KR102035830B1 - Preparation method of polyhedral oligomeric silsesquioxane - Google Patents

Preparation method of polyhedral oligomeric silsesquioxane Download PDF

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KR102035830B1
KR102035830B1 KR1020160028459A KR20160028459A KR102035830B1 KR 102035830 B1 KR102035830 B1 KR 102035830B1 KR 1020160028459 A KR1020160028459 A KR 1020160028459A KR 20160028459 A KR20160028459 A KR 20160028459A KR 102035830 B1 KR102035830 B1 KR 102035830B1
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trimethoxysilane
group
polyhedral oligomeric
oligomeric silsesquioxane
carbon atoms
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KR1020160028459A
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KR20170105350A (en
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최지영
송영지
최대승
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주식회사 엘지화학
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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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • 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

Abstract

The present invention relates to a process for producing polyhedral oligomeric silsesquioxanes. According to the preparation method it is possible to minimize the production of by-products of other structures and to synthesize polyhedral oligomeric silsesquioxane with high purity.

Description

Production method of polyhedral oligomeric silsesquioxane {PREPARATION METHOD OF POLYHEDRAL OLIGOMERIC SILSESQUIOXANE}

The present invention relates to a process for producing polyhedral oligomeric silsesquioxanes.

The siloxane structure consisting of Si-O-Si bonds is generally defined by four types (Q, T, D, M). Dual [RSiO 1 . 5 ] The polysiloxane represented by y has a T unit structure among four kinds, and its scientific name is polysilsesquioxane.

Polysilsesquioxane is synthesized using a hydrolysis-polymerization method, and a method using trialkoxysilane and a hydrolysis-polymerization method using trichlorosilane are widely known to date. The structure of the polysilsesquioxane thus synthesized is known to have a high regularity. However, as the device analysis technology in the chemical field is greatly developed, the structure is analyzed to have a cage structure, a ladder structure, or an irregular structure such as 6, 8, 10, and 12 dimers. Due to the mixing of these structures, the mechanical / physical properties expected when designing polymer structures are considered to be less than expected.

The present invention provides a process for providing polyhedral oligomeric silsesquioxanes of cage structure with high purity.

According to an embodiment of the present invention, a polyhedral oligomer seal comprising reacting a reaction mixture comprising a first silane compound represented by Formula 1, a second silane compound represented by Formula 2, and a nonionic fluorine-based surfactant A method for producing sesquioxane is provided.

[Formula 1]

R 1 -SiX 1 3

[Formula 2]

R 2 -A-SiX 2 3

In Formulas 1 and 2, A is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, -O-Si (R 3 ) (R 4 )-or -O-Si (R 3 ) (R 4 ) -R 5- ,

R 1 is a monovalent moiety derived from a hydrocarbon of 1 to 30 carbon atoms substituted with halogen,

R 2 is a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxy alkyl group having 2 to 30 carbon atoms, and a C 2 to Or a functional group selected from the group consisting of 30 epoxyalkoxy groups, alkenyl groups having 2 to 30 carbon atoms and alkenyloxy groups having 2 to 30 carbon atoms, or -OH, -NH 2 , -NH-R 6 , -NH 3 X 3 , A monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with one or more substituents selected from the group consisting of -COOH, -CONH 2 , -CN, -SH, a glycidyl group, a glycidyloxy group, and maleimide,

X 1 and X 2 are each independently an alkoxy group having 1 to 5 carbon atoms, Cl, Br or I,

R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, R 5 is an alkylene group having 1 to 12 carbon atoms,

R 6 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with an amino group, and X 3 is halogen.

In the method for preparing the polyhedral oligomeric silsesquioxane, the surfactant may include [alkyl [(fluoroalkyl) sulfonyl] amino] ethyl ester.

Such surfactant may be used in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the first and second silane compounds.

In the method for preparing the polyhedral oligomeric silsesquioxane, as the first silane compound, R 1 is trifluoromethyl, trifluoroethyl, trifluoropropyl, trifluorobutyl, pentafluorobutyl, trifluoropentyl , Pentafluoropentyl, heptafluoropentyl, trifluorohexyl, pentafluorohexyl, heptafluorohexyl, nonafluorohexyl, undecafluorohexyl, perfluorohexyl, trifluoroheptyl, pentafluoro Heptyl, heptafluoroheptyl, nonafluoroheptyl, undecafluoroheptyl, dodecafluoroheptyl, tridecafluoroheptyl, perfluoroheptyl, trifluorooctyl, pentafluorooctyl, heptafluorooctyl, Nonafluorooctyl, undecafluorooctyl, tridecafluorooctyl, pentadecafluorooctyl, perfluorooctyl, chloropropyl, (chloromethyl) phenyl, (chloromethyl) phenylethyl or Di-bromide can be used for all the ethyl compound.

As the second silane compound, R 2 is a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, and an epoxy cyclo It is a functional group selected from the group consisting of hexyl group, epoxycyclohexoxy group, vinyl group, allyl group and norbornene group or cyclohexanediol, trimethylolpropane, glycerol, 3-hydroxy-3-methylbutane, aminopropyl, aniline, N -Methylaminopropane, N-phenylaminopropane, N- (aminoethyl) aminopropane, propylammonium chloride, propylnitrile, propylthiol, glycidyloxypropane, N-propylmaleimide and maleamic acid Compounds which are monovalent residues derived from substituted hydrocarbons selected from can be used.

In the second silane compound, A is a single bond, methylene, ethylene, propylene, phenylene, -O-Si (CH 3 ) (CH 3 )-or -O-Si (CH 3 ) (CH 3 ) -CH 2 CH 2 CH 2- .

Specifically, as the first silane compound, (trifluoropropyl) trimethoxysilane, (trifluorobutyl) trimethoxysilane, (pentafluorobutyl) trimethoxysilane, (trifluoropentyl) tri Methoxysilane, (pentafluoropentyl) trimethoxysilane, (heptafluoropentyl) trimethoxysilane, (trifluorohexyl) trimethoxysilane, (pentafluorohexyl) trimethoxysilane, (hepta Fluorohexyl) trimethoxysilane, (nonnafluorohexyl) trimethoxysilane, (undecafluorohexyl) trimethoxysilane, (perfluorohexyl) trimethoxysilane, (trifluoroheptyl) tri Methoxysilane, (pentafluoroheptyl) trimethoxysilane, (heptafluoroheptyl) trimethoxysilane, (nonnafluoroheptyl) trimethoxysilane, (undecafluoroheptyl) trimethoxysilane, ( Dodecafluoroheptyl) trimethoxysilane, (tridecafluoroheptyl) trimethoxysilane, ( Perfluoroheptyl) trimethoxysilane, (trifluorooctyl) trimethoxysilane, (pentafluorooctyl) trimethoxysilane, (heptafluorooctyl) trimethoxysilane, (nonnafluorooctyl) tri Methoxysilane, (undecafluorooctyl) trimethoxysilane, (tridecafluorooctyl) trimethoxysilane, (pentadecafluorooctyl) trimethoxysilane, (perfluorooctyl) trimethoxysilane , (Chloropropyl) trimethoxysilane, [(chloromethyl) phenyl] trimethoxysilane, [(chloromethyl) phenylethyl] trimethoxysilane and (dibromoethyl) trimethoxysilane 1 or more types can be used.

