KR20050055274A - New membrane materials and their preparation process for the separation of volatile organic compounds(vocs) - Google Patents

Abstract

The present invention relates to a polymer composite membrane for separating and recovering an organic compound and a method for preparing the same, and more specifically, a double bond of a polyacetylene-based polymer having a side chain of a siloxane group and a lipophilic group is hydrosilylation reaction. Cross-linking to improve membrane damage and peeling from the support when used as a composite membrane, and improve permeation performance and mechanical strength to recover volatile organic vapors in petrochemical, gas station / oil storage, painting / printing / laundry, and organic solvents in wastewater. The present invention relates to a polymer composite membrane for separating and recovering an organic compound that can be widely used in various industrial fields requiring separation such as recovery and a manufacturing method thereof.

Description

New Membrane Materials and their Preparation Process for the Separation of Volatile Organic Compounds (VOCs)

The present invention relates to a polymer composite membrane for separating and recovering an organic compound and a method for preparing the same, and more particularly, a double bond of a silane group of a polysiloxane polymer and a polyacetylene polymer having a side chain of a bulky and lipophilic group is hydrolyzed. Crosslinked by the silylation reaction to improve membrane damage or peeling with the support when used as a composite membrane, and also improve permeability and mechanical strength to recover volatile organic vapor from petrochemical, gas station / reservoir, painting / printing / laundry and wastewater The present invention relates to a polymer composite membrane for separating and recovering organic compounds that can be widely used in various industrial fields requiring separation of organic solvents and the like, and a method of manufacturing the same.

In general, volatile organic compounds (VOCs) are generated from manufacturing processes and storage facilities of petrochemical plants, oil refineries, paint plants, printing plants, laundry plants, and fine chemical plants. It is a substance that causes photochemical smog by causing photochemical reaction with nitrogen compounds in the atmosphere and destroys the ozone layer in the atmosphere and is known as a very harmful substance to the human body.

With the recent increase in population and the development of industry, global greenhouse gas has increased due to the large amount of volatile organic compounds (steam and solvent), which causes environmental damage caused by climate change in many parts of the world and destroys ecosystems. As it is getting worse, there is a growing interest in preventing global warming and environmental pollution. Accordingly, the United States, EU countries, Japan, Canada, and other developed countries are intensively researching the generation status and treatment technology of environmental pollutants generated from production to sales of various products.

The European Free Trade Association promises to reduce emissions of volatile organic compounds (VOCs) by 30% or more in the base year (mostly 1980 or 1988) by 2000, and in Europe by 60% in 2007 and 70 by 2010. Pursuing an action plan for the% reduction target. In addition to strengthening trade and environmental regulations by the Uruguay Round, which is promoted around the world, exports are blocked when standards are not met for ISO-certified environmental marks by the International Organization for Standardization (ISO) Environmental Technology Committee. There is a serious problem in the existing process. In the United States, most states, Switzerland in 1989, Sweden in 1990 and Germany in 1991 regulated the recovery of gasoline when refueling. Was completed. Against this backdrop, the environmental plant market for separation of organic solvents has a global demand of approximately $ 10 billion as of 2001.

The volatile organics are treated in the air or in water by adsorption, absorption, cooling condensation, oxidation, vapor permeation through membrane and permeation evaporation. It has advantages and disadvantages for equipment cost.

In the recovery of organic vapor in the air, the adsorption method has a large scale such as additional installation of vacuum / pressurization pump and adsorption tower for adsorption and desorption of organic vapor, high risk of explosion due to adsorption heat, and actual olefin concentration of exhaust gas. Higher energy consumption is difficult to apply to the site. Absorption method has a problem that new pollutants are generated during the regeneration and incineration process, the cooling condensation method is cooled to a low temperature because the energy consumption is very high, the organic vapor has a disadvantage that can not be used when the concentration of organic vapor is low. In addition, the method of oxidizing the organic matter in the waste water has the disadvantage that the apparatus is large and energy-intensive.

