.054 [Example 8] Direct methanol fuel cell unit The film of the above-mentioned Example 3 was fabricated as a film electrode assembly cell with &amp; Nafi〇n_117 (4), and the performance of the sterol fuel cell unit was tested at 60 ° C. E-TEK PtRu/C (Pt content 20 wt%) was used for the anode. , cathode using e_tek

Pt/Cf medium (Pt content 20 wt%). The amount of the anode and the anode catalyst coating was _Pt/cm, and the area of the catalyst layer was 5 cm. The anode feed was an aqueous solution of decyl alcohol at a feed rate of 2 ml/mm. The cathode feed is oxygen and the feed rate is l〇〇ml/min. Please refer to the test results! Figure. The first drawing shows the test results for a sterol fuel cell, including the plot of current density versus potential, and the plot of power versus power density. As can be seen from the figure, the film property 9085-A51585-TW 42 201136953 of Example 3 can be slightly higher than Nafion-]. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and anyone skilled in the art can make modifications and retouching without departing from the essence of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

9085-A51585-TW 43 201136953 [Simplified Schematic] Sterol fuel cell single power Figure 1 is a polarization curve and power density of a cell test according to an embodiment of the present invention. [Main component symbol description] None 9085-A51585-TW 44

Claims (1)

201136953 VII. Patent application scope: 1 · A maleic imine derivative having the following chemical formula (1) or (II): (I) Where -fCR1R2|~ X] is p and R (R1 and R2 are -H, -CH3 or -F, p between 1 and 20, q between 1 and 100, a between 1 and 6), aromatic or polyoxane; and A is -S03H, -S02H, - S03H2, -Ρ03Η2, -Ρ04Η2 or COOH. (II) where 9085-A51585-TW 45 201136953 - Η, -CH3 or -i^ R (R and R are from 1 to 6), aroma #; 丨; 1~20, 9 between 卜100 ' a B For, and 〇3H2, -P03H2, p〇4H2, _c〇〇H, 〇H HN person k 0 八, ...r〇 or H, -CH- 2. Malay as described in claim i The acid imine derivative ^* 9 aromatic compound includes &quot;Ό H2 servant or ·〇Ά〇~〇^ 3· dimaleimide-derived copolymer having the following chemical formula Μ is an unsaturated monomer capable of radical polymerization; m is between 1 and 0000; η is between 1 and 10000; 9085-A5I585-TW 46 201136953 x] is -H ' -CH- sfe -n (R and R is 3 or -F 'p is between 1 and 20 'q between 1 and 6, and: 3⁄4: goes to 4; ι狖1~1〇〇' a) aroma compound or polyoxyalkylene; It is -S〇3H, -S〇2h, ·δ〇3Η2,·ρ〇-◦〇. This _Ρ〇4Η2 or 4. The method as claimed in claim 3, wherein the aromatic compound comprises, a composition comprising: a horse having the following chemical formula (I) or (Π) A quinone imine derivative or a maleic imide-derived copolymer having the following chemical formula (III); and a pulverized polymer, an inorganic oxide, an inorganic acid or a mixture thereof. (I) CHi—0- R2 'aq (R1 and , ϋΗ3 or 'F, p between 1 and 20, q between 卜, 100, ～1 to 6), aromatic compound or polyoxane, A It is -SO#, 9085-A51585-TW 47 201136953 -S02H, -S03H2, -Ρ03Η2, -P〇4H2 or -COOH. (II) Wherein Xl is ·^卞2^, RZ (R1 and R2 are -Η, -CH3 or -F, p is between 1 and 20, q is between 1 and 100, a is between 1 and 6), an aromatic compound or Polyoxane, B is -S03H, -S02H, -S03H2, -P03H2, -P〇4H2, -COOH, -Η, -CH3, u u A (III) wherein M is an unsaturated monomer capable of free radical polymerization, m is between 9085-A51585-TW 48 201136953 !〇〇0〇, between 1~]0000, and X is -fCR1R2-)^- C (R and R are -Η, -CH3 or _F, p is between 1 and ?η, ζυ 'q is between 1 and 100, a is between 1 and 6), aromatic compound or polyoxane, A Is -S03H, -S02H' -S03H2, -Ρ03Η2, -p〇4H2 or _c〇〇H. 6. The composition of claim 5, wherein the aryl compound comprises: ΌΆ〇·〇· 〇 • 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如The polymer includes a side-chain branched aminopropyl polydimethylsiloxane or a bis-aminopropyl polydimethylsiloxane in a crosslinked structure. The composition of claim 5, wherein the inorganic oxide comprises silica, montmorillonit or laponite. 9. The composition of claim 5, wherein the inorganic acid comprises zirconium phosphate or sulfonated silica. 