WO2007022367A2 - Preparation of polyhedral oligomeric silsesquioxane silanols and siloxides functionalized with olefinic groups - Google Patents
Preparation of polyhedral oligomeric silsesquioxane silanols and siloxides functionalized with olefinic groups Download PDFInfo
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- WO2007022367A2 WO2007022367A2 PCT/US2006/032166 US2006032166W WO2007022367A2 WO 2007022367 A2 WO2007022367 A2 WO 2007022367A2 US 2006032166 W US2006032166 W US 2006032166W WO 2007022367 A2 WO2007022367 A2 WO 2007022367A2
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- silanol
- siloxide
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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 System
- C07F7/02—Silicon compounds
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Definitions
- This invention relates to a process for functionalization of polyhedral oligomeric silsesquioxane silanols and siloxides with olefinic groups, enhancing their physical, chemical, and electronic properties, and their suitability for incorporation into catalytic, metallic, polymeric, electronic, medical, cosmetic, and biological products.
- Nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS).
- POSS and POS systems contain hybrid (i.e. organic-inorganic) compositions in which the internal cage framework is primarily comprised of rigid 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 and inorganic materials.
- POSS silanols bearing one or more different R groups on the same POSS silanol cage molecule It is especially desirable to produce POSS cages with reactive olefinic groups R 2 which can participate in other chemistry than that available to the R 1 groups and the silanols or siloxides ( Figure 1).
- the present invention describes synthetic methods of preparing POSS or POS cage compositions bearing combinations of hydrophobic, hydrophilic, saturated, unsaturated, and biologically active R groups on the same molecule.
- a synthetic process that renders polyhedral oligomeric silsesquioxane and polyhedral oligomeric silsesquioxane silanols and siloxides rapidly, in high yield, and containing wholly olefinic groups, or mixtures of olefinic and aromatic or alkyl, or biologically compatible groups is provided.
- the process involves the use of hydroxide bases with silane coupling agents of the formula R 1 SiX 3 and R 2 SiX 3 to form POSS cages functionalized with silanols of the formula types [(R 1 SiOi.s) 7-
- the olefin groups can be subsequently derivatized though oxidative addition reactions, reductive addition reactions, metathesis, or polymerization as a means to afford additional properties such as polarity, hydrophobicity, lubrication, and biological compatibility or to immobilize to the POSS cage while rendering the silanols or siioxides for surface modification, reactive silation, or association with metals or other materials.
- FIG. 1 shows a representative formula of a POSS cage bearing silanol/siloxide groups and two types of organic groups where the R 1 and R 2 groups are randomly incorporated into the cage.
- FIG. 2 shows a mass spectrum of products from Example 1. DEFINITION OF FORMULA REPRESENTATIONS FOR NANOSTRUCTURES
- Polysilsesquioxanes are materials represented by the formula [RSiO 1 5 ] ⁇
- R represents an 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, silicones, or aliphatic and aromatic groups).
- Polysilsesquioxanes may be either homoleptic or heteroleptic.
- the designation R includes R 1 and R 2 functionalities. 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, ONa, OLi, OK, OCs, Cl, Br, I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR 2 ), isocyanate (NCO), and R.
- m and n refer to the stoichiometry of the composition.
- # 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
- the present invention teaches a method for polyhedral oligomeric silsesquioxane (POSS) or polyhedral oligomeric silicate (POS) synthesis that renders mixtures of dissimilar R groups on the cage.
- a key feature of the invention is the use of synergistically tolerant stoichiometric ratios of R 1 SiX 3 and R 2 SiX 3 silane coupling agents which allow for statistical incorporation of two types of organic groups (R 1 and R 2 ) into the same cage while preserving the POSS silanol/siloxide groups. Additionally, the ability to prepare cages with R-groups bearing unsaturated functionality allows for the further functionalization of the POSS cage.
- Preferred POSS silanol formula types include [(R 1 SiO L s) 7 - X (R 2 SiO L5 )X(HOSiOL 5 )I] 18 , [(R 1 SiOLs) 6 -X(R 2 SiO 1 . 5 ) X (R 1 HOSiOi) 2- x(R 2 HOSiOi) x ] ⁇ 8) [(R 1 Si ⁇ L5 ) 2 -x(R 2 SiOi.
- POSS silanol/siloxides bearing a mixture of olefinic R 2 and aliphatic R 1 groups a valuable tool in the utility of this process is to maintain an approximately 15:85 to 25:75, and preferably a 20:80 molar ratio of the two R 1 SiX 3 and R 2 SiX 3 silane coupling agents. This is particularly effective when incorporating vinyl and isobutyl groups into the same POSS cage.
