WO2001087825A1 - Procedes, compositions et catalyseurs bi-fonctionnels pour la synthese de silice, verre, silicones et polymetallo-oxanes a basse temperature et a ph neutre - Google Patents

Procedes, compositions et catalyseurs bi-fonctionnels pour la synthese de silice, verre, silicones et polymetallo-oxanes a basse temperature et a ph neutre Download PDF

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Publication number
WO2001087825A1
WO2001087825A1 PCT/US2001/011481 US0111481W WO0187825A1 WO 2001087825 A1 WO2001087825 A1 WO 2001087825A1 US 0111481 W US0111481 W US 0111481W WO 0187825 A1 WO0187825 A1 WO 0187825A1
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WIPO (PCT)
Prior art keywords
reactant
catalyst
silicon
silica
halide
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PCT/US2001/011481
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English (en)
Inventor
Daniel E. Morse
Yan Zhou
Galen D. Stucky
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The Regents Of The University Of California
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Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Priority to AU2001255269A priority Critical patent/AU2001255269A1/en
Priority to US10/478,118 priority patent/US20040146445A1/en
Publication of WO2001087825A1 publication Critical patent/WO2001087825A1/fr
Priority to US10/807,004 priority patent/US7335717B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used

Definitions

  • the present invention relates to a process of synthesizing silica, glass, silicones, and polymetallooxanes, and to the catalytic composition used.
  • Silicon the second most abundant element on Earth, is widely used in the manufacture of siloxane-based semiconductors, glasses, ceramics, plastics, elastomers, resins, mesoporous molecular sieves and catalysts, optical fibers and coatings, insulators, moisture shields, photoluminescent polymers, and cosmetics [Auner, N. and Weis., J. (1998) Organosilicon Chemistry III: From Molecules to Materials, Wiley WCH; Auner, N. and Weis., J. Organosilicon Chemistry IV: From Molecules to Materials, Wiley WCH (in press); and Ball, P. (1997) Made to Measure: New Materials for the 21 st Century, Princeton University Press, Princeton, NJ, USA]. The manufacture of these materials typically requires high temperatures or the use of caustic chemicals.
  • amorphous silica the simplest siloxane [(Si0 2 ) n ]
  • amorphous silica the simplest siloxane [(Si0 2 ) n ]
  • is accomplished under mild physiological contitions producing a remarkable diversity of extremely structured shells, spines, fibers, and granules in many protists, diatoms, sponges, molluscs and higher plants [Simpson, T.L. and Volcani, B.E. (1981) Silicon and Siliceous Structures in Biological Systems, Springer- Verlag; and Voronkov, M.G., Zelchan, G.I. and Lukevits, E.J. (1997) Silicon and Life (2 nd ed.), Zinatne Publishing, Vilnius, Lithuania].
  • Hildebrand et al., made a significant breakthrough by cloning and characterizing the cDNA encoding the first silicic-acid [Si(OH) 4 ] transporter to be unequivocally identified [Hildebrand, M., Volcani, B.E., Gassman, W., & Schroeder, J.I. (1997) Nature 385, 688-689]. They showed, by analysis of the encoded protein and by injection of the mRNA (synthesized in vitro from the cloned cDNA) into Xenophus eggs, that the transporter protein forms a sodium-dependent transmembrane ion channel that mediates the transport of silicic acid.
  • this protein can account for the uptake of the silica precursor from the dilute pool of silicic acid in oceanic and fresh water, and similar transporters may pump silicic acid (or its conjugates) into the lumen of the silica-deposition vesicle (silicalamella), in which polycondensation (polymerization) is known to occur.
  • Kroger, et al. have cloned and characterized cDNAs encoding two families of protein (at least one of which is glycosylated) that contribute to the organic sheath surrounding the silica walls of a diatom [Kroger, N., Bergsdorf, C. and Sumper, M. (1994) EMBO J.
  • the present invention overcomes the drawbacks of prior efforts to synthesize materials of silica, glass, and polymetallooxanes at low temperatures and neutral pH.
  • the method of the present invention for synthesis of silica, silicone, glass, and polymetallo-oxane comprises placing a reactant, wherein the reactant comprises a silicon alkoxide, metal alkoxide, silicon halide or metal halide, or organic conjugates of the foregoing, in a container or mold having at least one predetermined dimension, whereby to determine the shape of the silica, silicone, glass, or polymetallo-oxane; and adding an effective amount of a catalyst to the reactant to form silica, silicone, glass, or polymetallooxane materials at about neutral pH and at an ambient temperature.
  • the predetermined dimension of the container or mold is microscopic, nanoscopic, or a combination thereof.
