WO2005123750A1 - Membrane d'enrichissement en oxygene a composes metallosiloxane-oxyde metallique contenant du metallosiloxane et son procede de preparation - Google Patents

Membrane d'enrichissement en oxygene a composes metallosiloxane-oxyde metallique contenant du metallosiloxane et son procede de preparation Download PDF

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Publication number
WO2005123750A1
WO2005123750A1 PCT/KR2005/001856 KR2005001856W WO2005123750A1 WO 2005123750 A1 WO2005123750 A1 WO 2005123750A1 KR 2005001856 W KR2005001856 W KR 2005001856W WO 2005123750 A1 WO2005123750 A1 WO 2005123750A1
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WO
WIPO (PCT)
Prior art keywords
unsubstituted
halogen
substituted
metallosiloxane
substrituted
Prior art date
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Ceased
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PCT/KR2005/001856
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English (en)
Inventor
Jae-Kun Yang
Suck-Eui Hong
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SILO CHEM CO Ltd
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SILO CHEM CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes

Definitions

  • the present invention relates to an oxygen enriching membrane which selectively increases oxygen content in the air, and a method for preparing the same, and more particularly to an oxygen enriching membrane having superior oxygen permeability and selectivity while maintaining superior mechanical strength, and a method for preparing the same.
  • the air we breathe consists of about 20.9% of oxygen and about 78.1 % of nitrogen.
  • a membrane that is selectively more permeable to oxygen than nitrogen in the air is called the oxygen enriching membrane.
  • Air passing through the oxygen enriching membrane has a relatively higher oxygen content.
  • the oxygen enriching membrane can improve fuel efficiency of internal combustion engines of vehicles, contributing to energy saving. Also, it can be widely used in the fields of medicine, oxidation processing, and environmental engineering which do not require high-level oxygen content.
  • the oxygen enriching membrane can i be utilized in the fields requiring nitrogen-rich environment, e.g., fermentation processes. Using the oxygen enriching membrane, it is possible to separate gas with a simple apparatus.
  • the first commercially successful oxygen enriching membrane was one having improved membrane strength through copolymerization of siloxane and carbonate (see W. J. Ward III, J. Membrane Sci., 1 , 99, 1976).
  • research was performed using a graft copolymer of styrene and dimethylsiloxane, introducing an amide into the main chain using tetramethyldisiloxane and aliphatic dicarboxylate, substituting a variety of siloxanes at the para position of polystyrene, and so forth (see Y. Kawakami, J. Polym.
  • the present invention provides a metallosiloxane-metallic oxide compound represented by Formula 1 below.
  • the invention also provides an oxygen enriching membrane comprising the metallosiloxane-metallic oxide compound, and a metallosiloxane compound represented by Formula 2 below or a mixture thereof.
  • the invention further provides a method for preparing a metallosiloxane-metallic oxide compound comprising the steps of treating the metallosiloxane compound represented by Formula 2 with heat and acid or base to dissociate it into the metallosiloxane ion represented by Formula 3 below and adsorbing the metallosiloxane ion on the surface of the metal oxide represented by Formula 1.
  • the invention further provides a method for preparing an oxygen enriching membrane comprising the steps of coating the metallosiloxane-metallic oxide compound powder represented by Formula 1 on woven or non-woven fabric and laminating another woven or non-woven fabric on the metallosiloxane-metallic oxide compound layer.
  • the invention further provides a method for preparing an oxygen enriching membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 in a polymerization monomer, polymerizing the polymerization monomer, and coating the resultant polymer on woven or non-woven fabric.
  • the invention further provides a method for preparing a membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 and an air-permeable foaming agent in polymer resin, foaming the air-permeable foaming agent, and processing the polymer resin into a membrane,
  • M 1 is a metal selected from the group consisting of aluminum, boron, manganese, chromium, lead, titanium, tin, and germanium
  • M 2 0 is an oxide of a metal selected from the group consisting of aluminum, arsenic, gold, boron, barium, beryllium, bismuth, calcium, niobium, cadmium, cerium, cobalt, chromium, cesium, copper, iron, gallium, germanium, mercury, indium, potassium, lanthanum, lithium, magnesium, manganese, molybdenum, iridium, sodium, nickel, osmium, lead, palladium, platinum, rubidium, rhodium, ruthenium, antimony, silicon, tin, strontium, tantalum, tellurium, thorium, titanium, thallium, uranium, vanadium, tungsten, zinc, and zirconium