The second silane compound may be (3- (meth) acryloxypropyl) trimethoxysilane, (2,3-dihydroxypropoxypropyl) trimethoxysilane, (3,4-dihydroxyhexyl Ethyl) trimethoxysilane, (3-hydroxy-3-methylbutyldimethylsiloxy) trimethoxysilane, (3,4-epoxyhexylpropyl) trimethoxysilane, (3,4-epoxyhexylethyldimethylsilane Trimethoxysilane, (3-aminopropyl) trimethoxysilane, (N-aminoethylaminopropyl) trimethoxysilane, (aminophenyl) trimethoxysilane, (N-phenylaminopropyl) trimethoxy Silane, (N-methylaminopropyl) trimethoxysilane, (3-cyanopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-glycidyloxypropyl) trimethoxy Silane, vinyltrimethoxysilane, allyltrimethoxysilane, (trimethoxysilyl) norbornene, N- [3- (trimethoxysilyl) propyl] maleimide and N- [3- (trimethoxysilyl) Ropil] it can be used at least one selected from the group consisting of horse LEA acid.

In the method for producing the polyhedral oligomeric silsesquioxane, the reaction mixture may be reacted in the presence of a base catalyst. In this case, ammonium hydroxide may be used as the base catalyst. The base catalyst may be used in an amount of 0.001 to 100 moles based on 100 moles of the total silane compound.

On the other hand, in the method for producing the polyhedral oligomeric silsesquioxane, the reaction mixture can be reacted under an organic solvent. In this case, an ether solvent may be used as the organic solvent.

In the method for preparing the polyhedral oligomeric silsesquioxane, the reaction mixture may be reacted at a temperature of 0 to 40 ° C. In addition, the reaction mixture may be reacted for 5 hours to 128 hours.

In the method for preparing a polyhedral oligomeric silsesquioxane, a polyhedral oligomeric silsesquioxane represented by the following Formula 3 may be provided.

[Formula 3]

(R 1 SiO 1.5 ) m (R 2 -A-SiO 1.5 ) n

In Formula 3, A is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, -O-Si (R 3 ) (R 4 )-or -O-Si (R 3 ) (R 4 ) -R 5- ,

R 1 is a monovalent moiety derived from a hydrocarbon of 1 to 30 carbon atoms substituted with halogen,

R 2 is a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxy alkyl group having 2 to 30 carbon atoms, and a C 2 to Or a functional group selected from the group consisting of 30 epoxyalkoxy groups, alkenyl groups having 2 to 30 carbon atoms and alkenyloxy groups having 2 to 30 carbon atoms, or -OH, -NH 2 , -NH-R 6 , -NH 3 X 3 , A monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with one or more substituents selected from the group consisting of -COOH, -CONH 2 , -CN, -SH, glycidyl group, glycidyloxy group and maleimide,

R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, R 5 is an alkylene group having 1 to 12 carbon atoms,

R 6 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with an amino group, and X 3 is halogen.

m and n are each independently an integer of 1 to 29, and the sum of m and n is an integer of 6 to 30.

Through the method for producing a polyhedral oligomeric silsesquioxane according to one embodiment of the present invention, it is possible to minimize the generation of by-products of other structures and to synthesize polyhedral oligomeric silsesquioxanes with high purity.

Hereinafter, a method for preparing a polyhedral oligomeric silsesquioxane according to a specific embodiment of the present invention will be described.

According to an embodiment of the present invention, a polyhedral oligomer seal comprising reacting a reaction mixture comprising a first silane compound represented by Formula 1, a second silane compound represented by Formula 2, and a nonionic fluorine-based surfactant A method for producing sesquioxane is provided.

[Formula 1]

R 1 -SiX 1 3

[Formula 2]

R 2 -A-SiX 2 3

In Formulas 1 and 2, A is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, -O-Si (R 3 ) (R 4 )-or -O-Si (R 3 ) (R 4 ) -R 5- ,

R 1 is a monovalent moiety derived from a hydrocarbon of 1 to 30 carbon atoms substituted with halogen,

R 2 is a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxy alkyl group having 2 to 30 carbon atoms, and a C 2 to Or a functional group selected from the group consisting of 30 epoxyalkoxy groups, alkenyl groups having 2 to 30 carbon atoms and alkenyloxy groups having 2 to 30 carbon atoms, or -OH, -NH 2 , -NH-R 6 , -NH 3 X 3 , A monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with one or more substituents selected from the group consisting of -COOH, -CONH 2 , -CN, -SH, a glycidyl group, a glycidyloxy group, and maleimide,

X 1 and X 2 are each independently an alkoxy group having 1 to 5 carbon atoms, Cl, Br or I,

R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, R 5 is an alkylene group having 1 to 12 carbon atoms,

R 6 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with an amino group, and X 3 is halogen.

As used herein, a hydrocarbon is a compound consisting of carbon and hydrogen, and is meant to include both unsaturated and saturated hydrocarbons including carbon-carbon double bonds and / or carbon-carbon triple bonds. The hydrocarbon may be linear, branched, cyclic, or include two or more of these structures. More specifically, the hydrocarbon may be alkanes, alkenes, alkynes or arenes, including straight, branched or cyclic structures, one or more of which is different. It may be substituted in the species. In this specification, a monovalent residue derived from a hydrocarbon or a monovalent residue derived from a substituted hydrocarbon means a monovalent radical in which one hydrogen radical is removed from a hydrocarbon or a substituted hydrocarbon.

Polysilsesquioxanes can have a variety of structures, such as random, ladder, cage and partial cage, and polysilsesquioxane having a double cage structure is a polyhedral oligomeric silsesqui It is called polyhedral oligomeric silsesquioxane. Such polyhedral oligomeric silsesquioxane is attracting attention in various fields because it is easy to introduce a plurality of functional functional groups and can effectively express the characteristics of the functional functional groups while using the silsesquioxane skeleton as a core.

However, through known methods for synthesizing polyhedral oligomeric silsesquioxanes, there has been a problem in that polysilsesquioxanes of random or ladder form in addition to polyhedral oligomeric silsesquioxanes are produced. In particular, in the case of the polyhedral oligomeric silsesquioxane substituted with a fluoroalkyl group, there is a problem that is difficult to obtain with high purity.

