CN101151298B - Process for assembly of poss monomers - Google Patents

Process for assembly of poss monomers Download PDF

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CN101151298B
CN101151298B CN2006800073735A CN200680007373A CN101151298B CN 101151298 B CN101151298 B CN 101151298B CN 2006800073735 A CN2006800073735 A CN 2006800073735A CN 200680007373 A CN200680007373 A CN 200680007373A CN 101151298 B CN101151298 B CN 101151298B
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ultra
alkali
sio
phosphonitrile
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CN101151298A (en
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J·J·施瓦布
安以中
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Hybrid Plastics Inc
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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

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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

The method of poss monomers assembling
The cross reference of related application and patent
The application requires in the U.S. Provisional Patent Application No.60/659 of submission on March 7th, 2005,722 right of priority.
Invention field
Usually, the present invention relates to be used for improving the method for the functionalized poss monomers performance that is incorporated into polymerization product and biological products.
Background of invention
The preferred examples of nanostructure chemical preparations is those based on the material of polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) cheaply.The polyhedral oligomeric silsesquioxane system contains hydridization (being organic and inorganic) compsn, and inside cage shape framework wherein mainly is made up of inorganic silicon-oxygen key.The outside of this nanostructure is coated with two reactive behavioies and reactionless active organo-functional group (R), and it guarantees consistency and tailorability between nanostructure and organic monomer and the polymkeric substance.At United States Patent(USP) No. 5,412,053 with United States Patent(USP) No. 5,484,867 in the nanostructure chemical preparations has been detailed these and other performance characteristic, its full content is hereby incorporated by.
Current engineering practice can be produced functionalized polyhedral oligomeric silsesquioxane molecule by high productivity, but some microelectronics, medical and biologic applications need higher purity or those can not use prior art easily or the chemical functionality who produces economically.Art methods is included in uses hydroxide bases, anion salt and bronsted acid catalyst (referring to US patented claim No.09/631,892 and 10 186,318 in polyhedral oligomeric silsesquioxane cages assembling process and the functionalized process thereof; And US patent No.6,770,724,6; 660,823,6,596; 821 and 3,390,163).Though known these approach generally are effectively, they are subject to the self-condensation (Fig. 1) that protonic acid and hydroxide bases both can the entering of catalysis polyhedral oligomeric silsesquioxane list cage be contained the oligomeric polyhedral oligomeric silsesquioxane cages of resin.Because it is coarse that their structure is a molecule, this resinoid microtronics, biology or medical on be unfavorable.In addition, the consistency between the dispersion-s of polyhedral oligomeric silsesquioxane molecule and they and the polymkeric substance depends on free energy of mixing equation (Δ G=Δ H-T Δ S) on thermodynamics.When the cage size is that single picture (monoscopic) and corresponding oligomer distribution are when being 1.0; Reaction active groups and polymkeric substance and surface reaction or interactional ability can help favourable enthalpy item (Δ H) widely on the attribute of R group and the polyhedral oligomeric silsesquioxane cages, and the entropy item (Δ S) of polyhedral oligomeric silsesquioxane is highly favourable simultaneously.
Therefore need on prior art, improve polyhedral oligomeric silsesquioxane cages assembling and functionalized monomer's method.The invention describes more improving one's methods of high purity and the accurate polyhedral oligomeric silsesquioxane system of molecule of a kind of production.