  • each of R 1 , R 2 , R 3 , and R 4 is hydrogen, halogen, unsubstituted or substrituted CrC 6 alkyl, unsubstituted or substrituted C 2 -C 6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted C- ⁇ -C-6 alkyl, C 2 -C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of R 6 Si R 6 halogen and R 7 where each of R 5 , R 6 , and R 7 is hydrogen, halogen, unsubstituted or halogen-substituted C ⁇ -C 6 alkyl, unsubstituted or halogen-substituted C 2 -C 6 alkenyl, or unsubstituted or halogen-substituted phenyl.
  • the polymerization monomer used in preparing the oxygen enriching membrane of the invention is at least one addition polymerization monomer selected from the group consisting of ethylene, propylene, methyl methacrylate, and styrene, or at least one condensation polymerization monomer selected from the group consisting of terephthalate/ethylene glycol, bisphenol-A/diphenyl carbonate, phenol/aldehyde, and urea/aldehyde.
  • the air-permeable foaming agent used in preparing the oxygen enriching membrane of the invention is at least one selected from the group consisting of azobicarbonamide, p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and dinitrosopentamethylenetetramine.
  • FIG. 1 is a schematic view of metallosiloxane compounds adhered on the surface of metal oxide particles.
  • FIG. 2 is a schematic view of the pendant model showing motion of the metallosiloxane unit caused by relative pressure difference across the membrane.
  • FIG. 3 is a schematic view of an apparatus for testing oxygen enriching performance of the oxygen enriching membrane according to an embodiment of the present invention. ⁇ Symbols used in the drawings> 1 : oxygen enriching membrane 2: pressure gauge 3: flow meter
  • the metallosiloxane represented by Formula 2 can be prepared from any compound having a siloxyl group. Because the distance from the central metal to oxygen atoms is longer than usual covalent bonds, the binding force between them is relatively weak. Accordingly, the bond between the metal and oxygen is relatively easily dissociated by heat, and an acid or base, to give the metallosiloxane ion repressed by Formula 3 according to Scheme 1 below. [Scheme 1]
  • the metallic oxide (M 2 0) is present in the form of particles.
  • the process of Scheme 2 occurs at the surface of a metallic oxide (M 2 0) particle and the resultant metallosiloxane-metallic oxide compound has a structure shown in FIG. 1. Since the metallosiloxane-metallic oxide compound of the invention is present in the form of particles and is used in a powder form, a means to fix the particles or powders is required. In the present invention, woven or non-woven fabric may be used to fix the metallosiloxane-metallic oxide compound.
  • the metallosiloxane-metallic oxide compound powder is coated on woven or non-woven fabric to a predetermined thickness and another woven or non-woven fabric is laminated thereon.
  • a lamination membrane in which metallosiloxane-metallic oxide compound powder layer(s) is formed between the woven or non-woven fabric is obtained.
  • the lamination membrane itself can be used as an oxygen enriching membrane. Also, it can be laminated along with other lamination membranes to be described later as oxygen enriching membranes.
  • separation of a gaseous mixture through a porous membrane can be explained by the following four principles. First, Knudsen diffusion occurs when the pore size is smaller than the mean free path of a specific gas molecule. Second, surface diffusion occurs by interaction with the pore surface. Third, capillary diffusion occurs by condensation of a specific liquid.
  • FIG. 2 is a schematic diagram for illustrating the pendant model. According to the pendant model, a plurality of metallosiloxane units protruding inside the pore move freely like cilia.
  • the metallosiloxane units align almost vertically to the direction of the pore, as seen in FIG. 2 (a). If the pressure is relatively high, the metallosiloxane units align almost parallel to the direction of the pore, as seen in FIG. 2 (b).
  • the oxygen enriching membrane of the present invention not only offers superior oxygen selectivity and permeability even with a low pressure difference, but also has good strength and is not easily torn thanks to the lamination membrane structure. Also, since it is prepared by fixing the metallosiloxai e-metallic oxide compound in the powder form on woven or non-woven fabric and laminating them repeatedly, membranes with uniform pore size can be produced in large amounts.
  • the metallosiloxane unit moves freely, so that superior permeability and selectivity are obtained even at low pressure. Since the compound having 4 to 1000 siloxane units, the m and n values in Formula 1 , is suspended and fixed to the metallic oxide (M 2 0), it offers good oxygen enriching performance even with a low pressure difference by the pendant model. Besides laminating the metallosiloxane-metallic oxide compound powder, a method of dissolving the metallosiloxane compound in a polymerization monomer and polymerizing the monomer to obtain a membrane is practicable. The metallosiloxane represented by Formula 2 dissolves well in most monomers of matrix polymer resins.