  • Other molecules or materials can be added to either the container or the reactant so that the molecule or material that is added is coated with the resulting synthesized silica, silicone, glass, or polymetallooxane.
  • a compatibilizing solvent including dimethylformamide or dimethylsulfoxide is added to the mixture prior to the addition of the catalyst.
  • the catalyst of the present invention comprises a compound having a nucleophilic functionality and a hydrogen-bonding acceptor group, whereby to assemble, hydrolyze, and condense the reactant at about neutral pH and at ambient temperature.
  • a silicified structure synthesized according to the above method is also disclosed, the structure assuming a shape determined by the container or mold.
  • the present invention also discloses a composition for use in synthesizing silica, silicone, glass, or polymetallooxane, the composition comprising a silicon alkoxide, metal alkoxide, silicon halide or metal halide and a catalyst that assembles, hydrolyzes, and condenses the silicon alkoxide, metal alkoxide, silicon halide or metal halide at about neutral pH and at ambient temperature.
  • a bifunctional catalyst comprising a compound having a nucleophilic functionality (such as, but not confined to -SH, -OH, etc.) and a hydrogen- bonding acceptor group (such as, but not confined to -NH, -NH 2 , etc.), whereby to assemble, hydrolyze, and condense a reactant of a silicon alkoxide, metal alkoxide, silicon halide or metal halide at about neutral pH and at ambient temperature.
  • the catalyst comprises such structures as Cysteamine, Hydroxylamine, Ethanolamine, Hydroxyalkylamines, and Mercaptoalkylamines.
  • Advantages of the invention over previously available technology include: (1) protection of acid-sensitive, alkali-sensitive, and heat-sensitive molecules, materials, objects or substances during the encapsulation or sealing process (in contrast to the exposure to acid, alkali, and/or heat required in present technologies; (2) the ability to rapidly coat, insulate, seal, encapsulate, package or sheath the sensitive materials and components itemized above, in either permeable or impermeable coatings of silica, glass or silicones with a wide range of physical (barrier and mechanical) properties, without their exposure to heat, and (3) the use of environmentally benign conditions for synthesis, with lower energy and capital costs than required by previously available technology.
  • the new catalysts and methods for their use described here make possible the synthesis of shape-controlled impermeable or semi-permeable coatings, membranes, sealants, encapsulants, insulators, polymers and materials of silica, glass, silicones and polymetallooxanes with unique advantages for the encapsulation and protection of sensitive materials and components at low temperatures and neutral pH, thus, without the requirement for exposure to any acid, alkali, or heat.
  • Potential applications include: coatings, sealants, insulators and encapsulants for a wide range of sensitive materials, including electronic, optoelectronic (photonic) circuits and components; medical implants and sensors; medical diagnostics based on immobilized or encapsulated enzymes, antibodies, living cells, receptors, hormones, and nucleic acids (DNA or RNA); sensors for chemical and biological toxic and infectious agents; foods; pharmaceuticals; biologicals; nutraceuticals; and cosmetics.
  • Figures 1(a-c) illustrate the luminescence of the photoprotein Green Fluorescent Protein (GFP) encapsulated in a silica gel produced from the reactant tetraethoxysilane with or without the added catalyst. No polymerization occurred without a catalyst (Fig. 1a), whereas gels formed to encapsulate the luminescent protein when the catalysts ethanolamine (Fig. 1b) or cysteamine (Fig. 1c) were added.
  • GFP photoprotein Green Fluorescent Protein
  • Figures 2(a-c) illustrate the activity of the bioluminescence-producing enzyme luciferase encapsulated in a silica gel produced from the reactant tetraethoxysilane, with or without added catalyst. No polymerization occurred without catalyst (Fig. 2a), whereas gels formed under the influence of the catalysts ethanolamine (Fig. 2b) and cysteamine (Fig. 2c ).
  • the catalysts of the present invention include but are not confined to such structures as Cysteamine, Hydroxylamine, Hydroxyalkylamine, and Mercaptoalkylamines, and include both a nucleophilic functionality (such as, but not confined to -SH, -OH, etc.) and a hydrogen-bonding acceptor group (such as, but not confined to -NH, -NH 2 , etc.).
  • the catalysts mimic the in vivo activity of proteins that control silicification in marine organisms.
  • the marine sponge, Tethya aurantia produces copious silica spicules (1-2mm length x 30 ⁇ m diameter) that constitute 75% of the dry weight of the organism.
  • spicules each contain a central axial filament of protein (1- 2mm length x 2 ⁇ m diameter) consisting of three very similar subunits named silicateins (for silica proteins) [Shimizu, K., Cha, J., Stucky, G.D., & Morse, D.E. (1998) Proc. Natl. Acad. Sci. 95, 6234-6238].
