TW200924846A - Siloxane membrane main ingredients - Google Patents

Abstract

This invention siloxane membrane main ingredients including modified solid containing double bonds of oligo-siloxane, proton conductive monomer and crosslinking agent, and modified absorbent compounds. This invention silicone membrane feature is that the double bond of oligo-siloxane is reaction products from hydroxypropyl-terminated dimethyl siloxane and glycidyl methacrylate. The weight of glycidyl methacrylate is below 30 percent as compared with the weight of hydroxypropyl-terminated dimethyl siloxane. Hydroxypropyl-terminated dimethyl siloxane, molecular weight range of 500 g/mol and 50000 g/mol, can be used in fuel cells and water gel membrane optical products.

Description

200924846 IX. Description of the Invention: [Technical Field] The present invention relates to a decane film, especially a siloxane film for a proton exchange membrane of a fuel cell. [Prior Art] 质 Proton Exchange Membrane Fuel Cell in Various Fuel Cells (Proton Exchange)

Membrane Fuel Cell (PEMFC) is a key technology for energy development technologies in various countries due to its material acquisition and temperature control (less than 1 〇 (rc) is simplified compared to other types of fuel cells. Proton Exchange Membrane , PEM) produces an electrochemical reaction site for the fuel cell. The two sides of the PEM generate oxidation and reduction reactions, and the hydrogen ions (H+) in the membrane are transferred from the water in the membrane to the cathode end at the anode end to participate in the reduction reaction, and the water is produced into water. The proton exchange membrane is a network structure, and the ions communicate with each other through the pores communicating therewith to form a pathway. The conduction modes of ions in the ion exchange membrane can be divided into two categories: one is a Macro-homogeneous model. The Stefan-Maxwell equation was used to study the ion conduction mode 'another' is P〇re-model. The transfer of hydrogen ions in the membrane is carried out in the form of a +, h wish. The transmission of a hydrogen ion poem 3 to 6 water molecules In order to match, the hydrogen ion of the towel is affected by the back_dif of the anode water molecule and the osmosis of the anode. The hydrogen ion is transported by the electrolyte membrane_electrocatalyst layer and oxygen 200924846 The reduction reaction produces water; therefore, if the water molecules in the membrane evaporate too much, the conductivity of the film will become unstable and unstable. For the proton exchange membrane fuel cell, the resistance of the film is disproportionate to the performance of the battery. The effect is; the higher the water content of the film, the smaller the resistance. The thinner the electrolyte membrane is, the easier it is to transfer hydrogen ions, but the too thin gas and oxygen will cause the Cross-over phenomenon, which will degrade the performance of the battery. The exchange membrane used in the early stage is benzene. The test acid and the formalin are condensed to form a film, but it will pollute the water produced by the PEMFC and greatly reduce the performance, so that the battery life will be shortened. The protons will be filtered by the cations. The electrolyte membrane is transported to the anode 'and with the oxygen water. The money ion is transported in the electric film. The hydrogen ion is about 4 to 6 water molecules, so the protons move in the polymer membrane. The water content of the membrane is related. The nature of water and methanol is similar (such as the similar dipole moment), so in proton conduction, sterols will interact with water molecules via electro-osmotic and diffusion (diffusi〇n). The movement moves from the anode to the cathode. Therefore, the moisturizing ability of the proton exchange membrane is very important. The suitable proton transfer membrane used by DMpc should have excellent hydrogen proton conductivity, but it is an electrical insulator. Most commercial membranes contain fluorocarbon. The polymer domain plus the side-linking branch sulf〇nic(iv) functional group is used for proton conduction. The ideal proton exchange membrane must have the following properties: (1) high proton conductivity (2) low electron conductivity (3) low fuel permeability (preventing hydrogen gas) , sterol and oxygen CrQSS0ver) 200924846 (4) Dimensional stability (dimensi〇nai to oil out) Good (5) Good mechanical strength (6) Low moisture content of the film, must have good ionic conductivity (7) The film is completely Under dry conditions, the impedance must be high (8) Chemical stability. At present, research on fuel cell proton exchange membranes at home and abroad focuses on improving its conductivity, crossover and dimensional stability of methanol. © Proton exchange membranes for PEMFC can be divided into: (1) Fluoride proton exchange membranes: such as Naf ion membrane, Aeiplex membrane 'XUS membrane # ° In the proton parent membrane fuel system, the requirement of proton exchange membrane is required To have good proton conductivity, mechanical strength and durability, Dufan, which was developed in 196 years, can meet the above requirements. The 〇n film is a charged carbon polymer, and the cation exchange ruthenium is made of polytetrafluoroethylene. The primary bond is a hydrophobic carbon-based carbon compound, and does not have a charge. The branch is a charged hydrophilic s. The "anion-based" and sor-bonded protons can move freely in the polyelectrolyte to form a conductive proton function. There are: high chemical stability, high mechanical strength, non-conducting, non-breathing and low proton conduction resistance. However, 'Nafion membrane is also too expensive, and can not prevent the transmission of methanol and cause the failure of Cr: This is because the total gas proton exchange membrane has a very high sterol permeability, and the high permeability of the Gaochun County is derived from the large channel formed by the extremely large ion 200924846 group, and the reason for the formation of this large channel and its The polymer structure is related to 'and the higher the concentration of sterol', the more serious the Crossover will be. This is the main cause of the DMFC performance degradation. (2) Hydrocarbon polymer materials and their composite materials: including sulfonated poly(phenylene oxide) * Sulfonated poly (phenylene sulfide) , sulfonated polysuIfone 'sulfonated polycarbonate > sulfonated polystyrene * sulfonated ❺ polyimide ' sulfonated polyqu Inoxaline, sulfonated (phosphonated) polyphosphazene » sulfonated polyetherefeskefone (S-PEEK), sulfonated polybenzimidazole (PBI), sulfonated polyethersuIfone (SPSU), sulfonated poly (aryl ether su If one)/Base»Poly (aryl ene ether sulfone) * poly ( 4-phenoxybe-nzoyl- 1,4-phenylene, poly-X2000 (PPBP) and other various polymer or inorganic composite materials.