However, membrane separation technology uses rubber-like polymers that can selectively pass only olefins from nitrogen. By simply installing membranes and condensers in existing equipment, organic compounds can be recovered effectively. As it is inexpensive and does not emit secondary pollutants and is an eco-friendly process that can reuse the expensive organic materials recovered, it is based on the environment and energy at the present time when awareness of the reduction of greenhouse gases by energy saving and prevention of environmental pollution is increasing. It is the most suitable process.

 Vapor permeation and pervaporation membrane separation processes for separating and recovering these volatile organic vapors from nitrogen, air, and water through a polymer membrane have a relatively short history of more than 20 years. Accordingly, research has been actively conducted in the United States, Germany, and Japan, where environmental awareness is advanced. In particular, MTR in the United States has commercialized a membrane separation process capable of treating such organic solvent-containing flue gas and wastewater. [Journal of Membrane Science , 1987, 31, 259-271, Journal of Membrane Science, 1998, 151, 55-62]. Nitto Denko of Japan [Polymer Journal, 1991, 23 (5), 491-499] and GKSS of Germany have conducted similar research to recover paraffinic gasoline vapors generated at gas stations, painting / laundry / chemical industry, and fine chemicals. Attempts to commercialize membrane separation plants for volatile organic solvents such as processes.

Since the efficiency of the membrane separation process is highly dependent on the permeability of the membrane material, the development of a superior membrane material is very important. As the membrane material used in the vapor permeation process, polydimethylsiloxane (hereinafter referred to as 'PDMS') membrane having a large free volume and high affinity for hydrocarbon-based vapor is commonly used. However, according to the results of the present study, polysiloxane-based polymer membranes are known to cause excessive swelling or delamination with the support when the concentration of the organic solvent is increased, and damage to the membrane is caused without careful attention to the use process. As a result, research into new membrane materials has been conducted, and studies of introducing chemical structures having high stability to organic solvents by adding fluorinated monomers have been conducted, but problems with membrane swelling have not been solved yet.

In addition, attention has been focused on polyacetylene-based membrane materials, which are new super-glassy polymers (US Pat. No. 6,879,431, US Pat. No. 5,688,307), that is, polytrimethylsilylpropine or polymethylpentine [Journal of Membrane Science 1996, 121, 243-250] has high selectivity for organic matter / gas or organic matter / water due to large free volume and organic solvent affinity and very high permeability [Journal of Membrane Science 2001, 186, 205-217, but it is known that there is a sudden decrease in the permeation characteristics with time of use [Macromolecular 2000, 33, 3747-3751] and weak mechanical strength.

Accordingly, in order to solve this problem, a fluoroene group is introduced into acetylene [Journal of Applied Polymer Science, 1991, 34, 1227-1232] to polymerize or fluorine surface treatment [Gas Sep. Purif., 1888, 2, 162-174], cross-linking through the introduction of hyperbranched polyacetylene and bisacryl azide [Journal of Polymer Science, Part B, 1998, 36, 959- [68], a study was conducted to develop a membrane for grafting a polysiloxane amine group to a methyl group of a polyacetylene-based polymer material or a composite of a PDMS membrane having a hydroxyl group at the end of a PDMS membrane material [Membrane Journal, Korea. 1999, 9 (2), 114-125; Journal of Applied Polymer Science 1994, 53, 317], thereby solving the problem of stability of the membrane permeability over time, but has not yet been applied to commercialization.

Accordingly, the present inventors have tried to improve the problems such as peeling phenomenon with the support due to excessive swelling of the conventional polysiloxane-based polymer membrane, and degradation of the permeation performance during long-term use of the polyacetylene-based polymer membrane, the silane of the polysiloxane-based polymer The double bond of the polyacetylene-based polymer having the side chain of the group and the lipophilic group is crosslinked by the hydrosilylation reaction, and the present invention has been completed to realize that it is possible to improve the permeability and mechanical strength problems as well as damage or peeling of the membrane. .