  • silicateins for silica proteins
  • the precursor solution or reactant mixture Prior to the start of the synthesis reaction (generally, but not necessarily initiated by addition of the catalyst), the precursor solution or reactant mixture is placed in a container or mold (of microscopic, microscopic and/or nanoscopic dimensions) to determine the shape of the final product. Additional levels of structural control can be imposed by organization with self-assembling surfactants, block copolymers (for example, poly(L-
  • the mold and the precursor solution or mixture also contain any molecules, materials, objects or substances to be coated, sealed or encapsulated by the resulting silica, glass, silicone or polymetallooxane.
  • Addition of the catalyst (and mixing with the precursor solution or mixture) then initiates rapid synthesis of the corresponding silica, glass, silicone or polymetallo-oxane at neutral pH, without the requirement for any heating, and without the requirement for exposure to any acid, alkali, or caustic chemicals.
  • a reactant including a silicon or metal alkoxide or halide (silicon or metal) (such as, tetraethoxysilane, also known as tetraethoxy-ortho-silicate), or organically substituted silicon or metal alkoxide or halide (such as, methyltriethoxysilane) is mixed with an effective amount (catalytic amount) of the catalyst (such as, a buffered aqueous solution of 0.1 M Cysteamine in 0.001 M tris-hydroxymethylaminomethane-HCI buffer at pH 7.0) with or without a compatibilizing solvent (such as, dimethylformamide or dimethylsulfoxide) to yield either one-phase or two-phase reaction mixtures, as desired.
  • Volume ratios of [reactant] : [catalyst] : [solvent] are in the range of about [1.0] : [0.01 - 1.0] : [0 -1.0]
  • polymerization is allowed to proceed either with or without further mixing, templating, molding, hydrodynamic shear, extrusion, or other liquid-processing methods, with or without added dopants, dyes, lumiphores, fluorors, enzymes, antibodies, receptors, cells or other physical, chemical or biological inclusions, at low temperature and neutral pH, for times ranges from 10 minutes to 24 hours, until the desired gel or solid polymer network is formed.
  • the final product may then be washed and dried, or maintained in various solvents, as appropriate for the specific application and compatible with the incorporated inclusions.
  • Figures 1 (a-c) and Figures 2(a-c) illustrate the efficacy of two specific catalysts of the present invention.
  • Figures 1(a-c) illustrate the luminescence of the photoprotein Green Fluorescent Protein (GFP) incorporated in silica gels produced from the reactant tetraethoxysilane, no polymerization to form a gel occurred at neutral pH and low temperature in the control condition without a catalyst (Fig. 1a), accordingly, no fluorescent protein is evident.
  • the luminescence of protein retained by progressively more cross-linked gels, which were formed under the influence of the catalysts Ethanolamine (Fig. 1b) and Cysteamine (Fig. 1c), was seen also at neutral pH and low temperature.
  • Figures 2(a-c) illustrate the activity of the bioluminescence-producing enzyme, luciferase, incorporated in silica gels produced from the reactant tetraethoxysilane, no polymerization to form a gel occurred at neutral pH and low temperature in the control condition without catalyst (Fig. 2a); accordingly, no enzyme was retained, and no luminescence was produced upon addition of the substrate (luciferin), retention of enzyme and production of light from luciferin, by progressively more cross-linked gels formed under the influence of the catalysts Ethanolamine (Fig. 2b) and Cysteamine (Fig. 2c ) under the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne des compositions catalytiques uniques et des procédés d'utilisation de ces compositions dans lesquelles les catalyseurs comprennent un fonctionnalité nucléophile et un groupe accepteur de liaison hydrogène et sont utilisés dans la synthèse de silice, verre, silicones et polymétallo-oxanes à de basses températures et à un pH voisin de la neutralité.
PCT/US2001/011481 1998-12-18 2001-04-04 Procedes, compositions et catalyseurs bi-fonctionnels pour la synthese de silice, verre, silicones et polymetallo-oxanes a basse temperature et a ph neutre WO2001087825A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2001255269A AU2001255269A1 (en) 2000-04-04 2001-04-04 Methods, compositions and bi-functional catalysts for synthesis of silica, glass, silicones
US10/478,118 US20040146445A1 (en) 2001-04-04 2001-04-04 Methods, compositions, and bi-functional catalysts for synthesis of silica, glass, silicones
US10/807,004 US7335717B2 (en) 1998-12-18 2004-03-22 Methods, compositions, and biomimetic catalysts for the synthesis of silica, polysilsequioxanes, polysiloxanes, non-silicon metalloid-oxygen networks, polymetallo-oxanes, and their organic or hydrido conjugates and derivatives

