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WO2006096775A2 - Methode d'assemblage de monomeres poss - Google Patents

Methode d'assemblage de monomeres poss Download PDF

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Publication number
WO2006096775A2
WO2006096775A2 PCT/US2006/008262 US2006008262W WO2006096775A2 WO 2006096775 A2 WO2006096775 A2 WO 2006096775A2 US 2006008262 W US2006008262 W US 2006008262W WO 2006096775 A2 WO2006096775 A2 WO 2006096775A2
Authority
WO
WIPO (PCT)
Prior art keywords
poss
superbase
mixture
sioi
utilized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2006/008262
Other languages
English (en)
Other versions
WO2006096775A3 (fr
Inventor
Joseph J. Schwab
Yi-Zhong An
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hybrid Plastics Inc
Original Assignee
Hybrid Plastics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hybrid Plastics Inc filed Critical Hybrid Plastics Inc
Priority to CN2006800073735A priority Critical patent/CN101151298B/zh
Priority to EP06737433A priority patent/EP1856190A4/fr
Priority to JP2008500875A priority patent/JP2008537731A/ja
Publication of WO2006096775A2 publication Critical patent/WO2006096775A2/fr
Anticipated expiration legal-status Critical
Publication of WO2006096775A3 publication Critical patent/WO2006096775A3/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms

Definitions

  • This invention relates generally to a process for enhancing the properties of functionalized POSS monomers for incorporation into polymeric and biological products.
  • Nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS).
  • POSS systems contain hybrid (i.e. organic-inorganic) compositions in which the internal cage like framework is primarily comprised of inorganic silicon-oxygen bonds.
  • the exterior of the nanostructure is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic monomers and polymers.
  • Prior art methods include the use of hydroxide base, anionic salts, and protic acid catalysts in the assembly of POSS cages and their functionalization (see US Patent Application Nos. 09/631 ,892 and 10/186,318, and US Patent Nos. 6,770,724; 6,660,823; 6,596,821 ; and 3,390,163).
  • POSS is highly favorable when the cage size is monoscopic and the corresponding distribution of oligomers is 1.0.
  • the present invention provides an improved synthesis process for polyhedral oligomeric silsesquioxanes which produces rapidly, in high yield, low resin content, and solvent free, monomer products suitable for use in polymerization, grafting and alloying applications.
  • the synthesis process uses phosphazene superbases in reaction with silane coupling agents of the formula R 1 SiX 3 to form POSS cages
  • silanols of the formula types [(R 1 SiOi. 5 ) 7 (HOSiOi. 5 )i] ⁇ 8, [(R 1 SiOi. 5 )6(R 1 HOSiOi) 2 ] ⁇ 8l [(R 1 SiO 1 . S) 2 (R 1 HOSiOi) 4 ]Z 6 , [(R 1 SiOi. 5 )4(R 1 HOSiOi) 3 ] ⁇ 7 .
  • the synthesis process can also involve the reaction of phosphazene superbases in reaction with silane coupling agents of the type R 2 SiX 3 to form polyfunctional POSS cages functionalized with R 2 groups of the formula types [(R 2 SiOi ,5)e] ⁇ 6, [(R 2 SiOi.5) 8 ] ⁇ 8, [(R 2 SiOi. 5 )io] ⁇ io, [(R 2 SiOi. 5 ) 12 ] ⁇ 12 and larger sized cages.
  • the resulting monomer is essentially free of impurities and has controllable properties through selection of composition, R groups, and nanostructure size and topology. Highly purified nanostructured POSS monomers are desirable as they exhibit improved filtration capability, reduced contamination and viscosity, more reliable polymerization, lower cost and waste reduction over impure systems.
  • a preferred process involves the reaction of POSS silanols of the formula [(R 1 SiOi. 5 ) 7 (HOSiOi. 5 )i] ⁇ 8 , [(R 1 Sid , 5 ) 6 (R 1 HOSiOi ) 2 ] ⁇ 8 , [(R 1 SiOi. 5 ) 4 (R 1 HOSiOi ) 3 ] ⁇ 7 with a silane coupling agent of the formula, R 2 R 3 R 4 SiX, R 2 R 3 SiX 2 , R 2 SiX 3 in the presence of a solvent and superbase.
  • FIG. 1 shows a comparison of the prior art and improved silation process
  • FIG. 2 shows a variety of the preferred phosphazene superbases
  • FIG. 3 shows the structure of the compound synthesized in Example 5.
  • Polysilsesquioxanes are materials represented by the formula [RSiO 1 5 ]..
  • ⁇ molar degree of polymerization
  • R represents organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic groups that may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides or which may contain fluorinated groups).
  • Polysilsesquioxanes may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.
  • POSS and POS nanostructure compositions are represented by the formula:
  • R is the same as defined above and X includes but is not limited to OH, Cl, Br 1 I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR 2 ) isocyanate (NCO), and R.
  • composition forms a nanostructure and the symbol # refers to the number of silicon atoms contained within the nanostructure.
  • the value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically
  • the present invention teaches an improved method of synthesis for POSS nanostructured chemicals yielding a higher purity and lower cost product than previously described.
  • phosphazene superbases to catalyze the assembly of POSS cages.
  • a range of phosphazenes are applicable and include polyphosphazenes which vary in molecular weight and composition. Phosphazene oligomers and molecules are preferentially utilized and in particular P
  • Variables influencing the process include the size, polydispersity, and composition of the nanostructured chemical, separation and isolation methods, and use of catalyst or cocatalysts, solvents and cosolvents. Additionally, kinetic and thermodynamic means of controlling the synthesis mechanism, rate, and product distribution are also known tools of the trade that can impact product quality and economics.
  • exo-norbomenylethyltrimethoxysilane 4.84 g, 20 mmole
  • Phosphazene superbase was then added and the mixture stirred for 2 days at 5°C.
  • the solution was then quenched with acetic acid (87mg) filtered, and volatiles removed, washed with additional methanol and dried to render a white product.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une méthode de synthèse d'oligomères de silsesquioxanes polyhédriques avec des superbases de phosphazène en vue de produire à haut rendement un monomère à faible teneur en résine, exempt de solvant et de métal-trace, pouvant être utilisé dans des applications microélectroniques, biologiques et medicales impliquant une polymérisation, un greffage ou une action d'allier.
PCT/US2006/008262 2005-03-07 2006-03-07 Methode d'assemblage de monomeres poss Ceased WO2006096775A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2006800073735A CN101151298B (zh) 2005-03-07 2006-03-07 多面体低聚倍半硅氧烷单体组装的方法
EP06737433A EP1856190A4 (fr) 2005-03-07 2006-03-07 Methode d'assemblage de monomeres poss
JP2008500875A JP2008537731A (ja) 2005-03-07 2006-03-07 Ｐｏｓｓモノマー構築のためのプロセス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65972205P 2005-03-07 2005-03-07
US60/659,722 2005-03-07

Publications (2)

Publication Number Publication Date
WO2006096775A2 true WO2006096775A2 (fr) 2006-09-14
WO2006096775A3 WO2006096775A3 (fr) 2007-09-20

Family

ID=36954009

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/008262 Ceased WO2006096775A2 (fr) 2005-03-07 2006-03-07 Methode d'assemblage de monomeres poss

Country Status (7)

