KR20020095382A - Cylindrical Polysiloxane Dendrimer - Google Patents

Abstract

PURPOSE: A novel cylinder-shaped polysiloxane dendrimer is provided, which can act like a nanotube and can have a variety of application by substituting the side chain terminal with various organic functional groups. CONSTITUTION: The cylinder-shaped polysiloxane dendrimer is represented by the formula 1, 2, 3 or 4. In the formula 1, R1 is an allyl group, an alkyl group, an aryl group, a pyridine derivative or a two kind of aryl group and n is an integer of 1-70; in the formula 2, a is 1 or 2 and n is an integer of 1-70; in the formula 3, R2 is an allyl group, an alkyl group, an aryl group, a pyridine derivative or a two kind of aryl group, b is 1 or 2 and n is an integer of 1-70; and in the formula 4, R3 is an allyl group, an alkyl group, an aryl group, a pyridine derivative or a two kind of aryl group and n is an integer of 1-70. The cylinder-shaped polysiloxane dendrimer is prepared by the substitution reaction in the presence of trimethylethtylene diamine or by the Si-H addition reaction in the presence of a platinum catalyst.

Description

Cylindrical Polysiloxane Dendrimer

The present invention relates to a novel cylindrical polysiloxane dendrimer, and more specifically, the polysiloxane is a copolymer such as a monomer structure-[R ₁ R ₂ SiO] ₄ -containing an oxygen atom between silicon-silicon atoms, wherein R ₁ R ₂ is intended to provide a cylindrical polysiloxane dendrimer that can be substituted with a variety of organic groups can act as nanotubes with excellent commercial applications.

In general, polysiloxane derivatives have already been studied for their low glass transition temperature (Tg) value and its very stable thermal stability [Warrick, EL, Forty Years of Firsts-the Recollections of a Dow Corning Pioneer]. , McGraw Hill, New York (1990).

In addition, carbosiloxane dendrimers having side chain structures of various shapes have been synthesized using the spatial flexibility of linear atoms, which are characteristic of these structures.

The following are examples of known organosiloxane dendrimers. Siloxane dendrimers [Rebrov, et al., Dokl. Acad. Nauk. SSSR, 309, 367 (1989) and Masamune, et al., J. Am. Chem. Soc., 112, 7077 (1990)], carbosiloxane dendrimers (Kakimoto, et al., Macromolecules, 24, 3469 (1991); Japanese Patent Laid-Open No. 7-17981 (17,98 / 1995) and Sheiko, et al., Macromol. Rapid Commun., 17, 283 (1996)] and carbosilane dendrimers (Roovers, et al., Macromolecules, 26 963 (1993) and Japanese Patent Application Laid-open No. Hei 8-311205 (311,205 / 1996). This document also describes carbosiloxane dendrimers in which siloxane bonds and silalkylene bonds are formed alternately. See Japanese Patent Application Laid-Open No. 7-17981 and Sheiko et al., Macromol. Rapid Commun., 17, 283 (1996).

In the case of a cylindrical polymer having a dendrimer-type development according to the present invention, the polymer having one or more functional groups in the linear structure is used as the core material, and the side chain structure is developed on the linear structure by using the dendrimer divergent synthesis method. It can be represented by the same structural formula. See DA Tomalia, et al., J. Am. Chem. Soc. 120, 2678 (1998).

Dendrimers are generally macromolecular compounds having a symmetrical structure, and are synthesized in a symmetrical circular structure from a core core material, whereas in the case of the cylindrical polysiloxane dendrimer of the present invention, the structure is a dendrimer-type development using a linear copolymer as a core. Through a large amount of functional groups are substituted in the side chain structure along the linear structure, the overall structure is expected to have the same applicability as nanotubes, and the research on the synthesis and application is being actively conducted. US Patent 4,694,064 (1986); Nadjet Ouali, et al., Macromolecules, 33, 6185 (2000); Holger Frey, Angew. Chem. Int. Ed., 37, No. 16, 2193 (1998); D. A. Tomalia, et al., J. Am. Chem. Soc., 120, 2678 (1998).

In the present invention, by using the reactivity of a plurality of functional Si-H contained in the polysiloxane has a low molecular weight distribution which is a highly branched structure in which siloxane bonds and silyloxy bonds having a dendrimer-based development using polysiloxane as a core material are alternated. Cylindrical polysiloxane dendrimers were synthesized, and the present invention was completed with the technical problem of the present invention in synthesizing a novel polysiloxane dendrimer having various applications by substituting various alkoxy functional groups at the side chain ends thereof.