❹ (3) Non-sulfonated polymer membranes: such as inorganic acid doped PBI and PBI-derived polymer materials. (4) Inorganic proton exchange membranes such as sulfonated polyphosphazene. The existing DMFC polymer electrolyte membranes are: sulfonated perfluorinated polymer membranes such as Gore-select from Gore, Nafion from Du Pont ’ Flemion 200924846 from Asahi Glass, Aciplex from Asahi Chemical Co., and the like. SPEEK : trade name Victrex, ICI ; Fuma-Tech Germany ; Axiva, Germany

Hydrated SPSU: trade name Udel-Modifiedby Nolte et al., Kerres et al. BI film: Celtec V ❹ Modified film

Nafion EwllOO : Du Pont Nafion/silica composite * CNR-TAE Institute Transformation & Storage of Energy » Italy BMI doped Nafion : Du Pont S-poly (arylether sulfone) : CNR-TAE Institute Transformation & Storage of Energy , Italy © S -poly(4-phenoxybenzoy 1-1.4-phenylene) :Maxdem Inc,

USA

Imidazole doped PEEK · Max Plank Institute FKF » Germany S-PEEK/PBI Blend : University of Stuttgart , Germany S-PSU/PBI Blend · Germany Patent documents: PBI-H3P〇4: US 5716727, 5525436, 6099988 200924846