Brief summary of the invention
The invention provides a kind of compound method of improved polyhedral oligomeric silsesquioxane, it can produce low resin content and solvent-free by high productivity fast, at the monomer product that all is suitable for aspect polymerization, grafting and the alloying.This compound method has been used with general formula and has been R 1SiX 3The ultra alkali of phosphonitrile of silane coupling agent reaction, formation is by the polyhedral oligomeric silsesquioxane cages of silanol functional, wherein the general formula of silanol is [(R 1SiO 1.5) 7(HOSiO 1.5) 1] Σ 8, [(R 1SiO 1.5)) 6(R 1HOSiO 1) 2] Σ 8, [(R 1SiO 1.5) 2(R 1HOSiO 1) 4] Σ 6, [(R 1SiO 1.5) 4(R 1HOSiO 1) 3] Σ 7This compound method can also comprise that ultra alkali of phosphonitrile and general formula are R 2SiX 3The reaction of silane coupling agent, form by R 2Group functionalization's polyfunctional group polyhedral oligomeric silsesquioxane cages and larger sized cage, R 2The general formula of group is [(R 2SiO 1.5) 6] Σ 6, [(R 2SiO 1.5) 8] Σ 8, [(R 2SiO 1.5) 10] Σ 10, [(R 2SiO 1.5) 12] Σ 12
Perhaps in the presence of solvent and ultra alkali, the ultra alkali of this phosphonitrile can be R at general formula 2R 3R 4SiX, R 2R 3SiX 2Or R 2SiX 3Silane coupling agent exist down and general formula is [(R 1SiO 1.5) 7(HOSiO 1.5) 1] Σ 8, [(R 1SiO 1.5) 6(R 1HOSiO 1) 2] Σ 8, [(R 1SiO 1.5) 4(R 1HOSiO 1) 3] Σ 7Silanol reaction time enough, the cancellation of HX wherein takes place and the poss monomers of simple function is provided, its general formula is [(R 1SiO 1.5) 8(R 2R 3R 4SiO 1)] Σ 9, [((R 1SiO 1.5) 8) 2(R 2R 3SiO 2)] Σ 17, [((R 1SiO 1.5) 8) 3(R 2SiO 3)] Σ 25, [(R 1SiO 1.5) 6(R 1SiO 1) 2(R 2R 3R 4SiO) 2] Σ 10, [(R 1SiO 1.5) 6(R 1SiO 1) 2(R 2R 3SiO 2)] Σ 9, [(R 1SiO 1.5) 6(R 1HOSiO 1) 1(R 2R 3SiO)] Σ 8, [(R 1SiO 1.5) 6(R 1(R 2R 3R 4SiO) SiO 1) (R 2R 3SiO)] Σ 9, [(R 1SiO 1.5) 4(R 1(R 2R 3R 4SiO) SiO 1) 3] Σ 10, [(R 1SiO 1.5) 7(R 2SiO 1.5) 1] Σ 8Resulting monomer has basically no impurity and through the selection to composition, R base and nanostructure size and topological framework, has controllable performance.Highly purified nanostructure poss monomers is desirable, because with respect to impure system, they demonstrate improved filtration capacity, the pollution of minimizing and viscosity, more reliable polyreaction, lower cost and Waste recovery.
A kind of preferable methods comprises that general formula is [(R 1SiO 1.5) 7(HOSiO 1.5) 1] Σ 8, [(R 1SiO 1.5) 6(R 1HOSiO 1) 2] Σ 8, [(R 1SiO 1.5) 4(R 1HOSiO 1) 3] Σ 7Polyhedral oligomeric silsesquioxane silanols and general formula be R 2R 3R 4SiX, R 2R 3SiX 2, R 2SiX 3The reaction of silane coupling agent in the presence of solvent and ultra alkali.
The accompanying drawing summary
Fig. 1 shows the contrast of prior art and improved silylanization (silation) method;
Fig. 2 shows the ultra alkali of various preferred phosphonitriles; With
Fig. 3 is presented at the structure of synthetic compound among the embodiment 5.
The definition of nanostructure expression formula
Be fine in order to understand chemistry of the present invention, the expression formula of polyhedral oligomeric sesquioxyalkane (polyhedral oligomeric silsesquioxane) and polyhedral oligomeric silicate (POS) nanostructure defines as follows:
Polysilsesquioxane is by general formula [RSiO 1.5] ∞The material of expression.Wherein ∞ representes the mole of polymerized degree; R=representes organic substituent (H, siloxy-, ring-type or linear aliphatic family or aromatic group; This group can contain reactive functional in addition like alcohol, ester, amine, ketone, alkene, ether or halogenide, or those can contain fluorinated groups).Polysilsesquioxane can be equal fragment (homoleptic) or assorted segmental (heteroleptic).All the fragment system only contains one type R group, and assorted fragment system contains more than one type R group.
Polyhedral oligomeric silsesquioxane and POS nanostructure are formed thing and are represented by following general formula:
[(RSiO 1.5) n] Σ #, represent equal fragment constituent
[(RSiO 1.5) n(R ' SiO 1.5) m] Σ #The assorted fragment constituent (wherein R ≠ R ') of expression
[(RSiO 1.5) n(RXSiO 1.0) m] Σ #Expression functionalized heteroleptic compsn (wherein the R group can be equivalent or with normal).