1 is a synthetic process diagram of a polysiloxane having a dendritic expansion according to the present invention

2 is a polysiloxane dendrimer in which the side chain ends of the present invention are substituted with various alkoxy functional groups.

3 is a structural diagram of a cylindrical polysiloxane dendrimer according to the present invention

Figure 4 is an elemental analysis, GPC data of a cylindrical polysiloxane dendrimer terminally substituted with an alkoxy functional group side chain ends according to the present invention

FIG. 5 is a ¹ H-nuclear magnetic resonance spectrum of a cylindrical polysiloxane dendrimer in which the side chain terminal is substituted with an alkoxy functional group according to the present invention. FIG.

1 is a synthetic process diagram of a polysiloxane having a dendrimer-type development according to the present invention, Figure 2 is a polysiloxane dendrimer substituted with various alkoxy functional groups in the side chain end according to the present invention, Figure 3 is a cylindrical polysiloxane dendrimer of the present invention As a structural diagram and the like,

The present invention has excellent commercial applicability by substituting various organic groups for R ₁ R ₂ constituting a polysiloxane which is a copolymer of a monomer structure-[R ₁ R ₂ SiO] ₄ -containing an oxygen atom between silicon-silicon atoms. To provide a cylindrical polysiloxane dendrimer that can play the same role as nanotubes.

That is, in the present invention, the substitution reaction by desalting in the presence of trimethylethylenediamine by using a chlorine atom as a reactive group on the terminal silicon atoms of the compounds of the various organic groups, or platinum to an unsaturated functional group present at the terminal in the compound Si-H addition reaction in the presence of a catalyst to obtain a polysiloxane dendrimer of the structure, such as the formula 1,2,3,4, and the present invention will be described in more detail based on the following formula.

Wherein R ¹ is allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, n is 1 to 70.

Polysiloxane compound having a side chain structure corresponding to the first generation of the material of the present invention has the general structure as shown above, the formula is a triclovinylsilane by using the reactivity of a plurality of functional Si-H bonded to the polysiloxane linear structure, A new first generation with three branches with dendrimer evolution by carrying out addition reaction with allyl alcohol and substitution reaction by desalting in the presence of trimethylethylenediamine with chlorine atoms as reactive groups on terminal silicon atoms in the compound Make a compound. This reaction is carried out in the presence of a platinum catalyst and each reaction proceeds through heating under an organic solvent which does not affect the reaction.

The product was identified through nuclear magnetic resonance spectra and found to have a low molecular weight distribution via GPC.

Wherein a is 1 to 2 and n is 1 to 70.

The present invention provides the platinum to the unsaturated functional groups present at the terminal of the compound for the purpose of controlling the branching unit branch to one or two by using the reactivity of the unsaturated functional group of the substance corresponding to R of the formula (1) Synthesis is carried out by addition of Si—H in the presence of a catalyst. The number a of methyl groups is 1-2, and synthesize | combined 2nd generation which has a chlorine atom on a terminal silicon atom. At this time, the number of chlorine atoms has 3-a. This reaction proceeds through heating under an organic solvent that does not affect the reaction.

The product of this reaction was confirmed through nuclear magnetic resonance spectra, and it was confirmed that it had a low molecular weight distribution through GPC.

Wherein R ² is allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, b is 1 to 2, n is 1 to 70.

1 to 1 through a process corresponding to a substitution reaction by desalting in the presence of trimethylethylenediamine by using a chlorine atom as a reactive group on a terminal silicon atom in a compound using the reactivity of chlorine bonded to the silicon atom of formula 2 as defined above Substitute two allyloxy groups. In this case, the number b of methyl groups bonded to the second generation silicon atom is 1 to 2, and the number of allyloxy groups to be substituted is substituted by the number corresponding to 3-b. This reaction proceeds through heating under an organic solvent that does not affect the reaction.

The product was identified through nuclear magnetic resonance spectra and found to have a low molecular weight distribution through GPC.

Wherein R ³ is allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, n is 1 to 70.

In the structure defined in Chemical Formula 2, a compound having a is 2 and Cl is 1 is subjected to a substitution reaction by desalting in the presence of trimethylethylenediamine by reacting a chlorine atom on a terminal silicon atom of the compound as a functional group. It substitutes the organofunctional groups 8-hydroxyquinoline, 5- (2-hydroxyethyl) -4-methylthiazole, p-pyridinepropanol, p-pyridinealdoxime, and cholresterol with various possible hydroxyl groups. This reaction proceeds through heating under an organic solvent that does not affect the reaction.

The product of this reaction was also confirmed by the nuclear magnetic resonance spectrum, it was confirmed to have a low molecular weight distribution through GPC.