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Application Number Priority Date Filing Date Title
US19456800P 2000-04-04 2000-04-04
US60/194,568 2000-04-04

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297678B2 (en) 2003-03-12 2007-11-20 Genencor International, Inc. Use of repeat sequence protein polymers in personal care compositions
US7361731B2 (en) 2002-05-20 2008-04-22 Genencor International, Inc. Peptide derivatives, and their use for the synthesis of silicon-based composite materials
US7381789B2 (en) 2002-05-20 2008-06-03 Genencor International, Inc. Synthesis of inorganic structures using templation and catalysis by self assembled repeat protein polymers
WO2008137502A1 (fr) * 2007-05-04 2008-11-13 University Of Massachusetts Compositions à base de silicates mésoporeux fortement condensés et procédés associés
US7456147B2 (en) 2003-05-14 2008-11-25 Dow Corning, Corporation Controlled release of active agents utilizing repeat sequence protein polymers
US7648925B2 (en) 2003-04-11 2010-01-19 Vitex Systems, Inc. Multilayer barrier stacks and methods of making multilayer barrier stacks
US7691806B2 (en) 2003-05-14 2010-04-06 Genencor International, Inc. Repeat sequence protein polymer active agent congjugates, methods and uses
US7767498B2 (en) 2005-08-25 2010-08-03 Vitex Systems, Inc. Encapsulated devices and method of making
US8273704B2 (en) 2003-03-12 2012-09-25 Danisco Us Inc. Use of repeat sequence protein polymers in personal care compositions
US8383755B2 (en) 2007-06-19 2013-02-26 Brock University Enzyme-medicated cross-linking of silicone polymers
US8590338B2 (en) 2009-12-31 2013-11-26 Samsung Mobile Display Co., Ltd. Evaporator with internal restriction
US8900366B2 (en) 2002-04-15 2014-12-02 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
US8955217B2 (en) 1999-10-25 2015-02-17 Samsung Display Co., Ltd. Method for edge sealing barrier films
CN104876223A (zh) * 2015-05-04 2015-09-02 河南师范大学 一种鸡蛋壳型二氧化硅微米球的制备方法
US9184410B2 (en) 2008-12-22 2015-11-10 Samsung Display Co., Ltd. Encapsulated white OLEDs having enhanced optical output
US9337446B2 (en) 2008-12-22 2016-05-10 Samsung Display Co., Ltd. Encapsulated RGB OLEDs having enhanced optical output
US9839940B2 (en) 2002-04-15 2017-12-12 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
US10950821B2 (en) 2007-01-26 2021-03-16 Samsung Display Co., Ltd. Method of encapsulating an environmentally sensitive device
CN115612860A (zh) * 2022-10-26 2023-01-17 云南驰宏资源综合利用有限公司 一种高硅锌焙烧矿的浸出方法