Accordingly, the present inventors have studied and studied a method of synthesizing polyhedral oligomeric silsesquioxane to find that polyhedral oligomeric silsesquioxane can be obtained with high purity when complementing precursor compatibility with organic solvents. The invention has been completed. Specifically, according to the manufacturing method of the embodiment, by reacting the reaction mixture containing the first silane compound and the second silane compound in the presence of a nonionic fluorine-based surfactant to minimize the generation of by-products of high molecular weight and polyhedral oligomeric silsesquioxane It is possible to improve the purity of.

The nonionic fluorine-based surfactant (which may be simply referred to herein as a 'surfactant') is a polyhedral oligomer by increasing the compatibility with a precursor for preparing a polyhedral oligomer silsesquioxane, ie, an organic solvent of a silane compound. The synthesis reaction of silsesquioxane can be induced to proceed evenly. Accordingly, it is expected that the yield of the polyhedral oligomeric silsesquioxane having a cage structure is further improved.

In particular, the use of non-fluorine based surfactants or cationic, anionic or amphoteric fluorine based surfactants is not sufficient to improve the purity and yield of polyhedral oligomeric silsesquioxanes. However, using a nonionic surfactant having a fluoroalkyl group as the surfactant can unexpectedly improve the purity and yield of the polyhedral oligomeric silsesquioxane.

In the production method of an embodiment of the present invention, commercially available products may be used as the surfactant, for example, FC-4430, FC-4432, FC-4434 (above, Novec manufactured by 3M); Commercial items, such as S-241, S-242, S-243, S-420, S-611, S-651, and S-386 (above, SURFLON by ASAHI GLASS), can be used. These can be used individually by 1 type or in combination of 2 or more type.

In particular, the surfactant may comprise [alkyl [(fluoroalkyl) sulfonyl] amino] ethyl ester. At this time, the carbon number of the alkyl group may be appropriately adjusted, for example, the carbon number may be adjusted to 1 to 6. The use of such surfactants can more effectively provide high purity polyhedral oligomeric silsesquioxanes. As the surfactant containing the [alkyl [(fluoroalkyl) sulfonyl] amino] ethyl ester, 3M's Novec series products can be used.

The surfactant may be used in an amount of about 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the first and second silane compounds. Within this range, it is possible to sufficiently increase the compatibility of the silane compound with respect to an organic solvent or the like to prepare a high purity polyhedral oligomeric silsesquioxane.

The first silane compound used in the preparation method of the above embodiment is a precursor for introducing a hydrocarbon group substituted by halogen into a polyhedral oligomeric silsesquioxane. In particular, as the first silane compound, a compound having a polyhedral oligomeric silsesquioxane containing low-refractive, water-repellent, oil-repellent, chemical-resistant, and slippery properties is used in a coating film containing a polyhedral oligomeric silsesquioxane using a compound wherein R 1 is a monovalent residue derived from a hydrocarbon substituted with fluorine. And wear resistance can be imparted.

Specifically, as the first silane compound, R 1 is trifluoromethyl, trifluoroethyl, trifluoropropyl, trifluorobutyl, pentafluorobutyl, trifluoropentyl, pentafluoropentyl, heptafluoro Lopentyl, trifluorohexyl, pentafluorohexyl, heptafluorohexyl, nonafluorohexyl, undecafluorohexyl, perfluorohexyl, trifluoroheptyl, pentafluoroheptyl, heptafluoroheptyl, nona Fluoroheptyl, undecafluoroheptyl, dodecafluoroheptyl, tridecafluoroheptyl, perfluoroheptyl, trifluorooctyl, pentafluorooctyl, heptafluorooctyl, nonafluorooctyl, undecafluoro Rooctyl ( 1H , 1H , 2H , 2H , 3H , 3H- perfluorooctyl), tridecafluorooctyl ( 1H , 1H , 2H , 2H- perfluorooctyl), pentadecafluorooctyl (1 H, 1 H -perfluorooctyl) , perfluorooctyl (perfluorooctyl), chloro Ropil, (chloromethyl) phenyl, (chloromethyl) can be phenylethyl or di-bromo compound using the parent ethyl. In addition, three X 1 in the first silane compound may be the same or different, and may be various leaving groups as defined above.

More specifically, the first silane compound is (trifluoropropyl) trimethoxysilane, (trifluorobutyl) trimethoxysilane, (pentafluorobutyl) trimethoxysilane, (trifluoropentyl) Trimethoxysilane, (pentafluoropentyl) trimethoxysilane, (heptafluoropentyl) trimethoxysilane, (trifluorohexyl) trimethoxysilane, (pentafluorohexyl) trimethoxysilane, ( Heptafluorohexyl) trimethoxysilane, (nonnafluorohexyl) trimethoxysilane, (undecafluorohexyl) trimethoxysilane, (perfluorohexyl) trimethoxysilane, (trifluoroheptyl) Trimethoxysilane, (pentafluoroheptyl) trimethoxysilane, (heptafluoroheptyl) trimethoxysilane, (nonnafluoroheptyl) trimethoxysilane, (undecafluoroheptyl) trimethoxysilane, (Dodecafluoroheptyl) trimethoxysilane, (tridecafluoroheptyl) trimethoxy Column, (perfluoroheptyl) trimethoxysilane, (trifluorooctyl) trimethoxysilane, (pentafluorooctyl) trimethoxysilane, (heptafluorooctyl) trimethoxysilane, (nonafluoro Octyl) trimethoxysilane, (undecafluorooctyl) trimethoxysilane, (tridecafluorooctyl) trimethoxysilane, (pentadecafluorooctyl) trimethoxysilane, (perfluorooctyl) tri Methoxysilane, (chloropropyl) trimethoxysilane, [(chloromethyl) phenyl] trimethoxysilane, [(chloromethyl) phenylethyl] trimethoxysilane, (dibromoethyl) trimethoxysilane, and the like. One or more types selected from the group consisting of can be used.

The second silane compound used in the preparation method of the above embodiment is a precursor for introducing a reactive functional group into the polyhedral oligomeric silsesquioxane. Such reactive functional groups can increase the hardness of the coating film including polyhedral oligomer silsesquioxane to impart scratch resistance and the like, as well as improve adhesion of the coating film to the substrate.

The reactive functional group R 2 of Formula 2 is a (meth) acryloyl group, (meth) acryloyloxy group, hydroxy group, mercapto group, carboxyl group, amino group, cyano group, glycidyl group, glycidyloxy group, carbon number of 2 to 30 An epoxyalkyl group, an epoxyalkoxy group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms and an alkenyloxy group having 2 to 30 carbon atoms, or -OH, -NH 2 , -NH-R 6 , Derived from hydrocarbons of 1 to 30 carbon atoms substituted with one or more substituents selected from the group consisting of -NH 3 X 3 , -COOH, -CONH 2 , -CN, -SH, glycidyl group, glycidyloxy group and maleimide One monovalent residue.