  • the metallosiloxane After dissolving the metallosiloxane in a monomer of a matrix polymer resin to an adequate concentration, it is stirred sufficiently and the monomer is polymerized. Then, a polymer is obtained in which the metallosiloxane is uniformly distributed in the matrix. The resultant matrix polymer is coated on woven or non-woven fabric to obtain a lamination membrane. The resultant lamination membrane can act as an oxygen enriching membrane. Also, it is possible to prepare a membrane using an air-permeable foaming agent. That is, the metallosiloxane is added to a polymer which has not yet solidified just after polymerization. The polymer is stirred so ⁇ that the metallosiloxane is dispersed uniformly.
  • Sample A Preparation of aluminosiloxane-metallic oxide compound 2.7 kg of silica (Si0 2 ) sieved to 80 mesh was put in a kneader. 300 g of aluminosiloxane (150 g of Sc.101 and Sc.011 each, Silochem LTD.) was mixed with the silica. Kneading was performed for 60 minutes while heating to 200-250 ° C and rotating at 60-120 rpm, to obtain a metallosiloxane-silica compound.
  • Sample B-1 Preparation of aluminosiloxane emulsion for fabric coating 100 mL of MMA (methyl methacrylate), 100 mL of EMA (ethyl methacrylate), and 20 g of aluminosiloxane were put in a beaker. The mixture was stirred at room temperature to completely dissolve it (a monomer solution was obtained). A mixture of 1000 mL of distilled water, 10 g of sorbitan monolaurate polyethylene oxide (Tween 20), a surfactant, and 0.1 g of APS (ammonium persulfate), an initiator, was added to the reactor. The mixture was heated to 40 ° C while stirring (a surfactant solution was obtained). The monomer solution was added to the surfactant solution in a dropwise fashion. Reaction was performed at 80 °C for 4 hours to obtain an aluminosiloxane emulsion for fabric coating.
  • MMA methyl methacrylate
  • EMA ethyl
  • Sample B-2 Preparation of aluminosiloxane emulsion for fabric foam coating 0.3 wt% per 100 wt% of the polymer of a foaming agent was added to the aluminosiloxane emulsion (sample B-1 ), and dispersed uniformly.
  • Sample B-3 Preparation of polymer foaming master batch comprising aluminosiloxane 200 g of aluminosiloxane and 0.3 wt% per 100 wt% of the polymer of an air-permeable foaming agent were mixed with 800 g of PP to prepare a master batch.
  • Preparation Example 1 Aluminosiloxane-metallic oxide compound coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
  • the aluminosiloxane-metallic oxide compound powder (sample A) was put on the fabric and the vibrator was turned on, so that the powder penetrated the fabric.
  • a 1 :1 mixture of those having a particle size of 60 mesh and 120 mesh or one having a particle size of 80 mesh was used.
  • Preparation Example 2 Aluminosiloxane emulsion coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm x 30 cm.
  • the fabric was immersed in the emulsion of sample B-1 , dried in the air, and heated in an oven at 180 °C for 30 minutes for crosslinking.
  • Preparation Example 3 Aluminosiloxane emulsion foamed fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
  • the fabric was immersed in the emulsion of sample B-2, dried in the air, and heated to 165 °C for foaming.
  • Preparation Example 4 Preparation of polymer foam membrane comprising aluminosiloxane The master batch of sample B-3 was put in a mold and heated to the foaming temperature to obtain a polymer foam membrane comprising aluminosiloxane.
  • Preparation Example 5 Napped fabric comprising aluminosiloxane Fabric comprising aluminosiloxane was napped for use as a support of the masks used in the examples.
  • An oxygen enriching membrane prepared by laminating a metallosiloxane-metallic oxide compound and dissolving metallosiloxane in a monomer or foaming metallosiloxane in a polymer resin by adding an air-permeable foaming agent has superior oxygen permeability and selectivity, and good strength. In addition, mass production becomes possible and high quality is attained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne une membrane d'enrichissement en oxygène contenant un composé métallosiloxane-oxyde métallique, un composé métallosiloxane ou un mélange de ceux-ci, et son procédé de préparation. La membrane d'enrichissement en oxygène de la présente invention présente une perméabilité de l'oxygène et une sélectivité supérieures ainsi qu'une bonne résistance, elle permet également une production à grande échelle et présente une grande qualité.
PCT/KR2005/001856 2004-06-16 2005-06-16 Membrane d'enrichissement en oxygene a composes metallosiloxane-oxyde metallique contenant du metallosiloxane et son procede de preparation Ceased WO2005123750A1 (fr)