Accordingly, an object of the present invention is to provide a novel polymer composite membrane having improved permeability and mechanical strength while improving stability such as damage and peeling of the membrane.

The present invention is a polymer composite membrane cross-linked polymer composite material,

The polymer composite membrane is characterized in that a double bond of a silane group of a polysiloxane polymer and a polyacetylene polymer having a side chain of a lipophilic group is crosslinked by a hydrosilylation reaction.

Hereinafter, the present invention will be described in more detail.

The present invention has a polysiloxane-based polymer, a hydrophobic rigid main chain structure and a side chain simultaneously to solve various disadvantages of the conventional polysiloxane-based polymer composite film and the polyacetylene-based polymer composite film. By mixing polyacetylene polymer having a high affinity and having the property of permeating organic compounds better than air or water at a specific ratio and crosslinking by hydrosilylation reaction, it is possible to compensate for the decrease in permeability of the polyacetylene-based polymer over time. It is to provide a novel polymer composite membrane and a method for preparing the same, which have excellent separation properties for volatile organic vapors and organic solvents in the air and water by solving the damage and peeling of the membrane due to excessive swelling of the chain formed by the polysiloxane-based polymer.

The present invention is characterized by a novel polymer composite membrane in which a double bond of a silane (Si-H) group of a polysiloxane polymer and a polyacetylene polymer having a lipophilic group side chain is crosslinked by a hydrosilylation reaction. The crosslinking reaction between the silane group and the double bond reduces the delamination of the membrane due to swelling of the silane group with respect to the organic solvent generated when the existing polysiloxane polymer is used alone, thereby improving the safety and mechanical strength of the membrane. By using a lipophilic group in the side chain of the polyacetylene polymer, which is a rigid structure, it forms a structure of a super glass polymer having a very large free volume of the polymer, and thus has a low diffusion resistance of an organic compound having a much larger volume than air or water. As a result, the solubility of organic compounds having high solubility is greatly improved.

As the polysiloxane-based polymer used in the present invention, a known one may be used, and polyhydromethylsilane is preferably used in terms of crosslinking performance and cost competitiveness. However, if the use of a polymer partially substituted with a silane group is less preferable because the cross-linking reaction is less likely to achieve the desired effect in the present invention.

The polyacetylene-based polymer that performs the hydrosilylation reaction with the polysiloxane-based polymer may be one having a large side chain that is affinity for the organic solvent, and the side chain has the property of expanding the rigid polyacetylene to have high solubility in the organic solvent. It shows low diffusion resistance and selective permeation of organic solvents rather than water or air. Such polyacetylene-based polymers may be of various types, but may be easy to manufacture and have high affinity for organic solvents, for example, (poly) trimethylsilylpropine, (poly) methylpentine or copolymers thereof.

The polysiloxane-based polymer and the polyacetylene-based polymer are used in a ratio of 30 to 70% by weight: 30 to 70% by weight, and when the amount of the polysiloxane-based polymer exceeds 70% by weight, the membrane is peeled off by swelling with an organic solvent. The phenomenon occurs severely, and when the polyacetylene-based polymer exceeds 70% by weight, there is a problem that the degradation of the permeation characteristics and the mechanical strength is obvious. Therefore, the present invention should be used in the specific range described above to obtain the effect to meet the purpose.

On the other hand, it will be described in more detail the manufacturing method of the polymer composite membrane according to the present invention.

First, a mixed polymer solution is prepared by dissolving a polysiloxane-based polymer and a polyacetylene-based polymer having a bulky and lipophilic group side chain in an organic solvent having a boiling point of 30 to 130 ° C. The organic solvent should not be chemically reacted while dissolving the two components used in the present invention, it is preferable to use a low boiling point of 30 ~ 100 ℃ in order to make the coating easy during the production of the composite film. In general, toluene or xylene, which are frequently used, is not preferable because the crosslinking reaction does not easily occur during continuous coating. For example, one or two or more selected from hexane, cyclohexane, dichloromethane, dichloroethane, pentane and heptane can be used.