The epoxy alkyl group having 2 to 30 carbon atoms may be a straight chain, branched chain or cyclic alkyl group including an epoxy group. Specifically, the epoxy alkyl group having 2 to 30 carbon atoms may be an epoxycyclohexyl group or the like.

An epoxyalkoxy group having 2 to 30 carbon atoms means a functional group in which the epoxy alkyl group having 2 to 30 carbon atoms is connected to A or Si of Formula 2 through -O-. Epoxy cyclohexoxy group etc. are mentioned as such a C2-C30 epoxy alkoxy group.

Alkenyl group having 2 to 30 carbon atoms means a monovalent moiety derived from straight, branched or cyclic alkene having 2 to 30 carbon atoms. Specifically, a C2-C30 alkenyl group is a vinyl group, an allyl group, norbornene group, etc. are mentioned.

An alkenyloxy group having 2 to 30 carbon atoms means a functional group in which the alkenyl group having 2 to 30 carbon atoms is connected to A or Si of Formula 2 through -O-. Vinyloxy, allyloxy, etc. are mentioned as such a C2-C30 alkenyloxy group.

At least one hydrogen of the hydrocarbon having 1 to 30 carbon atoms is -OH, -NH 2 , -NH-R 6 , -NH 3 X 3 , -COOH, -CONH 2 , -CN, -SH, glycidyl group, glyci Specific examples of the hydrocarbon substituted with one or more substituents selected from the group consisting of a dioxy group and maleimide may be as follows, but are not limited thereto.

The hydrocarbon having 1 to 30 carbon atoms substituted with a hydroxy group (—OH) may be substituted with one or more hydrogens of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such a hydroxy group (-OH) include cyclohexanediol, trimethylolpropane, glycerol, 3-hydroxy-3-methylbutane, and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with the amino group (—NH 2 ) may be substituted with at least one hydrogen of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such an amino group (-NH 2 ) include amino propane, aniline (aminobenzene), and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with a substituted amino group (-NH-R 6 ) may be substituted with one or more hydrogens of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms with -NH-R 6 . Accordingly, the carbon number of the hydrocarbon substituted with -NH-R 6 may exceed 30, and the upper limit of the total carbon number may be adjusted to 60 or less according to the upper limit of the carbon number of R 6 . Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with -NH-R 6 include N-methylaminopropane, N-phenylaminopropane, N- (aminoethyl) aminopropane, and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with an ammonium group (—NH 3 X 3 ) may be one in which at least one hydrogen of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms is substituted with an ammonium group. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such an ammonium group include propyl ammonium chloride and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with a cyano group (-CN) may be substituted with one or more hydrogens of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such a cyano group include propyl nitrile and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with a mercapto group (-SH) may be one in which at least one hydrogen of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms is substituted with a mercapto group. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such mercapto groups include propylthiol and the like.

The hydrocarbon having 1 to 30 carbon atoms substituted with a glycidyloxy group may be substituted with at least one hydrogen of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such glycidyloxy group include glycidyloxypropane.

The hydrocarbon having 1 to 30 carbon atoms substituted with maleimide may be substituted with one or more hydrogens of a straight, branched or cyclic hydrocarbon having 1 to 30 carbon atoms with maleimide. Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with such maleimide include N-propyl maleimide and the like.

And selected from the group consisting of -OH, -NH 2 , -NH-R 6 , -NH 3 X 3 , -COOH, -CONH 2 , -CN, -SH, glycidyl group, glycidyloxy group and maleimide Specific examples of the hydrocarbon having 1 to 30 carbon atoms substituted with two or more substituents include maleamic acid in which two hydrogens of ethene are substituted with -COOH and -CONH 2 in the substituents.

R 2 of Formula 2 may be a monovalent radical in which one hydrogen radical is removed from the above-described substituted hydrocarbon.

R 2 in Formula 2 may be directly connected to Si or may be connected to Si via A. In the former case A may be a single bond and in the latter case A may be a variety of divalent organic groups as defined above. Specifically, A is a single bond, methylene, ethylene, propylene, phenylene, -O-Si (CH 3 ) (CH 3 )-or -O-Si (CH 3 ) (CH 3 ) -CH 2 CH 2 CH 2 -and so on.

As in the first silane compound, the three X 2 of the second silane compound may be the same or different and may be various leaving groups as defined above.

More specifically, as the second silane compound, (3- (meth) acryloxypropyl) trimethoxysilane, (2,3-dihydroxypropoxypropyl) trimethoxysilane, (3,4-dihydro Oxyhexylethyl) trimethoxysilane, (3-hydroxy-3-methylbutyldimethylsiloxy) trimethoxysilane, (3,4-epoxyhexylpropyl) trimethoxysilane, (3,4-epoxyhexylethyl Dimethylsiloxy) trimethoxysilane, (3-aminopropyl) trimethoxysilane, (N-aminoethylaminopropyl) trimethoxysilane, (aminophenyl) trimethoxysilane, (N-phenylaminopropyl) tri Methoxysilane, (N-methylaminopropyl) trimethoxysilane, (3-cyanopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-glycidyloxypropyl) tri Methoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, (trimethoxysilyl) norbornene, N- [3- (trimethoxysilyl) propyl] maleimide and N- [3- (trimeth Sicily reel) propyl] can be used at least one selected from the group consisting of acid, such as the end of the LEA.

Polyhedral oligomeric silsesquioxane prepared through the production method according to the embodiment may be represented by the following formula (3).

[Formula 3]

(R 1 SiO 1.5 ) m (R 2 -A-SiO 1.5 ) n

In Formula 3, A, R 1 and R 2 are the same as defined in Formulas 1 and 2, and m and n are each independently an integer of 1 to 29, and the sum of m and n is an integer of 6 to 30.

M and n in the general formula (3) can be adjusted according to the molar ratio of the first silane compound and the second silane compound. Therefore, the use amount of the first silane compound and the second silane compound can be adjusted according to the structure of the polyhedral oligomeric silsesquioxane to be prepared. 4: For example, (. R 1 SiO 1 5 ) 4 (R 2 -A-SiO 1.5) 4 in the case to prepare a polyhedral oligomeric silsesquioxane with a first silane and a second silane compound about 4 It can be used in a molar ratio.

In the preparation method according to the embodiment, the first silane compound and the second silane compound may be reacted in the presence of a base catalyst. When the acid catalyst is used under such reaction conditions, it is possible to further increase the yield of the comparative product.