Polysulfone » polyaryl ether/inorganic : US 7008971 S-PEEK : US 6984713 SPES : US 6869986 , EP 0574791A1 S-PSU/PBI : DE 19817374A1 S-Polyaryletherketone : EP 574791A1 However, the above-mentioned films have some disadvantages, such as film formation. Because the solubility of the solvent is limited, the membrane of the acid Doping such as PBI/phosphoric acid is also easily depleted by the production of water to reduce the performance of the battery; for example, the heat stability is insufficient, the synthetic molding method is complicated, and the price is still high. In order to solve the above problems, the novel modified Shishioxue structure proton exchange membrane developed by the invention can make up for the price of the existing membrane material (such as Nafi〇n), limited molding, high permeability of methanol, high temperature. Proofs such as proton conductivity drop. SUMMARY OF THE INVENTION The main object of the present invention is to provide a decane film whose main solid components include a modified double oxygen-containing oxy-oligomer, a proton conductive monomer, a crosslinking agent, and a modification. a water-absorbing compound, and the modified double-bond-containing oxalate oligo is a hydroxyprop-terminated dimethyl siloxane and a glycidyl methacrylate. The reaction product. In the production of the film, it is only necessary to irradiate the agitated reaction product on the pet film with UV to harden it into a film without complicated synthesis steps to form a film. 11 200924846 The second aspect of the present invention provides the provision of oxygen-cutting thieves, adjusting the types, contents, and reaction conditions of other reactive monomers to produce various aspects of inaugurality, flexibility, and molding conditions. , _ low price and easy to obtain is also a big advantage. Based on the above objectives, the main solid components of the gambling gambling include the modification of the double-bonded yoke oxygen polymer, the proton conductive monomer, the crosslinking agent, and the modified water-absorbing compound. The oxoxane film of the present invention is characterized in that the modified double-bonded oxime oligopolymer oxime is hydroxypropyl terminated dimethyl siloxane (hydlOXypn) pyl_terminated dimethyl siloxane) and methyl acrylate Hydroxypropyl-terminated dimethyl sil〇 Xane) 3% by weight or less, hydroxypropyl-terminated dimethyl sil 〇 xane has a molecular weight ranging from 5 〇〇g/m〇i to 5 〇〇〇〇g/m The advantages and spirit of the present invention will be further understood from the following detailed description of the invention and the accompanying drawings. [Embodiment] The composition component of the oxirane film of the present invention comprises (丨) an oligomer of a ruthenium oxide containing a double bond, (2) a proton conductive monomer, (3) a crosslinking agent, (4) Water-absorbing monomer, (5) photoinitiator. In the production of the film, it is only necessary to use UV to irradiate the stirred reaction product on the PET film to harden it into a film without the need for a conventional complicated synthesis step to produce the film. At the same time, the oxime film of the present invention has high proton conductivity, heat resistance, chemical resistance xm, low sterol and gas transmission specificity, and conforms to the general requirements for a fuel cell proton exchange membrane. Specifically, the modified oxirane film of the present invention contains a double bond-containing oxane oligomer, which is a propyl-terminated dimethyl siloxane and a thiol-acrylic acid. The reaction product of glycidyl methacrylate, and the weight percentage of glycidyl 〇methacry1 ate is hydroxypropyl-terminated dimethyl si loxane The weight of 30% or less, propyl-terminated methoxy 〇 〇 〇 〇 〇 〇 ll ll ll ll 分子量 分子量 分子量 分子量 分子量 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在In the case of the above materials, the above-mentioned reactants can be adjusted to various types, contents, and reaction conditions of the other reaction monomers, and various membrane materials having different strengths, flexibility, and molding conditions can be produced, and at the same time, low prices and easy to obtain are also A big advantage. The procedure for making the oxime film of the present invention is as follows: 1. The above formulation was stirred with a magnet for 3 hours. 2. Place the evenly-mixed formulation on the PET film and spread it evenly with a spatula, then cover the other PET film. 3. Place in a UV light reaction bath (365 nm) for 600 seconds to form a film. The dream compound and its derivative (si 1 13 200924846 compounds and their derivatives) in the oxy-combustion film of the present invention can be based on the chemical structure, and can be based on the stone-bearing element and the age group It has both money and inorganic properties, and has many excellent properties such as heat resistance, weather resistance, electrical conductivity, electrical insulation, water repellency, non-toxicity and low surface tension. It can be used in the environment of _6〇ΐ~35〇ΐ, that is, the temperature record is more suitable for electronic parts and the like because of the good ship. The main chemical bonds of the siloxane molecular chain are (4) and si_c. The energy of the 矽 键 bond is 455 KJ/mal, which is higher than the 258 J 1 of the C-C bond and 258 KJ/m 〇 l of the c-〇 bond. The oxygenate is more thermally stable than the carbon oxide. However, the polar or partial ion heterozygosity on the Shixi oxygen bond also makes the sulfhydryl group on the Weizi have higher thermal stability and oxidation resistance than the methyl group of the carbon j. Therefore, Shixi oxygen-burning compound has thermal stability, oxidation resistance, good oxygen permeability, electrical insulation, good weather resistance and low stress. The tree sister adds the person's inspection. The Wei 6_ molecule can combine with the polymer to form a block, alternating (Alt_ting) and grafting gamma (1). The recording of polymer silk is mainly divided into three major directions: (1) Side chain riding ············································· (2) Riding······································································································ In order to explain the influence of the amount of each component in the siloxane oxide film on the strength, proton conductivity, high temperature stability and proton conductivity of the film, and the basic properties of the film such as film crosslink density and gas permeability. The correlation is described by identification methods including DSC, TGA, water and moisture loss measurement, methanol permeability, expansion ratio, and proton conductivity measurement. © Example of a naphthenic film of the present invention