Next, a platinum catalyst is added to the mixed polymer solution under a nitrogen atmosphere to coat the porous support. The platinum catalyst is the most commonly used catalyst for hydrosilylation, and it is preferable to use about 1-2 wt% of the two mixed components. The composite membrane prepared in the present invention is a thin film coating on a porous support such as known polysulfone or polyisamide, and may have a form such as an equilibrium, hollow fiber, tubular, or plate shape.

Finally, the coated porous support is slowly volatilized at room temperature, and then crosslinked at 100 to 120 ° C. for 1 to 2 hours to prepare a polymer composite membrane. The organic solvent used in the present invention has a low boiling point and is almost removed at the same time as crosslinking is formed at the above temperature.

The polymer composite membrane prepared by the above process is cross-linked two composite membranes having many conventional disadvantages by chemical reaction and coated on the support to produce a polymer composite membrane, and then mounted in a system for separating and recovering a known organic compound, Stability problems such as damage and peeling from the support, organic compound permeability and mechanical strength of the composite membrane are improved to improve petrochemical, gas station / reservoir, volatile organic vapor recovery of coating / printing / laundry and recovery of organic solvent in waste water. It can be widely used in many industrial fields where separation is required.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

100 g of polytrimethylsilylpropine and polyhydromethylsiloxane were prepared in 30/70 wt% ratio (a), 50/50 wt% ratio (b) and 70/30 wt% ratio (c), respectively, and then 1000 g. In methylene dichloride (MC). After the dissolved solution was stirred evenly, platinum catalyst was added again by 1% of the mixture and stirred in a nitrogen gas atmosphere. Thereafter, the coating was coated with a thickness of 5 μm on the porous polysulfone support, and the solvent was slowly volatilized at room temperature for 12 hours. Then, this was maintained at a high temperature of 120 ℃ for 1 hour to complete the crosslinking reaction to prepare a polymer composite membrane.

Swelling experiments were performed by dissolving each polymer composite membrane in hexane, and as a result, the degree of swelling was 100%, thereby confirming that the crosslinking reaction was successful.

Experimental Example 1

Gas permeation, aqueous phase separation and vapor permeability were measured using the polymer composite membranes of (a), (b) and (c) prepared in Example 1.

[Measurement of physical properties]

(1) gas permeation

Permeation experiments of ethene / nitrogen and propene / nitrogen gas were performed at room temperature. At this time, the permeation temperature was 10 ° C. The results of the permeation experiment are shown in Table 1 below.

The polymer composite membrane did not change its permeation characteristics even for a long time of more than 1 month, and no breakdown or peeling of the coating layer of the composite membrane was found.

division Ethane / nitrogen Propene / nitrogen Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) (a) 30/70 PC ₂ H ₄ (GPU) 1536 3136 PN ₂ (GPU) 90 89 αC ₂ H ₄ / N _2, 17 35 (b) 50/50 PC ₂ H ₄ (GPU) 3232 6232 PN ₂ (GPU) 161 161 αC ₂ H ₄ / N _2, 20 39 (c) 70/30 PC ₂ H ₄ (GPU) 4086 8086 PN ₂ (GPU) 281 281 αC ₂ H ₄ / N _2, 17 34

(2) Separation performance of aqueous phase

The experiment was performed under the conditions of 30 ° C. and 1 Torr using an aqueous solution containing 500 ppm of toluene, 1,1,1-trichloroethylene, dichloromethane, and ethyl acetate. The results for the separation performance are shown in Table 2 below.