As the base catalyst, various compounds used in the art to which the present invention pertains may be used without limitation. However, ammonium hydroxide may be used among various base catalysts to minimize side reactions and improve the synthesis yield of polyhedral oligomeric silsesquioxane. More specifically, as ammonium hydroxide, methylammonium hydroxide, tetramethylammonium hydroxide, ethylammonium hydroxide, tetraethylammonium hydroxide, or the like can be used. The amount of the base catalyst is not particularly limited, but may be used in an amount of 0.001 to 100 moles based on 100 moles of the total silane compound. Within this range, side reactions can be minimized and high-purity polyhedral oligomeric silsesquioxanes can be synthesized with high efficiency.

In addition, the preparation method according to the embodiment may react the reaction mixture under an organic solvent. Thereby, generation | occurrence | production of the by-product which has high molecular weight of a structure other than the polyhedral oligomer silsesquioxane which has a cage structure can be suppressed further. As the organic solvent, an organic solvent capable of exhibiting proper solubility with respect to the first and second silane compounds without affecting the reaction of the first and second silane compounds may be used without limitation. For example, an ether solvent such as diethyl ether or tetrahydrofuran may be used as the organic solvent.

In the preparation method according to the embodiment, the reaction mixture including the first and second silane compounds and the surfactant may be reacted at an appropriate temperature for an appropriate time. Although the reaction temperature and reaction time are not particularly limited, the reaction temperature may be adjusted to about 0 to 40 ℃, the reaction time may be adjusted to about 5 hours to 128 hours.

It is possible to synthesize polyhedral oligomeric silsesquioxanes in high yield within this range.

Polyhedral oligomeric silsesquioxane prepared by the above-described method has high purity and can also exhibit low refractive properties. For example, the polyhedral oligomeric silsesquioxane may have a refractive index of about 1.20 to 1.50 or about 1.30 to 1.48 measured by an Abbe refractometer.

Thus, a polyhedral oligomeric silsesquioxane exhibiting a low refractive index may be used in a low refractive layer of an antireflection film of a display device to implement a very low reflectance. In particular, the use of the polyhedral oligomeric silsesquioxane is expected to provide a high-quality anti-reflection film economically because it is possible to omit the high-temperature process for generating a low refractive index by generating existing bubbles.

Hereinafter, the operation and effect of the invention will be described in more detail with reference to specific examples. However, this is presented as an example of the invention, whereby the scope of the invention is not limited in any sense.

Example  1: polyhedral oligomer Silsesquioxane  synthesis

25 g (114.55 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 8.9 g (37.98 mmol) of (3-acryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant a (3M社the FC-4432) solution 9 g THF (tetrahydrofuran) dissolved in 140 mL 5% of N (CH 3) weight 4 OH aqueous solution of 9.2 g: a (N (CH 3) 4 OH molar number 100.93 mmol) was added . Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 21 g of a liquid polyhedral oligomeric silsesquioxane (TA62). The refractive index of TA62 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.411.

1 H NMR (400 MHz): 6.392 (2H, br), 6.122 (2H, br), 5.826 (2H, br), 4.129 (4H, br), 2.120 (12H, br), 1.735 (4H, br), 0.904 (12H, br), 0.724 (4H, br)

Example  2: polyhedral oligomer Silsesquioxane  synthesis

15 g (68.73 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 16.1 g (68.71 mmol) of (3-acryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorinated surfactant a (3M社the FC-4432) solution of 8.1 g THF (tetrahydrofuran) dissolved in 180 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 8.5 g: a (N (CH 3) 4 OH number of moles 93.25 mmol) was added . Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 200 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 19.5 g of a liquid polyhedral oligomeric silsesquioxane (TA44). The refractive index of TA44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.435.

1 H NMR (400 MHz): 6.392 (4H, br), 6.122 (4H, br), 5.826 (4H, br), 4.129 (8H, br), 2.120 (8H, br), 1.735 (8H, br), 0.904 (8H, br), 0.724 (8H, br)

Example  3: polyhedral oligomer Silsesquioxane  synthesis

8 g (36.66 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 25.7 g (109.68 mmol) of (3-acryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (3M社the FC-4432) solution of 8.7 g of THF (tetrahydrofuran) dissolved in 140 mL 5% of N (CH 3) weight 4 OH aqueous solution of 9.0 g: a (N (CH 3) 4 OH number of moles 98.74 mmol) was added . Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 20.8 g of a liquid polyhedral oligomeric silsesquioxane (TA26). The refractive index of TA26 measured by an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.453.

1 H NMR (400 MHz): 6.392 (6H, br), 6.122 (6H, br), 5.826 (6H, br), 4.129 (12H, br), 2.120 (4H, br), 1.735 (12H, br), 0.904 (4H, br), 0.724 (12H, br)

Example  4: polyhedral oligomer Silsesquioxane  synthesis

25 g (114.55 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 9.5 g (38.25 mmol) of (3-methacryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based interface surfactant (3M社the FC-4432) solution of 9 g of THF (tetrahydrofuran) dissolved in 140 mL of 5 wt% N (CH 3) 4 OH aqueous solution of 9.4 g (N (CH 3) 4 OH molar amount: 103.13 mmol) was added It was. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 22 g of a liquid polyhedral oligomeric silsesquioxane (TM62). The refractive index of TM62 measured with the Abbe refractometer (DTM-1, ATAGO company) was 1.409.

Example  5: polyhedral oligomer Silsesquioxane  synthesis

15 g (68.73 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 17.1 g (68.85 mmol) of (3-methacryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based interface surfactant (3M社the FC-4432) solution of 8.1 g of THF (tetrahydrofuran) dissolved in 130 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 8.5 g (N (CH 3) 4 OH molar number: 93.25 mmol) was added It was. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 200 mL of ethyl acetate, and the byproduct was extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 19 g of a liquid polyhedral oligomeric silsesquioxane (TM44). The refractive index of TM44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.437.

Example  6: polyhedral oligomer Silsesquioxane  synthesis

7 g (32.07 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 23.9 g (96.24 mmol) of (3-methacryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based interface surfactant (3M社the FC-4432) solution of 7.6 g of THF (tetrahydrofuran) dissolved in 120 mL of 5 wt% N (CH 3) 4 OH aqueous solution of 7.9 g (N (CH 3) 4 OH molar number: 86.67 mmol) was added It was. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 18 g of a liquid polyhedral oligomeric silsesquioxane (TM26). The refractive index of TM26 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.455.

Example  7: polyhedral oligomer Silsesquioxane  synthesis

20 g (91.64 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 7.2 g (30.46 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine surfactant (3M社the FC-4432) solution of 7.2 g of THF (tetrahydrofuran) dissolved in 110 mL of 5 wt% N (CH 3) 4 OH aqueous solution of 7.4 g (N (CH 3) 4 OH molar number: 81.18 mmol) of Added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 140 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 17 g of a liquid polyhedral oligomeric silsesquioxane (TG62). The refractive index of TG62 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.405.