More than all R identical with above-mentioned definition, and X includes but not limited to OH, Cl, Br, I, alkoxide (OR), formate (OCH), acetic ester (OCOR), acid (OCOH), ester (OCOR), superoxide (OOR), amine (NR 2), isocyanic ester (NCO) and R.Symbol m and n refer to stoichiometric composition.Symbol Σ indication compsn forms nanostructure, and symbol # refers to the Siliciumatom number that contains in nanostructure inside.The # value is the m+n sum normally, and wherein n is generally 1～24, and m is generally 1～12.Should be understood that Σ # can not obscure for being used for definite stoichiometric multiplier, because it just describes the whole system nanostructure characteristic of (having another name called the cage size).
Detailed description of the invention
The present invention narrated than before the more high purity described synthesize improving one's methods of polyhedral oligomeric silsesquioxane nano structural chemistry goods with more low-cost.
Key feature of the present invention is the formation through utilizing the ultra alkali of phosphonitrile to come the catalysis polyhedral oligomeric silsesquioxane cages.A large amount of phosphonitriles are suitable for, and comprise that those are at molecular weight and the discrepant polyphosphonitrile of composition.Preferred phosphonitrile oligopolymer and the molecule, particularly P1 type P (NtBu) (NH of using 2) 3, P2 type (H 2N) 3P=N-P (NH 2) 4, P3 type (H 2N) 3P=N-P (NH 2)-N=P (NH 2) 3, P4 type (H 2N) 3P=N-P (NH 2) 3=N-P (NH 2) 3-N=P (NH 2) 3The basicity of the ultra alkali of phosphonitrile increases with the increase of phosphorus atom number, and this provides valuable means when using these reagent.With respect to three silanols (trisilanol), the preferred depth of ultra alkali is 2mol%, but useful range comprises 0.1mol%～10mol%.
Be applied to the general method variable of all methods
As more typical situation in chemical process, there are many variablees to can be used for controlling purity, selectivity, speed and the mechanism of arbitrary method.The variable that influences method comprises the constituent of granularity, polymolecularity and nanostructure chemical preparations, separate and the use of partition method, catalyzer or promotor, solvent and solubility promoter.In addition, the dynamic (dynamical) and thermodynamic (al) means that control synthesis mechanism, speed and product distribute are known industry instruments, and they can influence quality product and economic benefit.
Embodiment 1
[(isobutyl-SiO 1.5) 7(methacryloyl propyl group SiO 1.0) 1] Σ 8Synthetic:
With [(isobutyl-SiO 1.5) 4(isobutyl-(OH) SiO 1.0) 3] Σ 7(688g, 0.87 mole) is dissolved in THF, adds methacryloyl propyl trimethoxy alkane (204g, 0.87 mole) and cooling solution to 5 ℃ then.(FW 234.32, and 15.72mmol), mixture at room temperature stirred 3 days to add the ultra alkali of phosphonitrile then.Use acetate (1.5g) quench solution then.Add 1 liter of methyl alcohol subsequently, mixture is stirred and filters.Drying solid obtains the pure white product of 75% productive rate.
Embodiment 2
[(ethyl SiO 1.5) 7(epoxypropyl SiO 1.0) 1] Σ 8Synthetic:
With [(ethyl SiO 1.5) 4(ethyl (OH) SiO 1.0) 3] Σ 7(50g 84mmol) is dissolved in methyl alcohol, add then the 3-glycidoxypropyltrime,hoxysilane (19.86g, 84mmol) and cooling solution to 5 ℃.(FW 234.32, and 15.72mmol), mixture stirred 3 days down at 5 ℃ to add the ultra alkali of phosphonitrile then.Use acetate (87mg) quench solution then, filter, remove volatile matter, drying obtains solid.With methyl alcohol (1400ml) wash solids, drying obtains the pure white product of 415g, and productive rate is 87%.
Embodiment 3
[(ethyl SiO 1.5) 7(ethyl norbornene SiO 1.0) 1] Σ 8Synthetic:
With [(ethyl SiO 1.5) 4(ethyl (OH) SiO 1.0) 3] Σ 7(12g 20mmol) is dissolved in methyl alcohol, add then outer-norbornenylethyl Trimethoxy silane (4.84g, 20mmol) and cooling solution to 5 ℃.Add the ultra alkali of phosphonitrile then, mixture stirred 2 days down at 5 ℃.Use acetate (87mg) quench solution then, filter, remove volatile matter, with other methanol wash, drying obtains white products.