Table 1 shows the representative composition of the initial production. The results obtained here are that the water content is changed according to the water-containing monomer and (4), and the water-repellent rate is expected to be reduced, but the degree of extraction is increased. The water content is formed by falling. In this initial formulation domain, sample 7 has the best properties, and its surface area, electrical conductivity, and strength 15 200924846 degrees are more balanced than other samples, and the conductivity is also the best (3〇ec: 2. Discussion _3 S/cm 8GC ' 1. lxiG-3 S/αη) 'With this step-by-step adjustment. Conductivity test 1·The film is a circle with a diameter of 35 mm as far as the constant temperature and humidity chamber. 2. After the system is stable, conduct conductivity test with ac Impedance. 3. The obtained impedance value is substituted into the formula to obtain the ion conductivity value. The test conditions are as follows: 频率 Frequency: 1000000~0.1Hz Amplitude: 10mV Test temperature: 30°C Measured humidity: RH95% 4. Select the frequency range of the test at 1 〇〇〇〇〇〇 makeup ~ 丨 Hz, set the AC The amplitude is 10 mV. If the signal is too much interference, the amplitude can be adjusted to 1〇〇mV and the direct voltage is set to 〇mV. The test piece was placed in the middle of the electrode under a constant temperature and humidity chamber. The AC impedance spectrum obtained after the analysis was analyzed to obtain the impedance value of the film, and the ionic conductivity of the film was obtained by substituting the impedance value (Rb) into the formula.

RbxA σ : conductivity, S/cm L : film thickness, cm

Rb: film resistance value, Ω 200924846 A : area of contact between the electrode and the film, cm2 sterol penetration test 1. The film to be tested is sandwiched between two glass cells, and both sides of the film are filled with a 3 M aqueous solution of sterol (A tank) and distilled water (B tank). 2. The volume of solution in tank A and tank B is 100 ml each, and the cell is kept at temperature 3 (TC. 3. 2 ml of solution of B tank is taken every hour at room temperature - three times, and the value is substituted by density meter. The concentration of sterol is measured by the measuring line to determine the amount of sterol permeation. Ο 4· Take points every hour for 10 hours to take a picture. Note: The calibration line is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% sterol water was measured by a densitometer. 5. The obtained sterol concentration was substituted into the following formula to determine the sterol permeation rate. ln(C4 - Cs(i)) = - ~

Ap

Cb and Ca : the methanol concentrations(wt%) in the receiving cell and the source cell, respectively.

Vb : the volume of the receiving cell (cm3) A : cross-sectional area of the membrane (cm2) L : the thickness of the membrane (cm) P : the methanol permeability (cm2/s) 17 200924846 t〇: termed the Time lag t〇= L2/6D (s) D : the methanol diffusion coefficient (cmVs) TGA test 1. Before the experiment, the residual gas in the furnace body and the pipeline was removed by introducing nitrogen gas at 20 cc/roin for 1 hour. 2. Each film sample is stored in a dry environment. 3. Take a sample of l〇mg~I5mg film and pulverize. © 4 For the broken sample, place it in a platinum plate and start to rub the cat. The test conditions are as follows:

Nitrogen flow rate: 60ml/min Heating rate: liTC/min Operating temperature range: 30°C~600°C Water absorption test test ©Heavy. The membrane is weighed after 3 hours under the 100 匚 supply box, which is the dryness of the membrane. 2. It is rubbed into pure water for 24 hours and is heavy, which is the wet weight of the membrane. Percentage of water absorption rate is 2% of the degree of change in weight before and after water absorption, this is SR= { (Ws ^ / 1

Wd) / Ws } xlOO% where: Ws: post-finance _ weight ° dry film weight This test is based on the ASTM D 570 specification. 18 200924846 Membrane moisture content Commercialized %fion-117 DuPont Company tested with a D 57〇, which contained 38 [experimental results of 37.4% similar to DuPont. The water content changes depending on the amount of the water-containing monomer S and the cross-linking component. The addition of the water-repellent monomer is as expected to lower the water content, but the strength is increased. This strength increase is not only caused by the decrease in water content, and is formed by ~r-r~~ One—_______ 2.5 0.06 〇.〇6 15 2.5 0.06 0.06L5 〇!〇3 o^og- 2·5 0.06 0.06 L5 〇1〇3 2.5 0.06 0.06~L5 〇!〇3~ 2.5 0.12 0.06 1.5 〇.〇 3 ~~〇.〇6 F 5 2.5 0.12 0.06 1.5 0.06 0.12 0.12 G 5 2.5 0.06 0.06 1.5 0.03 H 5 2.5 0.06 0.06 1.5 0.06 I 5 2.5 0.06 0.06 1.5 0.06 J 5 2.5 0.06 0.06 3 Table 2❹ 〇1. Modified Siloxane by reacting 100 parts of the hydroxypropyl-terminated dimethyl siloxane, (viscosity = 300 cS, Dow Corning Co), with the 20 parts of GMA for 3 hours at 80〇C in the presence of 0.1 part tertiary amine catalyst. -methacryloxypropyltrimethoxysilane » Dow Corning 200924846

Co. 3. Glycidyl Methacrylate (GMA), 99% 'Aldrich Chemical Co. 4. Hydroxyethyl Methacrylate (HEMA) ? Aldrich Chemical Co. 5. B0LT0RN P1000 (star) » dendritic polymer, average molecular weight of 1500 g/mole, hydroxyl Number 430-490, mg KOH/g © equivalent, Perstorp Specialty Chemicals AB. 6. IRGACURE 819 (Bis(2, 4, 6-trimethylbenzoyl-phenylphosphineoxide) » Ciba Chem. 7. 2-Acry1amido-2-methy1-1- Propanesu1fonic acid (Sulf-Acid), 99%, Aldrich Chemical Co. 8. Aerosil 300 (A300), fumed silica, BET surface area 300 © ±30 m2/g, average primary particle size 7 nm, Degussa Chemical Co. Trimethylolpropane triacrylate (TMPTA). In Table 2, the composition of each component is clearly listed. There are two modifiers. A300 is a nano-sized hydrophilic inorganic silica with a primary particle size of 7 nm and a Star code of branched-type 0H. Organic molecules, the effects of which can be seen in the following results. 20 200924846

SamDle Water content (%) A 33, B 40 C 40 D 43 E 38 F 40 G 44 — H 45 I 41 -- J 52 Table 3 Table 3 is the moisture content of the sample of the second component (standard deviation less than 5%) The sample A has a water content of 33%, and after adding 0.6 phr (based on si loxane), the water content increases to 44% (see sample 20), which is significantly increased from the nano-sized coriander. A high surface area with a hydrophilic surface of 0H (300±30, DIN66131). After the addition of the 0.6 component of the modified Star component (sample η), the water content was also effectively increased to 45%, which was also attributed to the high 〇H content in the composition, but the composition of the different modified plants could affect the water content. As shown in Sample I, the water content was smaller than that of Sample G at the same amount of 〇·6 phr, since GMA was a low water absorbing oil monomer. In addition to the modifier, doubling the content of the 官能acid functional monomer can also increase the moisture content to 52% (Sample J). After adding A300 and star components at the same time, it is no longer possible to increase the water content (see samples B, ^, D), and then increase the amount of crosslinker. As the crosslink density increases, the water content decreases (see samples D and E), A300 and star components. The increase is also effective for increasing the water content of highly crosslinked samples. 21 200924846 Conductivity