Example  8: polyhedral oligomer Silsesquioxane  synthesis

15 g (68.73 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 16.2 g (68.55 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine surfactant (3M社the FC-4432) solution of 8.1 g of THF (tetrahydrofuran) dissolved in 130 mL of 5 wt% N (CH 3) 4 OH aqueous solution of 8.5 g (N (CH 3) 4 OH molar number: 93.25 mmol) of Added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 19 g of a liquid polyhedral oligomeric silsesquioxane (TG44). The refractive index of TG44 measured by an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.435.

Example  9: polyhedral oligomer Silsesquioxane  synthesis

7 g (32.07 mmol) of (3,3,3-trifluoropropyl) trimethoxysilane, 22.7 g (96.05 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based 7.59 g of a surfactant (3-4 FC-4432) solution was dissolved in 120 mL of THF (tetrahydrofuran), and 7.9 g (N (CH 3 ) 4 OH mole number: 86.67 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 18 g of a liquid polyhedral oligomeric silsesquioxane (TG26). The refractive index of TG26 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.451.

Example  10: polyhedral oligomer Silsesquioxane  synthesis

25 g (67.88 mmol) of (nonafluorohexyl) trimethoxysilane, 5.3 g (22.62 mmol) of (3-acryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (FC- made by 3M) 4432) 5.8 g of solution was dissolved in 80 mL of THF (tetrahydrofuran) and 5.6 g (N (CH 3 ) 4 OH molar number: 61.44 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 21 g of a liquid polyhedral oligomeric silsesquioxane (NA62). The refractive index of NA62 measured with the Abbe refractometer (DTM-1, ATAGO company) was 1.373.

1 H NMR (400 MHz): 6.379 (2H, br), 6.108 (2H, br), 5.805 (2H, br), 4.118 (4H, br), 2.118 (12H, br), 1.753 (4H, br), 0.918 (12H, br), 0.705 (4H, br)

Example  11: polyhedral oligomer Silsesquioxane  synthesis

15 g (40.73 mmol) of (nonafluorohexyl) trimethoxysilane, 9.5 g (40.54 mmol) of (3-acryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (FC- made by 3M) 4432) 5.1 g of solution was dissolved in 75 mL of THF (tetrahydrofuran) and 5.0 g (N (CH 3 ) 4 OH molar number: 54.85 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 17 g of a liquid polyhedral oligomeric silsesquioxane (NA44). The refractive index of NA44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.404.

1 H NMR (400 MHz): 6.379 (4H, br), 6.108 (4H, br), 5.805 (4H, br), 4.118 (8H, br), 2.118 (8H, br), 1.753 (8H, br), 0.918 (8H, br), 0.705 (8H, br)

Example  12: polyhedral oligomer Silsesquioxane  synthesis

(Nonafluorohexyl) trimethoxysilane 7 g (19.01 mmol), (3-acryloxypropyl) trimethoxysilane 13.4 g (57.19 mmol), 1% by weight of nonionic fluorine-based surfactant (FC- made by 3M) 4432) 4.6 g of the solution was dissolved in 70 mL of THF (tetrahydrofuran) and 4.7 g (N (CH 3 ) 4 OH molar number: 51.56 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 120 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 13.5 g of a liquid polyhedral oligomeric silsesquioxane (NA26). The refractive index of NA26 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.433.

1 H NMR (400 MHz): 6.379 (6H, br), 6.108 (6H, br), 5.805 (6H, br), 4.118 (12H, br), 2.118 (4H, br), 1.753 (12H, br), 0.918 (4H, br), 0.705 (12H, br)

Example  13: polyhedral oligomer Silsesquioxane  synthesis

25 g (67.88 mmol) of (nonnafluorohexyl) trimethoxysilane, 5.6 g (22.55 mmol) of (3-methacryloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (FC made by 3M) 5.8 g of the solution was dissolved in 80 mL of THF (tetrahydrofuran) and 5.6 g (N (CH 3 ) 4 OH molar number: 61.44 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 21 g of a liquid polyhedral oligomeric silsesquioxane (NM62). The refractive index of NM62 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.374.

Example  14: polyhedral oligomer Silsesquioxane  synthesis

(Nonafluorohexyl) trimethoxysilane 20 g (54.31 mmol), (3-methacryloxypropyl) trimethoxysilane 13.5 g (54.36 mmol), 1% by weight of nonionic fluorine-based surfactant (FC made by 3M) -4432) was added 6.8 g of THF (tetrahydrofuran) dissolved in 100 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 6.7 g (N (CH 3) 4 OH number of moles: was added to 73.51 mmol). Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 23.5 g of a liquid polyhedral oligomeric silsesquioxane (NM44). The refractive index of NM44 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.406.

Example  15: polyhedral oligomer Silsesquioxane  synthesis

(Nonafluorohexyl) trimethoxysilane 10 g (27.15 mmol), (3-methacryloxypropyl) trimethoxysilane 20.2 g (81.34 mmol), 1% by weight of nonionic fluorine-based surfactant (FC made by 3M) -4432) was added 6.7 g of THF (tetrahydrofuran) dissolved in 100 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 6.7 g (N (CH 3) 4 OH number of moles: was added to 73.51 mmol). Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 20 g of a liquid polyhedral oligomeric silsesquioxane (NM26). The refractive index of NM26 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.438.

Example  16: polyhedral oligomer Silsesquioxane  synthesis

25 g (67.88 mmol) of (nonnafluorohexyl) trimethoxysilane, 5.3 g (22.43 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (manufactured by 3M Corporation) 5.8 g of FC-4432) solution was dissolved in 90 mL of THF (tetrahydrofuran) and 5.6 g (N (CH 3 ) 4 OH molar number: 61.44 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 21.5 g of a liquid polyhedral oligomeric silsesquioxane (NG62). The refractive index of NG62 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.372.

Example  17: polyhedral oligomer Silsesquioxane  synthesis

20 g (54.31 mmol) of (nonafluorohexyl) trimethoxysilane, 12.8 g (54.16 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (manufactured by 3M Corporation) 6.8 g of FC-4432) solution was dissolved in 100 mL of THF (tetrahydrofuran) and 6.7 g (N (CH 3 ) 4 OH molar number: 73.51 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 18.5 g of a liquid polyhedral oligomeric silsesquioxane (NG44). The refractive index of NG44 measured by the Abbe refractometer (DTM-1, ATAGO company) was 1.402.