- POSS silanol/siloxide cages in which all R groups are olefinic can also be prepared in a similar manner through variation of the ratio to the extreme of 100:0. The process is valid for all conceivable compositional ranges of R 1 SiX 3 and R 2 SiX 3 .
- Olefinic groups on POSS cages can be subsequently derivatized though any number of oxidation or addition reactions. These include metathesis (U.S. Patent No. 5,942,638) or oxidation reactions (U.S. Patent Nos. 6,100,417 and 6,767,930), addition reactions (U.S. Patent Nos. 5,939,576 and 5,047,492), or polymerizations.
- This advancement in the art of POSS provides the ability to carry out chemical derivatization of the R groups while maintaining nonreactive R groups on the cage and reactive silanol/siloxide groups.
- Variables influencing the process include the size, polydispersity, and composition of the nanostructured chemicals, 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.
- the desired mixed R group POSS cages were then extracted into an organic layer through the addition of pentane (100 ml_), and aqueous NaCI.
- the organic layer was then washed with a 4 wt.-% HCI solution (3 x 100 ml_), and the volatiles were removed under reduced pressure.
- the desired products were collected as white solids and verified by MALDI-TOF and 1 H NMR spectroscopy.
- MALDI-TOF spectra include M/Z for the parent POSS formula and an associated sodium atom from the ablation matrix. See Figure 2.
- the desired product was extracted into an organic layer by addingiOOml of pentane and stirring for 30 minutes followed by addition of NaCI.
- the pentane layer was removed and washed three additional times with 100ml of a 4wt% HCL solution.
- the organic volatiles were removed under reduced pressure and the desired product was isolated (9.6g, 55.8%) as white solid in the compound was analyzed using MALDI-TOF-MS and identified as [((CH 3 ) 2 CHCH 2 )SiOi .5) 4 ((CH 2 CH)(OH)SiOi ,o)3] ⁇ 7 .
- reaction mixture was quenched into a solution of water (150 mL) and phosphoric acid (2.02 mL, 1.5 eq relative to LiOH » H 2 O).
- An oily phase separated and was stirred for 1 hr. Hexane/THF were added to the quench to give a homogeneous organic phase and the organic phase washed with successive portions. of water and saturated brine.
- the organic phase was separated, dried over MgSO 4 , filtered and then removed by rotary evaporation to provide a foamy solid which was dried by vacuum to provide 7.Og (98%) of a mixture of the desired
- polymeric resin [((C-C 6 H 9 )CH 2 CH 2 SiOi .5) 4 ((c-C 6 H 9 )CH 2 CH 2 (OH)SiOi .ofel ⁇ oo in a
- reaction mixture was then quenched into a solution of water (150 ml_) and phosphoric acid (1.82 imL, 1.5 eq relative to LiOH»H 2 O) and the heterogeneous quench mixture stirred for 1 hr. Hexane/THF were added to the quench to give a homogeneous organic phase and the organic phase washed with successive portions of water and saturated brine. The organic phase was separated, dried over MgSO 4 , filtered and then the solvent removed by rotary evaporation to provide a white solid which was stirred with acetone and collected by vacuum filtration to provide 5.4g (93%) of the desired product.
- reaction mixture was warmed to room temperature and allowed to stir for 16 hr.
- the reaction was quenched with 1 N HCI (1OmL) and hexane (10 mL) added.
- the mixture was stirred well and the organic phase separated and washed once with saturated brine.
- the solvent was removed by rotary evaporation to give a solid paste, which upon stirring with acetone (50 mL) and methanol (50 mL) gave a white solid which was collected by vacuum filtration, washed with methanol and dried to provide 4.01 g (72%) of the product as a white solid.
- MCM zeolite type catalyst materials were prepared under the same conditions with variation of the [(C4H 9 SiOi.5)4(C3H5SiOi.5)3((H3C) 2 HCOTiOi.5)i] ⁇ 8)/t ⁇ tra ⁇ thylorthosilicate (TEOS) molar ratio.
- Water 6.0 g (0.33 mol) was mixed with 4.77 g NH 4 OH (30 wt.-% NH 3 ; 0.07 mol NH 3 ) and stirred for 1 min.
- To this solution was added 0.33 g cetyltrimethylammonium bromide CTABr (0.91 mol) and the solution was stirred for 0.5 h at room temperature.
- Example 17 General procedure for Hydroformylation of Olefinic POSS.