Sample Conductivity (S/cm, A 2.6xlO'J B 1.8xl0'3 C 9.2xl (TD 7.3xl (T a 4.6xl (T 1.9x10° H 2.5xl〇-JI l.lxlO· 3 J 1.5xl〇-3 Table 4 The conductivity of each sample is shown in Table 4. The conductivity of the original sample A is 2. 6xi〇-3s/cm. Increasing the Sulfonic monomer multiple (sample J) can not increase the conductivity. On the contrary, this result may be due to the fact that the addition of Sulfonic monomer has exceeded the saturation solubility, affecting the photoreaction and affecting the grafting amount. The excessive water content may also affect the conductivity. After the addition of A300, the conductivity decreases slightly to丨.9xl〇-3s/cni, the addition of inorganic particles increases the conduction path, although it increases the water content but does not effectively increase the conductivity. However, the addition of the organic star component to the conductivity scale is not like fiber, such as the sample h its conductivity© In 2·S/cm′, the value of sample A is about the same. In this case, the 〇H group/initiality and the hydrophilicity of 3 water are not like the sample, and the GMA is reduced, so the conductivity is also sample I. Decrease more. If you enter the program and add the rainbow component at the same time, it will also reduce the conductivity, such as ^ mur s / em ' Λ value compared to the sample (a) The sample c is & (4) 4 S/cm' is significantly lower than the sample G and !, which shows that when the deletion and the modified coffee component are shared, the change is _-the average of the arithmetic, and there are interactions and additions, and the consideration is 22 200924846 Below the water content, this may be due to the interaction between A300 and GMA modified star surface components, which affects proton conduction. When A300 and two star components are used, the conductivity of the sample decreases again. The results of samples D, E and F. The lowest conductivity is found in sample D (7.3×10_5 S/cm), but the conductivity increases again when the crosslinker increases (see samples E, F). Compare the three samples with The conductivity of the above sample can be seen here. The interaction between the crosslinker and the A300 and star components can be seen. 0 The thermal stability of the si loxane film made by TGA analysis can be understood by TGA analysis, and the heat reaction of each formula is TGA. (10) The cracking behavior of (4) component (4) at high temperature is known from the initial cracking temperature (the temperature at which the material shows the temperature at which the material is subjected to thermal cracking, and the rate of thermal cracking can be determined by the temperature at the maximum rate of cracking) and Ti. At the same-heating rate The smaller the vta is, the faster the cracking rate is. The number of peaks of the tga micro-spectrum also represents how many kinds of cracking reactions may be carried out. The weight loss of each system is 1 and the most heterogeneous amount is also the same. Cheng 23 200924846

Sample TiCC) Tpl(°C) TP2(°C) TP3fC) Residual amount (%) A 168.5 232.1 309.8 411.3 5.2 B 169.4 227.7 304.5 406.9 6.3 C 176.5 226.8 310.7 406.0 5.8 D 172.9 230.3 308.0—" 404.3 7,0 E 175.6 232.1 307.1 409.6 5.6 F 169.4 236.5 308.0 406.0 7.8 G 169.4 245.3 310.7 407.8 8.1 H 172.0 240.9 304.5 407.8 7.4 I 175.6 239.1 310.7 412.2 8,2 J 17L2 200.3 302.7 408.7 92 Table 5 Table 5 shows the thermal cracking of representative samples TGA Temperature and final residual amount of thermogravimetric analysis test results, from the TGA spectrum of sample A, it can be seen that the film is divided into three main stages of cracking, water volatilization before 100 °C, starting from 1702⁄4 for the Sulfonic functional group to start the loss in the continuation film The HEM acrylic monomer' Sulfonic monomer cc bond cracking opens the first stage weight loss. The weight loss of this part by TGA analysis was nearly 4%, which was close to the HEMA and Sulfonic monomer content. The second stage is at 25 baht. (: Near the beginning, the highest rate occurs at 309 of Tp2. 8 °C 'The weight loss of this part is about 1〇%, as long as it is due to the CC grafting composition on the Mengyangyuan key'. The cleavage loss of the si loxane composition begins. The weight loss of this part is about 40%. The difference in the third stage loss is less than 5% depending on the sample. Since the TGA map is similar here, only the representative three samples are listed here. The data 'from the data of sample J shows that an excess of unreacted Sulfonic monomer can cause an acrylic-like structure with a low degree of reaction cross-linking, and the first-stage cracking is accelerated, which is consistent with the foregoing result, and the residual amount is increased by about 80% ( 5. 2% increase to 9.2%) This should be attributed to 24 200924846 *