The polymer membrane did not change permeation characteristics for a long time of more than 1 month, and the coating membrane was not destroyed or peeled off.

division toluene 1,1,1-trichloro ethylene Dichloromethane Ethyl acetate Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ water) 944 375 489 317 Transmission rate (L / ㎡ · hr) 0.4 0.1 0.1 0.1 50/50 Selectivity (/ water) 2351 1068 921 135 Transmission rate (L / ㎡ · hr) 0.2 0.5 0.4 0.3 70/30 Selectivity (/ water) 3046 1449 831 821 Transmission rate (L / ㎡ · hr) 0.3 0.3 0.4 0.1

(3) Vapor permeation performance

Experiments were performed under a condition of 30 ° C. and 10 Torr using a mixed gas containing 500 ppm of benzene, 1,1,1-trichloroethylene, dichloromethane, and ethyl acetate in the air. The results for the separation performance are shown in Table 3 below.

The polymer membrane did not change permeation characteristics for a long time of more than 1 month, and the coating membrane was not destroyed or peeled off.

division benzene 1,1,1-trichloro ethylene Dichloromethane Ethyl acetate Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ air) 44 35 43 31 Transmission rate (L / ㎡ · hr) 0.3 0.1 0.1 0.1 50/50 Selectivity (/ air) 35 16 41 41 Transmission rate (L / ㎡ · hr) 0.1 0.2 0.1 0.3 70/30 Selectivity (/ air) 61 24 63 52 Transmission rate (L / ㎡ · hr) 0.2 0.1 0.2 0.1

Example 2

A polymer composite membrane was prepared in the same manner as in Example 1, using polydimethylsiloxane having 20% substitution of a silane group in the main chain instead of polyhydromethylsiloxane.

The swelling experiment was performed by dissolving the polymer composite membrane prepared above in hexane, and as a result, the degree of swelling was 100%, thereby confirming that the crosslinking reaction was successful.

Experimental Example 2

In order to determine the vapor permeation performance of the polymer composite membrane prepared in Example 2, the experiment was performed under the condition of -10 ℃, 10 Torr using a mixed gas containing 2500 ppm of pentane, hexane, heptane, octane in the air . The results for the separation performance are shown in Table 4 below. In addition, the change of permeation characteristics did not occur for a long time over 1 month, and the coating layer was not destroyed or peeled off.

division Pentane Hexane Heptane octane Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ air) 22 16 22 12 Transmission rate (L / ㎡ · hr) 0.3 0.3 0.4 0.3 50/50 Selectivity (/ air) 11 22 19 13 Transmission rate (L / ㎡ · hr) 0.2 0.2 0.4 0.4 70/30 Selectivity (/ air) 24 28 15 16 Transmission rate (L / ㎡ · hr) 0.3 0.2 0.2 0.3

Example 3

500 g of methylene was prepared by making 100 g of polymethylpentine and polyhydromethylsiloxane in 30/70 wt% ratio (a), 50/50 wt% ratio (b) and 70/30 wt% ratio (c), respectively. It was dissolved in dichloride (MC) together. After the dissolved solution was stirred evenly, the platinum catalyst was added again by 1% of the mixture and stirred in a nitrogen gas atmosphere. Then, after coating the porous polyimide hollow fiber support with a thickness of 2 ㎛, and maintained for 10 seconds under a high temperature wind of 140 ℃ to complete the crosslinking reaction to prepare a polymer composite membrane. Swelling experiments were performed by dissolving each of the polymer composite membranes in hexane, and as a result, the degree of swelling was 80%, thereby confirming that the crosslinking reaction was successful.

Experimental Example 3

The polymer composite membrane prepared in Example 3 was carried out in the same manner as in Experimental Example 1 and Experimental Example 2, and the results are shown in Tables 5, 6, 7, and 8 below.