Applications Claiming Priority (2)

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KR1020040044444A KR20050119375A (ko) 2004-06-16 2004-06-16 금속 실록산을 이용한 산소부화막 및 그의 제조방법
KR10-2004-0044444 2004-06-16

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1914267A1 (fr) * 2006-10-17 2008-04-23 J & J Chemical Co. Agent gonflant modifié en surface par un composé siloxylé métallique et composition de polymère le comprenant
JP2008101210A (ja) * 2006-10-17 2008-05-01 J & J Chemical Co Ltd 発泡剤改質方法
US8512870B2 (en) 2009-12-30 2013-08-20 Cheil Industries, Inc. Transparent resin for encapsulation material and electronic device including the same
US8552251B2 (en) 2010-10-08 2013-10-08 Kimberly-Clark Worldwide, Inc. Article with health-benefit agent delivery system
US9238348B2 (en) 2010-10-08 2016-01-19 Kimberly-Clark Worldwide, Inc. Method of manufacture of article for delivering health-benefit agent
CN113244964A (zh) * 2021-06-03 2021-08-13 陕西延长石油（集团）有限责任公司 金属配合物催化剂及碳酸二苯酯的合成工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912880A (zh) * 2021-08-23 2022-01-11 四川新达粘胶科技有限公司 一种富氧膜及其制备方法

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Publication number Priority date Publication date Assignee Title
JPS61291018A (ja) * 1985-06-17 1986-12-20 Teijin Ltd 気体透過性積層体
KR20010018930A (ko) * 1999-08-24 2001-03-15 한정련 새로운 산소부화막

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JPS61291018A (ja) * 1985-06-17 1986-12-20 Teijin Ltd 気体透過性積層体
KR20010018930A (ko) * 1999-08-24 2001-03-15 한정련 새로운 산소부화막

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Title
LAI J.Y. ET AL: "TPX/Siloxane Blend Membrane for Oxygen", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 34, no. 2, 1987, pages 559 - 569 *
ZHANG J.-Y.: "Facilitated Oxygen Transport in a Novel Silicone Polymer Membrane Containing Carboxylic Cobalt Groups", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 90, no. 4, 2003, pages 1038 - 1044 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1914267A1 (fr) * 2006-10-17 2008-04-23 J & J Chemical Co. Agent gonflant modifié en surface par un composé siloxylé métallique et composition de polymère le comprenant
JP2008101210A (ja) * 2006-10-17 2008-05-01 J & J Chemical Co Ltd 発泡剤改質方法
EP1921107A3 (fr) * 2006-10-17 2008-12-24 J & J Chemical Co. Procédé de modification d'un agent d'expansion
US7939573B2 (en) 2006-10-17 2011-05-10 J & J Chemical Co. Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same
US8512870B2 (en) 2009-12-30 2013-08-20 Cheil Industries, Inc. Transparent resin for encapsulation material and electronic device including the same
US8552251B2 (en) 2010-10-08 2013-10-08 Kimberly-Clark Worldwide, Inc. Article with health-benefit agent delivery system
US9238348B2 (en) 2010-10-08 2016-01-19 Kimberly-Clark Worldwide, Inc. Method of manufacture of article for delivering health-benefit agent
CN113244964A (zh) * 2021-06-03 2021-08-13 陕西延长石油（集团）有限责任公司 金属配合物催化剂及碳酸二苯酯的合成工艺

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KR20050119375A (ko) 2005-12-21
TW200617016A (en) 2006-06-01

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