The role of Sulfonic acid g-based is to form a coffee factory at high temperatures. The addition of trace A300 had a significant effect on the cleavage of the -13⁄4 segment, with Tpl increasing from 232. π to 245·3. 〇 and the most, the residual amount is also increased' This indicates that the surface of the fine crucible can change the cracking mechanism of the film component. The addition of the modified star component also has a similar effect on cleavage. For example, sample H increases the initial cleavage temperature and increases Tpl, but causes Tp2 and Tp3 to decrease by about 4, while sample I increases Ti by 7 °C. The effect of Tpl is the same as that of the sample, but it does not affect the deduction 2, such as 3, and this also affects the different effects of the modified star component, and the residual amount is also increased as the latter. Codified with the star ingredients, the county solution has no additive effect. As seen in the samples B and C, compared with the above-mentioned single component addition, the trend is similar. The shirt-GMA has a higher Ti, but the Τρ1 is lower than the muscle, and the influence of τρΐ and τρ2 is smaller. The use of the star_ component is more similar, which represents a significant effect on the acrylic component. It can also be seen from the TGA _ spectrum that it is added to the face or the shirt - the ingredients must be, the first stage of the cracking has - the shoulder peak exists, and the residual when sharing is less than the use alone. This also clearly confirms that when the cracking mechanism changes and the coffee component is used in its entirety, the effect on Ti is much more significant than that on Tp. Increasing the cross-linking agent content can increase the first-order, initial temperature, but the effect on Τρ is small (Sample7), and the addition of multiple modifiers does not promote the cracking stability at high cross-linking agent concentration. 25 200924846 Mechanical properties of membranes

Sample Tensile Stress (kg/cm2) Tensile strmn (%) A 3.58 18 B 2.87 11 C 8.02 22 D 8.48 21 E 9.95 22 F 10.86 31 G 6.59 14 H 7.76 20 I 12.89 23 J 1.075 10 Table VIΟ Each formulated film The mechanical properties are listed in Table 6. Here, each sil〇xane film is extremely soft, and the elongation is also good, but n〇tCh-Sensitive, excess Sulf〇nic component (sample J) is poor in reaction and solubility. Both stress and ductility are much lower than those of sample A. The addition of A300 is effective in increasing the strength' but the ductility is degraded due to the presence of inorganic particles. However, the strength and softness of the original sample A film can be effectively improved by adding the star component. This result is very noticeable in terms of the amount of addition. The stgx_GMA modifier can get the highest intensity (~4 times). When the A300 and the star components are shared, the interaction can be seen. The 纣Hong-hydrolytic modifier is shared with the A300, and the strain is greatly reduced. The strain is also greatly reduced, but the star_GM_A300 is more suitable for the degree and softness than the other side, but the ratio _ star_GMA It is poor, and the miscellaneous A300 and star hydrolysis samples are excellent. The results of sample D when the three were used together were similar to those of sample C, that is, the negative effects caused by A3GG and star-hydrolysis have been eliminated. The addition of a double crosslinker increases the tensile strength (sample E), but does not affect the change 26 200924846 (compared to sample E). At this higher crosslink density, the addition amount of the three modified components can be said to increase the strength from 9.95 Kg/cm2 to 10.86 Kg/cm2 (sample F), but the strain is greatly increased to 31%' The results show that the amount of modified trace components and crosslinker can be adjusted to achieve the best strength and softness. The sterol permeability of the membranes of each formulation prepared by the sterol permeability is shown in Tables VII and VIII. From the table, the relative rate of methanol permeation and the transmittance of each film are shown. The sterol permeability of Naf i〇nl丨7 under the same article is 5. 04x10-5 (unit: wt% / hr X dish) Based on this, it can be seen that the transmittance of all the formulated membranes is less than that of Nafi〇n ,. Although most of the oxalate membranes have higher water content than Nafion 117, the sterol permeability does not increase with water content. It was confirmed that the sterol permeation selectivity of the formulation component was significantly higher than that of Nafi〇n 117. For sample A, the basic transmittance value was L 95χ1〇_5, and after adding A3〇〇, it was slightly decreased to 1.57x10 5 'This is A300 Sil The ica inorganic particles increased the methanol diffusion path. After adding star-hydrolysis, the transmittance increased slightly to 2.13χ1〇-5 (sample H), but after adding Mtar-GMA, the lower the original sample was 14_-5 (sample 〇, This also corresponds to the former