Example  18: polyhedral oligomer Silsesquioxane  synthesis

10 g (27.15 mmol) of (nonnafluorohexyl) trimethoxysilane, 19.3 g (81.66 mmol) of (3-glycidyloxypropyl) trimethoxysilane, 1% by weight of nonionic fluorine-based surfactant (manufactured by 3M Corporation) 6.6 g of FC-4432) solution was dissolved in 110 mL of THF (tetrahydrofuran) and 6.7 g (N (CH 3 ) 4 OH molar number: 73.51 mmol) of 5% by weight aqueous N (CH 3 ) 4 OH solution was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 20 g of a liquid polyhedral oligomeric silsesquioxane (NG26). The refractive index of NG26 measured by an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.435.

Example  19: polyhedral oligomer Silsesquioxane  synthesis

( 1H , 1H , 2H , 2H -perfluorooctyl) trimethoxysilane 25 g (53.39 mmol), (3-acryloxypropyl) trimethoxysilane 4.2 g (17.92 mmol), 1 wt% the non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 4.8 g of THF (tetrahydrofuran) dissolved in 65 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 4.4 g (N (CH 3) 4 OH number of moles: 48.27 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 11.5 g of a liquid polyhedral oligomeric silsesquioxane (HA62). The refractive index of HA62 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.370.

Example  20: polyhedral oligomer Silsesquioxane  synthesis

(1 H, 1 H, 2 H, 2 H - perfluorooctyl) silane 20 g (42.71 mmol), ( 3- acryloxypropyl) trimethoxysilane 10 g (42.68 mmol), 1 % by weight the non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 5.6 g of THF (tetrahydrofuran) dissolved in 80 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 5.3 g (N (CH 3) 4 OH number of moles: 58.15 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 17.5 g of a liquid polyhedral oligomeric silsesquioxane (HA44). The refractive index of HA44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.391.

Example  21: polyhedral oligomer Silsesquioxane  synthesis

(1 H, 1 H, 2 H, 2 H - perfluorooctyl) silane 15 g (32.03 mmol), ( 3- acryloxypropyl) trimethoxysilane 22.5 g (96.02 mmol), 1 % by weight the non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 8.0 g of THF (tetrahydrofuran) dissolved in 120 mL 5% of N (CH 3) weight 4 OH aqueous solution of 7.9 g (N (CH 3) 4 OH number of moles: 86.67 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 200 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 26 g of a liquid polyhedral oligomeric silsesquioxane (HA26). The refractive index of HA26 measured by an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.427.

Example  22: polyhedral oligomer Silsesquioxane  synthesis

( 1H , 1H , 2H , 2H -perfluorooctyl) trimethoxysilane 25 g (53.39 mmol), (3-methacryloxypropyl) trimethoxysilane 4.4 g (17.72 mmol), 1 weight % of non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 4.9 g of THF (tetrahydrofuran) dissolved in 65 mL of N 5% by weight of (CH 3) 4 OH 4.4 g aqueous solution (N (CH 3) 4 OH number of moles : 48.27 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 12 g of a liquid polyhedral oligomeric silsesquioxane (HM62). The refractive index of HM62 measured with the Abbe refractometer (DTM-1, ATAGO company) was 1.373.

Example  23: polyhedral oligomer Silsesquioxane  synthesis

( 1H , 1H , 2H , 2H -perfluorooctyl) trimethoxysilane 20 g (42.71 mmol), (3-methacryloxypropyl) trimethoxysilane 10.6 g (42.68 mmol), 1 weight dissolve% of non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 5.6 g in THF (tetrahydrofuran) 80 mL 5% by weight of N (CH 3) 4 OH aqueous solution of 5.3 g (N (CH 3) 4 OH number of moles : 58.15 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 19.5 g of a liquid polyhedral oligomeric silsesquioxane (HM44). The refractive index of HM44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.394.

Example  24: polyhedral oligomer Silsesquioxane  synthesis

( 1H , 1H , 2H , 2H -perfluorooctyl) trimethoxysilane 15 g (32.03 mmol), (3-methacryloxypropyl) trimethoxysilane 23.9 g (96.24 mmol), 1 weight % non-ionic fluorochemical surfactant (3M社the FC-4432) was added 8.0 g of THF (tetrahydrofuran) dissolved in 120 mL 5% of N (CH 3) weight 4 OH aqueous solution of 7.9 g (N (CH 3) 4 OH number of moles : 86.67 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 21 g of a liquid polyhedral oligomeric silsesquioxane (HM26). The refractive index of HM26 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.434.

Example  25: polyhedral oligomer Silsesquioxane  synthesis

( 1H , 1H , 2H , 2H -perfluorooctyl) trimethoxysilane 30 g (64.06 mmol), (3-glycidyloxypropyl) trimethoxysilane 5 g (21.16 mmol), 1 5.8 g of a solution of wt% nonionic fluorine-based surfactant (FC-4432 manufactured by 3M) was dissolved in 80 mL of THF (tetrahydrofuran), and 5.3 g of N (CH 3 ) 4 OH aqueous solution 5.3 g (N (CH 3 ) 4 OH Molar number: 58.15 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 14 g of a liquid polyhedral oligomeric silsesquioxane (HG62). The refractive index of HG62 measured with the Abbe refractometer (DTM-1, ATAGO company) was 1.369.

Example  26: polyhedral oligomer Silsesquioxane  synthesis

(1 H, 1 H, 2 H, 2 H - perfluorooctyl) silane 20 g (42.71 mmol), ( 3- glycidyloxy propyl) trimethoxysilane 10.1 g (42.74 mmol), 1 5.6 g of a solution of wt% nonionic fluorine-based surfactant (FC-4432 manufactured by 3M) was dissolved in 80 mL of THF (tetrahydrofuran), and 5.3 g of N (CH 3 ) 4 OH aqueous solution 5.3 g (N (CH 3 ) 4 OH Molar number: 58.15 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under reduced pressure, dissolved in 150 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 17.5 g of a liquid polyhedral oligomeric silsesquioxane (HG44). The refractive index of HG44 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.389.

Example  27: polyhedral oligomer Silsesquioxane  synthesis

(1 H, 1 H, 2 H, 2 H - perfluorooctyl) silane 15 g (32.03 mmol), ( 3- glycidyloxy propyl) trimethoxysilane 22.7 g (96.05 mmol), 1 of 5% by weight dissolved non-ionic fluorochemical surfactant (3M社the FC-4432) solution of 8.0 g of the% by weight in THF (tetrahydrofuran) 120 mL N ( CH 3) 4 OH aqueous solution of 7.9 g (N (CH 3) 4 OH Molar number: 86.67 mmol) was added. Thereafter, the reaction mixture was stirred at room temperature for 72 hours. After the reaction was completed, the reaction product was dried under a reduced pressure, dissolved in 190 mL of ethyl acetate, and the by-products were extracted four times with an aqueous NaCl solution. Thereafter, the organic layer was dried over MgSO 4 , filtered, and the filtrate was dried under reduced pressure to obtain 25 g of a liquid polyhedral oligomeric silsesquioxane (HG26). The refractive index of HG26 measured with an Abbe refractometer (DTM-1, ATAGO Co., Ltd.) was 1.431.

