EP1856190A2 - Process for assembly of poss monomers - Google Patents

Process for assembly of poss monomers

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Publication number
EP1856190A2
EP1856190A2 EP06737433A EP06737433A EP1856190A2 EP 1856190 A2 EP1856190 A2 EP 1856190A2 EP 06737433 A EP06737433 A EP 06737433A EP 06737433 A EP06737433 A EP 06737433A EP 1856190 A2 EP1856190 A2 EP 1856190A2
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP06737433A
Other languages
German (de)
French (fr)
Other versions
EP1856190A4 (en
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
Publication of EP1856190A2 publication Critical patent/EP1856190A2/en
Publication of EP1856190A4 publication Critical patent/EP1856190A4/en
Withdrawn legal-status Critical Current

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    • 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
    • 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

A synthesis process for polyhedral oligomeric silsesquioxanes using phosphazene superbases to produce in high yield a low resin content, solvent free, and trace metal free monomer suitable for use in microelectronic, biological, and medical applications involving polymerization, grafting, and alloying.

Description

PROCESS FOR ASSEMBLY OF POSS MONOMERS
Cross-Reference to Related Applications and Patents
This application claims priority from U.S. Provisional Patent Application Serial No. 60/659,722 Filed March 7, 2005.
Field of the Invention
This invention relates generally to a process for enhancing the properties of functionalized POSS monomers for incorporation into polymeric and biological products.
BACKGROUND OF THE INVENTION
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. These and other properties and features of nanostructured chemicals are discussed in detail in U.S. Pat. Nos. 5,412,053 and U.S. Pat. No. 5,484,867, both of which are expressly incorporated herein by reference in their entirety.
Current engineering practices produce functionalized POSS molecules in high yield but certain microelectronic, medical, and biological applications require higher purity or chemical functionalities that are not readily or economically produced using the prior art. 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). While these approaches are known to be generally effective, they are limited in that both protic acids and hydroxide bases can also catalyze the self-condensation of POSS individual cages into oligomerized POSS cage containing resins (Figure 1). Such resins are not desirable in microelectronics, biological or medical applications, as their structure is molecularly imprecise. Furthermore, the dispersion of the POSS molecules and their compatibility with polymers is thermodynamically governed by the free energy of
mixing equation (ΔG = ΔH-TΔS). The nature of the R group and ability of the
reactive groups on the POSS cage to react or interact with polymers and surfaces
greatly contributes to a favorable enthalpic (ΔH) term while the entropic term (ΔS) for
POSS is highly favorable when the cage size is monoscopic and the corresponding distribution of oligomers is 1.0.
Consequently a need exists for improvement upon the prior art methods of POSS cage assembly and functionalized monomers. An improved process yielding, higher purity, and molecularly precise POSS systems is described.
SUMMARY OF THE INVENTION
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 R1SiX3 to form POSS cages
functionalized with silanols of the formula types [(R1SiOi.5)7(HOSiOi.5)i]∑8, [(R1SiOi.5)6(R1HOSiOi)2]∑8l [(R1 SiO1. S)2(R1HOSiOi)4]Z6, [(R1SiOi.5)4(R1HOSiOi)3]∑7. The synthesis process can also involve the reaction of phosphazene superbases in reaction with silane coupling agents of the type R2SiX3 to form polyfunctional POSS cages functionalized with R2 groups of the formula types [(R2SiOi ,5)e]∑6, [(R2SiOi.5)8]∑8, [(R2SiOi.5)io]∑io, [(R2SiOi.5)12]∑12 and larger sized cages.
Alternately the phosphazene superbases can be reacted with POSS silanols
of the formula [(R1SiOi.5)7(HOSiOi.B)i]Σ8, [(R1SiO11B)6(R1HOSiOi)2]X8, [(R1 SiOi.δMR1 HOSiOi )3]∑7 in the presence of a silane coupling agent of the formula R2R3R4SiX, R2R3SiX2, or R2SiX3 for sufficient time in the presence of a solvent and superbase where the elimination of HX occurs and renders a monofunctional POSS monomer of the formula [(R1SiO1^)8(R2 R3R4SiOi)]∑9, [((R1SiOi.5)8)2(R2 R3SiO2)]Σi7, [((R1SiOi.5)8)3(R2SiO3)]∑25j [(R1SiOi.5)6(R1SiOi)2(R2R3R4SiO)2]Σio, [(R1SiOi.5)6(R1SiOi)2(R2R3SiO2)]Σ9, [(R1SiOi.5)6(R1HOSiOi)i(R2R3SiO)]∑8,
[(R1SiO1.5)6(R1(R2R3R4SiO)SiO1)(R2R3SiO)]Σ9, [(R1SiOLs)4(RVR2R3R4SiO)SiOi)3]ZiO, [(R1SiOi.5)7(R2SiOi.5)i]∑8) respectively. 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 [(R1SiOi.5)7(HOSiOi.5)i]∑8, [(R1 Sid ,5)6(R1 HOSiOi )2]∑8, [(R1 SiOi.5)4(R1 HOSiOi )3]∑7 with a silane coupling agent of the formula, R2R3R4SiX, R2R3SiX2, R2SiX3 in the presence of a solvent and superbase. BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a comparison of the prior art and improved silation process;