Embodiment 4
[(cyclohexyl SiO 1.5) 7(amino-ethyl aminopropyl SiO 1.0) 1] Σ 8Synthetic:
With [(cyclohexyl SiO 1.5) 4(cyclohexyl (OH) SiO 1.0) 3] Σ 7(10g 10.3mmol) is dissolved in THF, and (2.32g, 10.27mmol), (FW 234.32, and 15.72mmol), mixture at room temperature stirs to add the ultra alkali of phosphonitrile then to add 3-(N-amino-ethyl) TSL 8330 then.Then with the acetate quench solution and add methyl alcohol.Remove the volatile matter drying prods and obtain pure white solid with 62% productive rate.
Embodiment 5
[(phenyl SiO 1.5) 7(aminopropyl SiO 1.0) 1] Σ 8Synthetic:
With [(phenyl SiO 1.5) 4(phenyl (OH) SiO 1.0) 3] Σ 7(5.9g 6.3mol) is dissolved in toluene, and (2.0g, 11mmol) 3-TSL 8330 at room temperature stirred 12 hours then in interpolation then.Add acetonitrile and filtering solution, drying prods obtains pure white solid with 40% productive rate.
Although in order to explain that the present invention has provided some representative embodiment and detailed description; But those of skill in the art should understand, and under not departing from like the prerequisite of the defined scope of the present invention of additional claims, can carry out various changes to method and apparatus disclosed herein.

Claims (14)

1. the method for preparing functionalized poss monomers is included in and makes polyhedral oligomeric silsesquioxane silanols under the existence of organic solvent and the ultra alkali of phosphonitrile and have general formula R SiX 3The step of silane coupling agent reaction; Wherein R is selected from hydrogen; Siloxy-and ring-type or linear aliphatic, aromatics and olefin group, wherein said group can contain and be selected from alcohol, ester, amine, ketone, alkene, ether and halid reactive functional groups, and can contain and fluoridize substituting group;
X is selected from Cl, Br, I, OR, OCOH, OCOR, OOR, NR 2, NCO and R; And
Each R and each X can be identical or different.
2. the process of claim 1 wherein that X is OH, manthanoate or acetic ester.
3. the process of claim 1 wherein that the ultra alkali of phosphonitrile is selected from P (NtBu) (NH 2) 3, (H 2N) 3P=N-P (NH 2) 4, (H 2N) P=N-P (NH 2)-N=P (NH 2) 3(H 2N) 3P=N-P (NH 2) 3=N-P (NH 2) 3-N=P (NH 2) 3
4. the process of claim 1 wherein that the mixture reaction that makes different silane coupling agents prepares functionalized poss monomers.
5. the process of claim 1 wherein that the mixture that uses the ultra alkali of different phosphonitriles is as homogeneous catalyst or coreagent.
6. the process of claim 1 wherein the mixture that uses different solvents.
7. the process of claim 1 wherein and use continuous processing that functionalized poss monomers is provided, it uses the ultra alkali of phosphonitrile as heterogeneous catalyst or coreagent.
8. the method for preparing functionalized poss monomers, the existence that is included in organic solvent and the ultra alkali of phosphonitrile is down with the step of silane coupling agent silication polyhedral oligomeric silsesquioxane silanols, and the general formula of silane coupling agent is selected from RSiX 3, R 2SiX 2And R 3SiX, wherein:
R is selected from hydrogen, and siloxy-and ring-type or linear aliphatic, aromatics and olefin group, wherein said group can contain and be selected from alcohol, ester, amine, ketone, alkene, ether and halid reactive functional groups, and can contain and fluoridize substituting group;
X is selected from Cl, Br, I, OR, OCOH, OCOR, OOR, NR 2, NCO and R; And
Each R and each X can be identical or different.
9. the method for claim 8, wherein X is OH, manthanoate or acetic ester.
10. the method for claim 8, wherein the ultra alkali of phosphonitrile is selected from P (NtBu) (NH 2) 3, (H 2N) 3P=N-P (NH 2) 4, (H 2N) P=N-P (NH 2)-N=P (NH 2) 3(H 2N) 3P=N-P (NH 2) 3=N-P (NH 2) 3-N=P (NH 2) 3
11. the method for claim 8, wherein the mixture with different polyhedral oligomeric silsesquioxane silanols and silane coupling agent carries out silication.
12. the method for claim 8, the mixture that wherein uses the ultra alkali of different phosphonitriles is as homogeneous catalyst or coreagent.
13. the method for claim 8 is wherein used the mixture of different solvents.
14. the method for claim 8 is wherein used continuous silicification, it uses the ultra alkali of phosphonitrile as heterogeneous catalyst or coreagent.
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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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