- a solution of PtCI 2 (Sixantphos), (0.016 g, 0.019 mmol) and SnCI 2 (0.0036 g, 0.019 mmol) in CH 2 CI 2 (5 mL) was stirred for 1 hour, than transferred into a stainless steel autoclave (100 mL internal volume). Additional CH 2 CI 2 (15 mL) was added, followed by heating of the autoclave to 60 0 C and subsequent inlet of synthesis gas (CO / H 2 ratio 1 :1) to 40 bar.
- synthesis gas CO / H 2 ratio 1 :1
- the autoclave was allowed to equilibrate for one hour, than a solution of silsesquioxane in CH 2 CI 2 (total volume, 10 mL) was added, and the reaction was run at 60 °C/40 bar for 17 hours.
- the autoclave was cooled in ice and depressurized, after which the reaction mixture was evaporated to dryness. Pentane (20 mL) was added, and the catalyst was filtered off. Evaporation of the filtrate gave the hydroformylated POSS product.
- the products were characterized by multinuclear NMR spectroscopy.
- Other hydroformylation catalysts such as [Rh(Acac)/(CO) 2 ]/Xantphos can also be utilized.
Abstract
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Priority Applications (2)
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JP2008527138A JP2009504890A (en) | 2005-08-16 | 2006-08-16 | Preparation of polyhedral oligomeric silsesquioxane silanols and siloxanes functionalized with olefinic groups |
EP06801756A EP1931687A4 (en) | 2005-08-16 | 2006-08-16 | Preparation of polyhedral oligomeric silsesquioxane silanols and siloxides functionalized with olefinic groups |
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US70896605P | 2005-08-16 | 2005-08-16 | |
US60/708,966 | 2005-08-16 |
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WO2007022367A2 true WO2007022367A2 (en) | 2007-02-22 |
WO2007022367A3 WO2007022367A3 (en) | 2009-04-30 |
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EP (1) | EP1931687A4 (en) |
JP (1) | JP2009504890A (en) |
KR (1) | KR20080036148A (en) |
CN (1) | CN101568546A (en) |
RU (1) | RU2008110068A (en) |
TW (1) | TW200722430A (en) |
WO (1) | WO2007022367A2 (en) |
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JP2008138203A (en) * | 2006-11-29 | 2008-06-19 | Dongjin Semichem Co Ltd | Monomer, polymer, and organic composition containing the same for forming organic anti-reflection film |
EP1957563B1 (en) * | 2005-11-28 | 2010-04-28 | The Welding Institute | Process for the production of organosilsesquioxanes |
CN102492078A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Acrylic acid and polyhedral silsesquioxane copolymerized hydrogel, its preparation method and its purpose |
US9035009B2 (en) | 2007-04-17 | 2015-05-19 | Kaneka Corporation | Polyhedral polysiloxane modified product and composition using the modified product |
US9688851B2 (en) | 2010-05-28 | 2017-06-27 | Kaneka Corporation | Polysiloxane composition, hardened material and optical device |
US9698320B2 (en) | 2010-09-22 | 2017-07-04 | Kaneka Corporation | Modified product of polyhedral structure polysiloxane, polyhedral structure polysiloxane composition, cured product, and optical semiconductor device |
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JP5119843B2 (en) * | 2007-10-09 | 2013-01-16 | 宇部興産株式会社 | Method for producing cage-type silsesquioxane derivative |
CN102010438A (en) * | 2010-11-11 | 2011-04-13 | 陕西科技大学 | Amino-containing cage type silsesquioxane and preparation method thereof |
JP6202431B2 (en) * | 2012-09-04 | 2017-09-27 | 学校法人神奈川大学 | Cage-type silsesquioxane derivatives |
EP2865704A1 (en) * | 2013-10-28 | 2015-04-29 | Huntsman International Llc | Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions |
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JPH08113648A (en) * | 1994-10-18 | 1996-05-07 | Showa Denko Kk | Production of silyl-terminated polysilsesquioxane |
JP3635180B2 (en) * | 1997-02-24 | 2005-04-06 | ダウ コーニング アジア株式会社 | Silylated polymethylsilsesquioxane, process for producing the same, and composition using the same |
US5942638A (en) * | 1998-01-05 | 1999-08-24 | The United States Of America As Represented By The Secretary Of The Air Force | Method of functionalizing polycyclic silicones and the resulting compounds |
EP1208105B1 (en) * | 1999-08-04 | 2006-10-04 | Hybrid Plastics | Process for the formation of polyhedral oligomeric silsesquioxanes |