(1) gas permeation

division Ethane / nitrogen Propene / nitrogen Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) (a) 30/70 PC ₂ H ₄ (barrel) 1330 2880 PN ₂ (barrel) 180 180 αC ₂ H ₄ / N _2, 8 16 (b) 50/50 PC ₂ H ₄ (barrel) 2232 4232 PN ₂ (barrel) 111 111 αC ₂ H ₄ / N _2, 22 40 (c) 70/30 PC ₂ H ₄ (barrel) 3066 6306 PN ₂ (barrel) 181 181 αC ₂ H ₄ / N _2, 17 35

(2) Separation performance of aqueous phase

division toluene 1,1,1-trichloro ethylene Dichloromethane Ethyl acetate Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ water) 744 575 222 417 Transmission rate (L / ㎡ · hr) 0.2 0.1 0.1 0.1 50/50 Selectivity (/ water) 1351 1023 421 535 Transmission rate (L / ㎡ · hr) 0.1 0.2 0.2 0.1 70/30 Selectivity (/ water) 2046 1265 631 721 Transmission rate (L / ㎡ · hr) 0.2 0.2 0.1 0.1

(3) Steam permeation performance

Classification (500 ppm) benzene 1,1,1-trichloro ethylene Dichloromethane Ethyl acetate Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ air) 42 45 43 27 Transmission rate (L / ㎡ · hr) 0.1 0.1 0.1 0.1 50/50 Selectivity (/ air) 57 22 22 31 Transmission rate (L / ㎡ · hr) 0.1 0.1 0.1 0.1 70/30 Selectivity (/ air) 53 33 33 42 Transmission rate (L / ㎡ · hr) 0.2 0.1 0.1 0.1

Classification (2500 ppm) Pentane Hexane Heptane octane Polytrimethylsilylpropine / polyhydromethylsiloxane (% by weight) 30/70 Selectivity (/ air) 42 26 22 17 Transmission rate (L / ㎡ · hr) 0.3 0.3 0.4 0.3 50/50 Selectivity (/ air) 31 32 19 12 Transmission rate (L / ㎡ · hr) 0.2 0.2 0.4 0.4 70/30 Selectivity (/ air) 24 38 23 11 Transmission rate (L / ㎡ · hr) 0.3 0.2 0.2 0.3

Comparative Example 1

A polymer composite membrane was prepared in the same manner as in Example 1, using 100 g of polytrimethylsilylpropine. As a result of performing the swelling experiment by dissolving the prepared membrane in hexane, the coating layer was completely melted and thus could not function as a composite membrane.

Experimental Example 4

In order to determine the gas permeation performance of the polymer composite membrane prepared in Comparative Example 1 was carried out in the same manner as Experimental Example 1 with ethene / nitrogen, propene / nitrogen and the results are shown in the following Table 9, by measuring the vapor permeability The results are shown in Table 10 below.

(1) gas transmission

division Initial measurement 1 week 2 weeks 1 month PC ₂ H ₄ (GPU) 34816 15312 6556 - PN ₂ (GPU) 5647 3088 1640 - αC ₂ H ₄ / N _2, 6 5 4 -

As shown in Table 9, within two weeks, the permeability was reduced to 1/5 and the selectivity was decreased. After one month, the coating layer was destroyed and the permeability could not be measured. This phenomenon is more severe in C ₃ H ₆ / N ₂ .

(2) Steam permeation performance

division Initial measurement 2 weeks past 1 month Benzene (500 ppm) Selectivity (/ air) 1461 650 - Transmission rate (L / ㎡ · hr) 1.4 0.1 - Dichloromethane (500 ppm) Selectivity (/ air) 219 79 One Transmission rate (L / ㎡ · hr) 1.3 0.1 -

As shown in Table 10, as a result of performing for a long time of 1 month or more, the transmittance was not able to be measured due to degradation of the permeation characteristics and breakthrough of the coating layer.

Comparative Example 2

A polymer composite membrane was prepared in the same manner as in Example 1 except that the reaction was carried out at a ratio of 10/90% by weight of polytrimethylsilylpropine and polyhydromethylsiloxane.