It is stated that the star-monomers of different treatments do not cause properties to the membrane. Here, since the water content of star_GM is lower than that of star-hydrolysis, the transmittance is low. #Adding the Sulfonic monomer in the sample A, the membrane structure reaction is changed due to the increase in water content, and the methanol permeability is higher than that of the sample A. When A300 is shared with the star component: the methanol permeability increases (see sample and C). 'Star-GMA is used at this time, and the star_hydrolyzed transmittance is higher. This is opposite to the sample η and 27 200924846 I. Interaction with the star component on membrane sterol permeability properties' This should be related to the surface interaction properties of the A300 and star components. However, when star-hydrolysis is shared with star-GMA (sample D), the sterol permeability is the lowest, 1.44x10 5 (same as sample I). Increasing the cross-linking agent and the amount of the three modified components (samples E and F) did not contribute to a decrease in methanol permeability. The results show that the chemical structure of the membrane and the degree of cross-linking under the action of the main X component of the methanol permeability can be changed by a single factor. By the detailed description of the above preferred embodiments, it is desirable to more clearly describe the present invention. The features and spirit of the invention are not limited by the preferred embodiments disclosed above. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. [Simple description of the diagram] None [Key component symbol description] None 28

Claims (1)

200924846 X. Patent application scope: 1. A siloxane oxide film, the main solid components include modified siloxane oligomers containing double bonds, proton conductive monomers, cross-linking agents, and modified water-absorbing compounds. The invention is characterized in that the modified double-bonded oxime-burning polymer is a reaction of propyl-terminated dimethyl siloxane and glycidyl methacrylate. The product, and the weight percentage of glycyl idyl methacrylate is 30% by weight of hydroxypropyl-terminated dimethyl siloxane, hydroxypropyl terminated The hydroxypropyl-terminated dimethyl siloxane has a molecular weight ranging from 500 g/mol to 50,000 g/mol. ❹ 2. The alkane membrane according to claim 1, wherein the proton conductive monomer is 2-propenylamine-2-mercapto-1-propanesulfonic acid (2-Acrylamido-2-methy1- 1-propanesulfonic acid). 3. The alkane membrane according to claim 1, wherein the crosslinking agent is trihydroxymethyl propane triacrylate 29 200924846 (Triraethylolpropane triacrylate) ° 4. As described in claim 1 a siloxane film, wherein the modified water absorbing compound is hydroxyethyl methacrylate (HEMA). 5. The oxirane film according to claim 1, wherein the water absorbing compound is modified. It can also be dendritic polymer ° 6. The alkane film according to claim 5, wherein the dendritic polymer has a number average molecular weight of 1500 g/mole and a hydroxyl number of 430-490 (mg KOH/g equivalent) ° ^ 7. The alkane film according to claim 1, wherein the modified water-absorbing compound is Si yi i mai. 8. The alkane film according to claim 7, wherein the Silica Fume has a BET surface area of 300 ± 30 m 2 /g and an average primary particle diameter of 7 nm. 30 200924846 VII. Designation of representative representatives: (1) The representative representative of the case is: ( ). (2) A brief description of the component symbols of this representative figure: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: ❹