Comparative example  1 to 27: polyhedral oligomer Silsesquioxane  synthesis

Polyhedral oligomeric silsesquioxane was synthesized in the same manner as in Examples 1 to 27, except that the nonionic fluorine-based surfactant solution was not used in Examples 1 to 27.

Comparative example  28: polyhedral oligomer Silsesquioxane  synthesis

Polyhedral oligomer sils in the same manner as in Example 1, except that 0.23% by weight of anionic non-fluorine-based surfactant (sodium dodecyl sulfate (SDS) solution of SIGMA ALDRICH) instead of the non-ionic fluorine-based surfactant solution was used. Quioxane was synthesized.

Comparative example  29: polyhedral oligomer Silsesquioxane  synthesis

A polyhedral oligomeric silsesquioxane was synthesized in the same manner as in Example 1 except that 0.23% by weight of an anionic fluorine-based surfactant (S-211 manufactured by ASAHI GLASS) was used instead of the nonionic fluorine-based surfactant solution. It was.

Test Example : Polyhedral Oligomer Silsesquioxane  Purity evaluation

The purity of the polyhedral oligomeric silsesquioxanes prepared in Examples 2, 11, Comparative Example 2, Comparative Example 11, Comparative Examples 28 and 29 was determined by area percent using GPC (Gel Permeation Chromatography). In this case, polystyrene was used as a standard sample, THF was used as a solvent, and an evaporative light scattering (ELS) detector was used as a detector.

Example 2 Comparative Example 2 Example 11 Comparative Example 11 Comparative Example 28 Comparative Example 29 GPC [Area%] 85.0 75.0 83.7 67.3 74.0 79.0

Referring to Table 1, it is confirmed that the polyhedral oligomeric silsesquioxane prepared according to Examples 2 and 11 has a higher purity than Comparative Examples 2 and 11 without using a surfactant. In addition, it was confirmed that the polyhedral oligomeric silsesquioxane prepared according to Examples 2 and 11 also had high purity, compared to Comparative Example 28 using a non-fluorine-based surfactant and Comparative Example 29 using an anionic fluorine-based surfactant. It is thus confirmed that according to the preparation method of one embodiment of the present invention, it is possible to provide a polyhedral oligomeric silsesquioxane of remarkably improved purity.

Claims (16)

Reacting a reaction mixture comprising a first silane compound represented by Formula 1, a second silane compound represented by Formula 2, and a nonionic fluorine-based surfactant,
Method for preparing a polyhedral oligomeric silsesquioxane represented by the following formula (3) to produce a polyhedral oligomeric silsesquioxane having a cage structure:
[Formula 1]
R 1 -SiX 1 3
[Formula 2]
R 2 -A-SiX 2 3
[Formula 3]
(R 1 SiO 1.5 ) m (R 2 -A-SiO 1.5 ) n
In Chemical Formulas 1 to 3, A is a single bond or an alkylene group having 1 to 10 carbon atoms,
R 1 is an alkyl group having 1 to 30 carbon atoms substituted with fluoro,
R 2 is a functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group, a glycidyl group, and a glycidyloxy group,
X 1 and X 2 are each independently an alkoxy group having 1 to 5 carbon atoms,
m and n are each independently an integer of 1 to 29, and the sum of m and n is an integer of 6 to 30.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein the nonionic fluorine-based surfactant is [alkyl [(fluoroalkyl) sulfonyl] amino] ethyl ester.
The method of claim 1, wherein the nonionic fluorine-based surfactant is used at 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the first and second silane compounds.
A compound according to claim 1, wherein R 1 is trifluoromethyl, trifluoroethyl, trifluoropropyl, trifluorobutyl, pentafluorobutyl, trifluoropentyl, pentafluoropentyl, Heptafluoropentyl, trifluorohexyl, pentafluorohexyl, heptafluorohexyl, nonafluorohexyl, undecafluorohexyl, perfluorohexyl, trifluoroheptyl, pentafluoroheptyl, heptafluoroheptyl , Nonafluoroheptyl, undecafluoroheptyl, dodecafluoroheptyl, tridecafluoroheptyl, perfluoroheptyl, trifluorooctyl, pentafluorooctyl, heptafluorooctyl, nonafluorooctyl, unde A method for producing a polyhedral oligomeric silsesquioxane using a compound which is carfluorooctyl, tridecafluorooctyl, pentadecafluorooctyl, or perfluorooctyl.
delete The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein a compound in which A is propylene is used as the second silane compound.
The compound according to claim 1, wherein the first silane compound is (trifluoropropyl) trimethoxysilane, (trifluorobutyl) trimethoxysilane, (pentafluorobutyl) trimethoxysilane, (trifluoropentyl Trimethoxysilane, (pentafluoropentyl) trimethoxysilane, (heptafluoropentyl) trimethoxysilane, (trifluorohexyl) trimethoxysilane, (pentafluorohexyl) trimethoxysilane, (Heptafluorohexyl) trimethoxysilane, (nonnafluorohexyl) trimethoxysilane, (undecafluorohexyl) trimethoxysilane, (perfluorohexyl) trimethoxysilane, (trifluoroheptyl ) Trimethoxysilane, (pentafluoroheptyl) trimethoxysilane, (heptafluoroheptyl) trimethoxysilane, (nonafluoroheptyl) trimethoxysilane, (undecafluoroheptyl) trimethoxysilane , (Dodecafluoroheptyl) trimethoxysilane, (tridecafluoroheptyl) trimethoxysil , (Perfluoroheptyl) trimethoxysilane, (trifluorooctyl) trimethoxysilane, (pentafluorooctyl) trimethoxysilane, (heptafluorooctyl) trimethoxysilane, (nonafluorooctyl Trimethoxysilane, (undecafluorooctyl) trimethoxysilane, (tridecafluorooctyl) trimethoxysilane, (pentadecafluorooctyl) trimethoxysilane, and (perfluorooctyl) tri A method for producing a polyhedral oligomeric silsesquioxane using at least one member selected from the group consisting of methoxysilane.
delete The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein the reaction mixture is reacted in the presence of a base catalyst.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 9, wherein ammonium hydroxide is used as the base catalyst.
The method of claim 9, wherein the base catalyst is used in an amount of 0.001 to 100 moles based on 100 moles of the total silane compound.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein the reaction mixture is reacted under an organic solvent.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 12, wherein an ether solvent is used as the organic solvent.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein the reaction mixture is reacted at a temperature of 0 ° C to 40 ° C.
The method for producing a polyhedral oligomeric silsesquioxane according to claim 1, wherein the reaction mixture is reacted for 5 to 128 hours.
delete
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