FIG. 2 shows a variety of the preferred phosphazene superbases; and
FIG. 3 shows the structure of the compound synthesized in Example 5.
DEFINITION OF FORMULA REPRESENTATIONS FOR NANOSTRUCTURES
For the purposes of understanding this invention's chemical compositions the following definition for formula representations of Polyhedral Oligomeric Silsesquioxane (POSS) and Polyhedral Oligomeric Silicate (POS) nanostructures is made.
Polysilsesquioxanes are materials represented by the formula [RSiO1 5]..
where ∞ represents molar degree of polymerization and 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:
[(RSiO1.5)n]∑# for homoleptic compositions
[(RSiO-j ^)n(R1SiO1.5)m]∑# for heteroleptic compositions (where R ≠ R') [(RSiO1 -5)Ii(RXSiO1 0)m]∑# for functionaiized heteroleptic compositions (where R
groups can be equivalent or in equivalent)
In all of the above R is the same as defined above and X includes but is not limited to OH, Cl, Br1 I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R.
The symbols m and n refer to the stoichiometry of the composition. The symbol ∑
indicates that the 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
from 1 to 12. It should be noted that ∑# is not to be confused as a multiplier for
determining stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).
DETAILED DESCRIPTION OF THE INVENTION The present invention teaches an improved method of synthesis for POSS nanostructured chemicals yielding a higher purity and lower cost product than previously described.
The key feature of the invention is the use of 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
1 type P(NtBu)(NHa)3, P2 type (H2N)3P=N-P(NHa)4, P3 type (H2N)3P=N-P(NH2)- N=P(NH2)3l P4 type (HaN)3P=N-P(NH2)3=N-P(NH2)3-N=P(NH2)3. The basicity of phosphazene superbases increase with increasing number of phosphorous atoms and this provides a valuable tool in the utility of this reagent. The preferred concentration of superbase relative to trisilanol is 2 mol % but a useful range includes 0.1 mol % to 10 mol %.
General Process Variables Applicable To AU Processes
As is typical with chemical processes there are a number of variables that can be used to control the purity, selectivity, rate and mechanism of any process. 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.
Example 1.
Synthesis of [(isobutylSiOi .5)7(methacrylpropylSiOi .0)1 ]∑β:
[(isobutylSiOi .5)4(isobutyl(OH)SiOi .0)3.17 (688 g, 0.87 mole) was dissolved in THF
followed by addition of methacrylpropyltrimethoxysilane (204 g, 0.87 mole) and the solution was cooled to 5°C. Phosphazene superbase (FW 234.32, 15.72 mmol) was then added and the mixture stirred at room temperature for 3 days. The solution was then quenched with acetic acid (1.5g). Then 1 liter of methanol was added and the mixture was stirred and filtered. The solid was dried to render pure white product in 75% yield.
Example 2.
Synthesis of [(EtSiOi .5)7(glycidalSiOi .0)1 ]∑8=
[(EtSiOi .5)4(Et(OH)SiOi .o)3]∑7 (50 g, 84 mmole) was dissolved in methanol followed by addition of 3-glycidoxypropyltrimethoxysilane (19.86 g, 84 mmole) and the solution was cooled to 50C. Phosphazene superbase (FW 234.32, 15.72 mmol) was then added and the mixture stirred for 3 days at 50C. The solution was then quenched with acetic acid (87mg) filtered, and volatiles removed and dried to render a solid. The solid was washed with methanol (1400 ml) and dried to render 415 g of pure white product in 87% yield.
Example 3.
Synthesis of [(EtSiOi ,5)7(ethylnorborneneSiOi .0)1 ]∑a-m
[(EtSiOi .5)4(Et(OH)SiOi ,o)3]∑7 (12 g, 20 mmole) was dissolved in methanol
followed by addition of exo-norbomenylethyltrimethoxysilane (4.84 g, 20 mmole) and the solution was cooled to 5°C. 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.
Example 4.
Synthesis of [(CyclohexylSiOi ,5)7(aminoethylaminpropylSiOi .0)1 ]∑s:
[(CyclohexylSiOi .5)4(Cyclohexyl(OH)SiOi .o)3]∑7 (10 g, 10.3 mmole) was dissolved
in THF followed by addition of 3-(N-aminoethyl)aminopropyltrimethoxysilane (2.32 g, 10.27 mmole) and phosphazene superbase (FW 234.32, 15.72 mmol) was then added and the mixture stirred at room temperature. The solution was then quenched with acetic acid methanol was added. The volatiles were removed and product dried to render a pure white solid in 62% yield. Example 5.
Synthesis of [(PhenylSiOi .5)7(aminopropylSiOi .0)1 ]γ8-
[(PhenylSiOi .5)4(Phenyl(OH)SiOi .o)3]∑7 (5.9g, 6.3mol) was dissolved in toluene
followed by addition of (2.Og, 11 mmol) 3-aminopropyltrimethoxysilane and was then stirred at room temperature for 12 hours. Acetonitrile was added and the solution was filtered and product dried to render a pure white solid in 40% yield.
While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention which is defined in the appended claims.
What is claimed is:

Claims

1. A method for preparing functionalized POSS monomers comprising the step of reacting a silane coupling agent having the formula RSiX3 in the presence of a solvent and a phosphazene superbase.
2. The method of claim 1 , wherein the superbase is selected from the group consisting of P1 , P2, P3, and P4 type phosphazenes.
3. The method of claim 1 , wherein a mixture of different silane coupling agents are reacted to prepare the functionalized POSS monomers.
4. The method of claim 1 , wherein a mixture of different superbases are utilized as homogeneous catalysts or coreagents.
5. The method of claim 1 , wherein a mixture of different solvents is utilized.
6. The method of claim 1 , wherein a continuous process rendering functionalized POSS monomers is utilized using the superbase as a heterogeneous catalyst or coreagent.
7. A method for preparing functionalized POSS monomers comprising the step of silating a POSS silanol with a silane coupling agent having a formula selected from the group consisting of RSi X3, R1R2 Si X2, and R1R2R3 Si X, in the presence of a solvent and a phosphazene superbase.
8. The method of claim 7, wherein the superbase is selected from the group consisting of P1 , P2, P3, and P4 type phosphazenes.
9. The method of claim 7, wherein a mixture of different POSS silanols and silane coupling agents are silated.
10. The method of claim 7, wherein a mixture of different superbases are utilized as homogeneous catalysts or coreagents.
11. The method of claim 7, wherein a mixture of different solvents is utilized.
12. The method of claim 7, wherein a continuous silation process is utilized using the superbase as a heterogeneous catalyst or coreagent.
EP06737433A 2005-03-07 2006-03-07 Process for assembly of poss monomers Withdrawn EP1856190A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65972205P 2005-03-07 2005-03-07
PCT/US2006/008262 WO2006096775A2 (en) 2005-03-07 2006-03-07 Process for assembly of poss monomers

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EP1856190A2 true EP1856190A2 (en) 2007-11-21
EP1856190A4 EP1856190A4 (en) 2011-02-09

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JP (1) JP2008537731A (en)
KR (1) KR101208460B1 (en)
CN (1) CN101151298B (en)
RU (1) RU2007137027A (en)
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WO (1) WO2006096775A2 (en)

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US7915436B2 (en) * 2008-11-03 2011-03-29 3M Innovative Properties Company Phosphorus-containing silsesquioxane derivatives as flame retardants
EP2865704A1 (en) * 2013-10-28 2015-04-29 Huntsman International Llc Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions
CN116102734B (en) * 2022-12-29 2023-10-24 广州硅碳新材料有限公司 Phosphorus-nitrogen-containing cage polysilsesquioxane, preparation method thereof and application thereof as crusting and carbonizing agent

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EP1856190A4 (en) 2011-02-09
JP2008537731A (en) 2008-09-25
WO2006096775A2 (en) 2006-09-14
RU2007137027A (en) 2009-04-20
CN101151298A (en) 2008-03-26
KR20080002803A (en) 2008-01-04
WO2006096775A3 (en) 2007-09-20
TW200702361A (en) 2007-01-16
CN101151298B (en) 2012-07-11
KR101208460B1 (en) 2012-12-05

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