US6911518B2 (en) * | 1999-12-23 | 2005-06-28 | Hybrid Plastics, Llc | Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities |
US6100417A (en) * | 1999-08-31 | 2000-08-08 | The United States Of America As Represented By The Secretary Of The Air Force | Functionalizing olefin bearing silsesquioxanes |
JP2001089662A (en) * | 1999-09-22 | 2001-04-03 | Kanegafuchi Chem Ind Co Ltd | Curable composition and method of producing molding using the same |
JP2002088157A (en) * | 2000-09-12 | 2002-03-27 | Kanegafuchi Chem Ind Co Ltd | Ladder type silsesquioxane compound containing styryl group as substituent group and method for producing the same |
WO2003064490A2 (en) * | 2001-06-27 | 2003-08-07 | Hybrid Plastics Llp | Process for the functionalization of polyhedral oligomeric silsesquioxanes |
WO2003042292A2 (en) * | 2001-11-17 | 2003-05-22 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Polyolefin compositions, method for the production thereof and the use of these compositions |
JP4742212B2 (en) * | 2002-08-06 | 2011-08-10 | Jnc株式会社 | Process for producing silsesquioxane derivative and silsesquioxane derivative |
JP4256756B2 (en) * | 2002-09-30 | 2009-04-22 | 新日鐵化学株式会社 | Method for producing cage-type silsesquioxane resin having functional group |
JP4734832B2 (en) * | 2003-05-14 | 2011-07-27 | ナガセケムテックス株式会社 | Encapsulant for optical element |
JP2005187381A (en) * | 2003-12-25 | 2005-07-14 | Asahi Kasei Corp | Method for refining silicon compound |
JP4409397B2 (en) * | 2004-09-27 | 2010-02-03 | 新日鐵化学株式会社 | Silicone resin composition and molded body |
JP2006282725A (en) * | 2005-03-31 | 2006-10-19 | Kri Inc | Silicon-containing new optically active compound |
TW200700427A (en) * | 2005-05-25 | 2007-01-01 | Hybrid Plastics Inc | Process for continuous production of olefin polyhedral oligomeric silsesquioxane cages |
JP2007015991A (en) * | 2005-07-08 | 2007-01-25 | Tokyo Univ Of Science | Method for producing basket-formed silsesquioxane |
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- 2006-08-16 TW TW095130107A patent/TW200722430A/en unknown
- 2006-08-16 EP EP06801756A patent/EP1931687A4/en not_active Withdrawn
- 2006-08-16 WO PCT/US2006/032166 patent/WO2007022367A2/en active Application Filing
- 2006-08-16 JP JP2008527138A patent/JP2009504890A/en active Pending
- 2006-08-16 CN CNA2006800296930A patent/CN101568546A/en active Pending
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1957563B1 (en) * | 2005-11-28 | 2010-04-28 | The Welding Institute | Process for the production of organosilsesquioxanes |
JP2008138203A (en) * | 2006-11-29 | 2008-06-19 | Dongjin Semichem Co Ltd | Monomer, polymer, and organic composition containing the same for forming organic anti-reflection film |
US9035009B2 (en) | 2007-04-17 | 2015-05-19 | Kaneka Corporation | Polyhedral polysiloxane modified product and composition using the modified product |
US9416231B2 (en) | 2007-04-17 | 2016-08-16 | Kaneka Corporation | Polyhedral polysiloxane modified product and composition using the modified product |
US9422405B2 (en) | 2007-04-17 | 2016-08-23 | Kaneka Corporation | Polyhedral polysiloxane modified product and composition using the modified product |
US9688851B2 (en) | 2010-05-28 | 2017-06-27 | Kaneka Corporation | Polysiloxane composition, hardened material and optical device |
US9822248B2 (en) | 2010-05-28 | 2017-11-21 | Kaneka Corporation | Polysiloxane composition, hardened material and optical device |
US9698320B2 (en) | 2010-09-22 | 2017-07-04 | Kaneka Corporation | Modified product of polyhedral structure polysiloxane, polyhedral structure polysiloxane composition, cured product, and optical semiconductor device |
CN102492078A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Acrylic acid and polyhedral silsesquioxane copolymerized hydrogel, its preparation method and its purpose |
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Publication number | Publication date |
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JP2009504890A (en) | 2009-02-05 |
EP1931687A4 (en) | 2011-05-04 |
CN101568546A (en) | 2009-10-28 |
RU2008110068A (en) | 2009-09-27 |
EP1931687A2 (en) | 2008-06-18 |
TW200722430A (en) | 2007-06-16 |
KR20080036148A (en) | 2008-04-24 |
WO2007022367A3 (en) | 2009-04-30 |
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