10. The composition of claim 5, wherein the maleic imine derivative or the maleimide-derived copolymer and the stone-containing polymer, inorganic oxide, inorganic acid or The weight ratio of the mixture is between 1/3 and 1/20. 9085-A51585-TW 49 201136953 11. A film comprising: a maleimide derivative having the following chemical formula (1) or (II) or a maleimide-derived copolymer having the following chemical formula (111). (I) C 〇- (R1 and R- are -H, -CH3 or ·F, p is in the range of 20, q is in the dip (10), 3 is in the range of 1 to 6), aromatic or polyoxane, and A is - S03H, -S02H, -S03H2, machine H2, _p〇4h2 or _c〇〇H. 〇(R1 and 9085-A51585-TW 50 201136953 -S-H R2 is -Η, -CH3 or, p is between 1 and 20, q is between 〇〇, a is between 1 and 6), aromatic compound or Polyoxane, b is _3〇3}1. -S〇2H' -S03H2 &gt; -P03H2 &gt; -P〇4H2 ^ -COOH. _H ^ -CH3 [__I v 〇 Ό OH or (III) wherein M is an unsaturated monomer capable of free radical polymerization, m is between 10000, n is between U0000, and χ is -fCR1R2^- temporarily. V ... ' (R and R are -Η, -CH3 or _f, p: two 20? between 1 and 100, a between 1 and 6), aromatic compound = alkane, A is _ s〇3H, _s〇2H, _s〇U, -P〇4H2 ^-COOH 〇- J 12. The film according to claim 1, wherein the m-type composite comprises a film according to claim 11 in which the film is a proton of θ ^ 9085-A51585-TW 51 201136953. Conductive membrane. 14. The film of claim 13, wherein the proton conductive film is applied to a fuel cell. The film comprises: a composition comprising a maleic imine derivative having the following chemical formula (I) or (H) or a maleimide-derived copolymer having the following chemical formula (ΠΙ) And a stone-containing polymer, an inorganic oxide, an inorganic acid or a mixture thereof. Where X4^cr1r2V, R, _H, -CH3 or -F' P is between K20 and (R a is between 1 - 丄Λ 丄 2 ϋ, q is between 1 and 1 SO:: or AI, AM Na 2, hui 9085-A51585 -TW 52 201136953 (Π) / ,. , —f-CH-V-Ο-- —(-CR1R2^— [ l2 a Jq where X is P, R (R) and R2 are -Η, -CH3 or -F, p is between 1 and 20 , q is between 1 and 100, a is between 1 and 6), aromatic compound or polyoxyalkylene, B is -S03H, -S〇2H, -S03H2, -P03H2, -P04H2, -C00H, -Η, -CH3, / Η H n A (III) wherein M is an unsaturated monomer capable of radical polymerization, m is between -fCR1R2|-1 to 10000, η is between 1 and 10000, and X] is Ρ, 9085-A51585-TW 53 201136953 (R1 and R2 are -Η, -CH3 or -F, p is between 1 and 20' q is between 1 and 100, a is between 1 and 6), aromatic compound or polyoxane, and A is _S03H. -S〇2H, -S〇3H2, -P〇3h2, ~p〇4H2 or -COOH. 16. The sputum as described in claim 15 wherein the fragrant or ~Ό·〇Ό·〇·〇-〇 The film according to claim 15, wherein the zeolitic polymer comprises a side chain of aminopropyl polydimethylsil xane or a crosslinked structure - bis-aminopropyl p〇lydimethylsil xane. 18. The film of claim 15 wherein the inorganic oxide comprises silica, montmorillonit or laponite. 19. The method according to claim 15, wherein the inorganic acid comprises zirc〇nium ph〇sphate or sulfonated silica 〇20, as described in claim 15 a film in which the ratio of the acid imine derivative or the maleimide-derived copolymer to the lanthanoid polymer, the inorganic oxide, the inorganic acid or the mixture thereof is between 1/3 and 1/2 Å. The film 9085-A51585-TW according to claim 15 wherein the thin film 54 201136953 is a proton conductive film. 22. The thin raft of claim 21, wherein the proton conducting vibration is applied to a fuel cell. A battery comprising: a cathode and an anode; and a film according to the nth aspect of the patent application, disposed between the dangerous electrode and the anode. '^= 24. The battery of claim 23, wherein the battery For a fuel cell. Wherein the fuel is the fuel. The fuel of the battery as described in claim 24 is hydrogen. 2 6 _ The fuel cell of the battery as described in claim 24 is sterol. 27. A battery comprising: a cathode and an anode; For example, between the thin anode and the anode described in claim 15 of the patent application scope. The battery set in the yin 28=the patent application scope item 27 is a fuel cell.八中^亥电池 29_ The fuel of the battery as described in claim 28 is hydrogen. Wherein the fuel 30. The fuel cell of the battery tank of claim 28 is methanol. ^The fuel electric 9085-A51585-TW 55