Experimental Example 5

In order to determine the vapor permeation performance of the polymer composite membrane prepared in Comparative Example 2 was measured by the same method as in Experiment 1, the results are shown in Table 11 below.

division Initial measurement 2 weeks past 1 month Benzene (500 ppm) Selectivity (/ air) 1241 450 - Transmission rate (L / ㎡ · hr) 1.1 0.1 - Dichloromethane (500 ppm) Selectivity (/ air) 119 69 One Transmission rate (L / ㎡ · hr) 0.9 0.1 -

As shown in Table 11, after performing for a long period of more than 1 month, the transmittance could not be measured due to the degradation of the permeation characteristics and the breakdown of the coating layer.

Comparative Example 3

A polymer composite membrane was prepared in the same manner as in Example 5, using a commercial polydimethylsiloxane (Sylgard 184) and a curing agent in a ratio of 9: 1% by weight.

Experimental Example 6

In order to determine the vapor permeation performance of the polymer composite membrane prepared in Comparative Example 3, it was measured in the same manner as in Experimental Example 2 and the results are shown in Table 12.

Classification (2500 ppm) Initial measurement 1 month 2 months Pentane Selectivity (/ air) 13 10 One Transmission rate (L / ㎡ · hr) 0.3 0.4 - octane Selectivity (/ air) 16 One One Transmission rate (L / ㎡ · hr) 0.3 - -

As shown in Table 12, in the case of pentane, two months or more continuous experiments and octane were found to have excessive swelling during use. A sharp drop occurred.

As shown in Tables 1 to 6 shown in Experimental Examples 1 to 6 to determine the permeability of the polymer composite membranes prepared in Examples 1 to 3 and Comparative Examples 1 to 3, the polymers crosslinked by the chemical reaction according to the present invention It was found that the membrane showed excellent permeability and stability of the membrane. In addition, when the mixing ratio of the polymer of Comparative Example 2 was used outside the scope of the present invention in a ratio of 10/90% by weight it was confirmed that the desired effect can not be obtained.

As described above, the crosslinking of the polysiloxane-based polymer and the polyacetylene-based polymer having a specific side chain can form a polymer composite membrane having improved stability, permeability, and mechanical strength. It can be widely used in various industrial fields requiring separation of volatile organic vapor recovery, recovery of organic solvent in waste water, and the like.

Claims (6)

In the polymer composite membrane of the polymer composite material cross-linked, A silane group of a polysiloxane polymer, A polymer composite membrane, wherein a double bond of a polyacetylene-based polymer having a side chain of a lipophilic group is crosslinked by a hydrosilylation reaction. The polymer composite membrane of claim 1, wherein the polysiloxane polymer and the polyacetylene polymer having a lipophilic group side chain are used in an amount of 30 to 70 wt%: 30 to 70 wt%. The polymer composite membrane according to claim 1, wherein the polyacetylene-based polymer is (poly) trimethylsilylpropine, (poly) methylpentine or a copolymer thereof. The polymer composite membrane according to claim 1, wherein the polymer separation membrane is manufactured in an equilibrium, hollow fiber, tubular or plate shape. Preparing a mixed polymer solution by dissolving a polysiloxane polymer and a polyacetylene polymer having a lipophilic group side chain in an organic solvent having a boiling point of 30 to 100 ° C .; 1 to 2% by weight of platinum catalyst based on the mixed polymer is added under a nitrogen atmosphere to coat a thin film on the porous support; And The coated porous support was volatilized at room temperature, and then crosslinked at 100 to 120 ° C. for 1 to 2 hours. Method for producing a polymer composite membrane, characterized in that made. The method of claim 5, wherein the organic solvent is one or more selected from hexane, cyclohexane, dichloromethane, dichloroethane, pentane, heptane and octane.