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JPH05284979A (ja) * 1992-04-13 1993-11-02 Nippon Seibutsu Sangyo Kk 微生物菌体ｓｋｓを使用したシリカの製造法
WO2000035993A1 (fr) * 1998-12-18 2000-06-22 The Regents Of The University Of California Procedes, compositions et catalyseurs biomimetiques pour syntheses in vitro de silice, de polysilsequioxane, de polysiloxane et de polymetallo-oxanes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124418A (en) * 1973-04-19 1978-11-07 Thiokol Corporation Siloxane-coated ammonium perchlorate and propellant compositions made therewith
US4212826A (en) * 1978-06-16 1980-07-15 Wakunaga Yakuhin Kabushiki Kaisha Process for producing cysteamines and/or cystamines
US5166435A (en) * 1983-12-06 1992-11-24 Akzo N.V. Process for the preparation of a hydroxylamine
JPH05284979A (ja) * 1992-04-13 1993-11-02 Nippon Seibutsu Sangyo Kk 微生物菌体ｓｋｓを使用したシリカの製造法
WO2000035993A1 (fr) * 1998-12-18 2000-06-22 The Regents Of The University Of California Procedes, compositions et catalyseurs biomimetiques pour syntheses in vitro de silice, de polysilsequioxane, de polysiloxane et de polymetallo-oxanes

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8955217B2 (en) 1999-10-25 2015-02-17 Samsung Display Co., Ltd. Method for edge sealing barrier films
US8900366B2 (en) 2002-04-15 2014-12-02 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
US9839940B2 (en) 2002-04-15 2017-12-12 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
US7361731B2 (en) 2002-05-20 2008-04-22 Genencor International, Inc. Peptide derivatives, and their use for the synthesis of silicon-based composite materials
US7381789B2 (en) 2002-05-20 2008-06-03 Genencor International, Inc. Synthesis of inorganic structures using templation and catalysis by self assembled repeat protein polymers
US7297678B2 (en) 2003-03-12 2007-11-20 Genencor International, Inc. Use of repeat sequence protein polymers in personal care compositions
US8048859B2 (en) 2003-03-12 2011-11-01 Danisco Us Inc. Use of repeat sequence protein polymers in personal care compositions
US8273704B2 (en) 2003-03-12 2012-09-25 Danisco Us Inc. Use of repeat sequence protein polymers in personal care compositions
US7648925B2 (en) 2003-04-11 2010-01-19 Vitex Systems, Inc. Multilayer barrier stacks and methods of making multilayer barrier stacks
US7456147B2 (en) 2003-05-14 2008-11-25 Dow Corning, Corporation Controlled release of active agents utilizing repeat sequence protein polymers
US7691806B2 (en) 2003-05-14 2010-04-06 Genencor International, Inc. Repeat sequence protein polymer active agent congjugates, methods and uses
US7767498B2 (en) 2005-08-25 2010-08-03 Vitex Systems, Inc. Encapsulated devices and method of making
US10950821B2 (en) 2007-01-26 2021-03-16 Samsung Display Co., Ltd. Method of encapsulating an environmentally sensitive device
US7740821B2 (en) 2007-05-04 2010-06-22 The University Of Massachusetts Highly condensed mesoporous silicate compositions and methods
WO2008137502A1 (fr) * 2007-05-04 2008-11-13 University Of Massachusetts Compositions à base de silicates mésoporeux fortement condensés et procédés associés
US8383755B2 (en) 2007-06-19 2013-02-26 Brock University Enzyme-medicated cross-linking of silicone polymers
US9337446B2 (en) 2008-12-22 2016-05-10 Samsung Display Co., Ltd. Encapsulated RGB OLEDs having enhanced optical output
US9184410B2 (en) 2008-12-22 2015-11-10 Samsung Display Co., Ltd. Encapsulated white OLEDs having enhanced optical output
US9362530B2 (en) 2008-12-22 2016-06-07 Samsung Display Co., Ltd. Encapsulated white OLEDs having enhanced optical output
US8904819B2 (en) 2009-12-31 2014-12-09 Samsung Display Co., Ltd. Evaporator with internal restriction
US8590338B2 (en) 2009-12-31 2013-11-26 Samsung Mobile Display Co., Ltd. Evaporator with internal restriction
CN104876223A (zh) * 2015-05-04 2015-09-02 河南师范大学 一种鸡蛋壳型二氧化硅微米球的制备方法
CN115612860A (zh) * 2022-10-26 2023-01-17 云南驰宏资源综合利用有限公司 一种高硅锌焙烧矿的浸出方法
CN115612860B (zh) * 2022-10-26 2023-09-19 云南驰宏资源综合利用有限公司 一种高硅锌焙烧矿的浸出方法

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