Country Link
EP (1) EP1856190A4 (fr)
JP (1) JP2008537731A (fr)
KR (1) KR101208460B1 (fr)
CN (1) CN101151298B (fr)
RU (1) RU2007137027A (fr)
TW (1) TWI433871B (fr)
WO (1) WO2006096775A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101376662B (zh) * 2007-08-31 2011-05-25 中国石油天然气股份有限公司 有机硅混合环体的精制方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7915436B2 (en) * 2008-11-03 2011-03-29 3M Innovative Properties Company Phosphorus-containing silsesquioxane derivatives as flame retardants
EP2865704A1 (fr) * 2013-10-28 2015-04-29 Huntsman International Llc Synthèse et utilisation de compositions de catalyseur comprenant des silsesquioxanes oligomères polyèdres métallisés
CN116102734B (zh) * 2022-12-29 2023-10-24 广州硅碳新材料有限公司 一种含磷氮笼型聚倍半硅氧烷、其制备方法及其作为结壳成炭剂的用途
CN120033324B (zh) * 2025-03-04 2025-11-25 重庆太蓝新能源有限公司 非水电解液和锂二次电池

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510441A (en) * 1993-07-15 1996-04-23 General Electric Company Process for producing octamethyltrisiloxane
US5420221A (en) * 1993-07-15 1995-05-30 General Electric Company Process for the production of linear organosiloxane polymers by disproportionation
US5457220A (en) * 1994-04-29 1995-10-10 General Electric Company Process for the production of crosslinked siloxanes by disproportionation
US5688888A (en) * 1996-04-08 1997-11-18 General Electric Company Peralkylated phosphazene base-catalyzed silanol condensation method
US5855962A (en) * 1997-01-09 1999-01-05 International Business Machines Corporation Flowable spin-on insulator
GB9703552D0 (en) * 1997-02-20 1997-04-09 Dow Corning Polymerisation of cyclosiloxanes in the presence of fillers
DE19719340A1 (de) * 1997-05-07 1998-11-12 Wacker Chemie Gmbh Verfahren zum Äquilibrieren und/oder Kondensieren von Organosiliciumverbindungen
US6770724B1 (en) * 1998-03-03 2004-08-03 The United States Of America As Represented By The Secretary Of The Air Force Altering of poss rings
GB9827068D0 (en) * 1998-12-09 1999-02-03 Dow Corning Polymerisation of siloxanes
CN1214034C (zh) * 1999-08-04 2005-08-10 杂混复合塑料公司 形成多面体低聚倍半硅氧烷的方法
WO2003064490A2 (fr) 2001-06-27 2003-08-07 Hybrid Plastics Llp Procede de fonctionnalisation de silsesquioxanes oligomeres polyhedriques
DE10156619A1 (de) * 2001-11-17 2003-05-28 Creavis Tech & Innovation Gmbh Verfahren zur Herstellung funktionalisierter oligomerer Silasesquioxane sowie deren Verwendung
JP4033731B2 (ja) * 2002-07-22 2008-01-16 旭化成株式会社 ケイ素化合物の製造法
SG149034A1 (en) * 2003-12-18 2009-01-29 Hybrid Plastics Inc Polyhedral oligomeric silsesquioxanes and metallized polyhedral oligomeric silsesquioxanes as coatings, composites and additives
WO2006132656A2 (fr) * 2004-09-10 2006-12-14 Hybrid Plastics, Inc. Resines nanocomposites destinees a etre utilisees a des temperatures elevees
JP2008523220A (ja) * 2004-12-07 2008-07-03 ハイブリッド・プラスティックス・インコーポレイテッド 高精製多面体オリゴマー状シルセスキオキサンモノマー

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of EP1856190A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101376662B (zh) * 2007-08-31 2011-05-25 中国石油天然气股份有限公司 有机硅混合环体的精制方法

Also Published As

Publication number Publication date
JP2008537731A (ja) 2008-09-25
WO2006096775A3 (fr) 2007-09-20
RU2007137027A (ru) 2009-04-20
KR101208460B1 (ko) 2012-12-05
EP1856190A2 (fr) 2007-11-21
CN101151298A (zh) 2008-03-26
EP1856190A4 (fr) 2011-02-09
TW200702361A (en) 2007-01-16
KR20080002803A (ko) 2008-01-04
CN101151298B (zh) 2012-07-11
TWI433871B (zh) 2014-04-11

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