Hereinafter, various embodiments of the present invention will be described in more detail below.

Example 1

Molecular Formula 1

9.25 g (41.75 mmol) of Compound 2 shown in FIG. 1 obtained by reacting polysiloxane with trichloro vinylsilane in the presence of Pt / C was dissolved in 25 m of toluene in 8.14 g (140.15 mmol) allyl alcohol and 17.47 g (150.52 mmol) trimethyl. Ethylenediamine was dissolved in 100 ml of toluene and added dropwise for 1 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 1 hour to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered through hexane to give 9.89 g (34.52 mmol) of the product. After liquid chromatography (LC) with toluene, the solvent was distilled off to yield 8.89 g (31.03 mmol, 74.33%) of a colorless translucent gel product.

Example 2

Molecular Formula 2

1.55 g (5.40 mmol) of the product G1-3A obtained in Example 1 was dissolved in 15 ml of toluene and 5.79 g (50.33 mmol) of dichloromethyl silane was stirred for 3 hours in the presence of Pt / C, followed by stirring under reflux for 24 hours. .

¹ H-nuclear magnetic resonance spectra confirmed that the reaction was completed, and then filtered under gas nitrogen with hexane to remove excess solvent of dichloromethyl silane by distillation under reduced pressure. 2.84 g (4.49 mmol, 83.53%) of colorless transparent gel was obtained. The product was obtained.

Example 3

Molecular Formula 3

In a solution of 1.99 g (3.15 mmol) of the product G2P-6Cl obtained in Example 2 in 35 ml of toluene, 1.70 g (29.27 mmol) allyl alcohol and 2.66 g (22.88 mmol) trimethylethylenediamine were dissolved in 50 ml of toluene and added dropwise for 0.5 hour. It was.

After stirring for 12 hours at room temperature, the reaction was confirmed to be complete by ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with hexane to give 2.22 g (2.92 mmol) of the product. After liquid chromatography with toluene, the solvent was distilled off to yield 1.78 g (2.34 mmol, 71.20%) of a colorless translucent gel product.

Example 4

Molecular Formula 4

8.89 g (31.03 mmol) and 14.42 g (152.40 mmol) of chlorodimethyl silane obtained in Example 1 were dissolved in 50 ml of toluene, stirred for 2 hours under Pt / C, and stirred under reflux for 27 hours.

¹ H-nuclear magnetic resonance spectra confirmed that the reaction was completed, and then filtered under gaseous nitrogen using a pentane solvent to remove chlorodimethyl silane, a solvent and excess reactant, by distillation under reduced pressure. 14.50 g (25.42 mmol, 82.67%) of a colorless transparent gel. The product of was obtained.

Example 5

Molecular Formula 5

0.76 g (4.82 mmol) 8-hydroxyquinoline and 0.56 g (4.82 mmol) trimethylethylene in which 0.66 g (1.16 mmol) of the product G2P-3Cl obtained in Example 4 was dissolved in a solution of 10 m of toluene in a vacuum for 20 minutes. Diamine was dissolved in 25 ml of toluene and added dropwise for 0.5 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 2 hours to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was subjected to liquid chromatography with toluene: THF = 1: 1, and then the solvent was distilled off to obtain 0.40 g (0.45 mmol, 26.88%) of a colorless translucent gel product.

Example 6

Molecular Formula 6

0.64 g (1.10 mmol) of the product G2P-3Cl obtained in Example 4 was dissolved in 10 m of toluene, and 0.54 g (3.77 mmol) 4-methyl-5-thiazole ethanol and 1.00 g (8.60 mmol) trimethylethylenediamine were dissolved in toluene. It was dissolved in 25ml and added dropwise for 0.5 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 2 hours to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was subjected to liquid chromatography with toluene: THF = 7: 3, and then the solvent was distilled off to obtain 0.41 g (0.57 mmol, 52.38%) of a colorless translucent gel product.

Example 7

Molecular Formula 7

0.78 g (1.36 mmol) of the product G2P-3Cl obtained in Example 4 was dissolved in 10 m of toluene and 0.57 g (10.26 mmol) allyl alcohol and 1.09 g (9.37 mmol) trimethylethylenediamine were dissolved in 25 ml of toluene for 0.5 hour. Was added drop wise.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 1 hour to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was subjected to liquid chromatography with toluene, and then the solvent was distilled off to give 0.65 g (1.02 mmol, 75.24%) of a colorless translucent gel product.

Example 8

Molecular Formula 8

0.78 g (1.36 mmol) of the product G2P-3Cl obtained in Example 4 was dissolved in 10 m of toluene and dried in a vacuum for 10 minutes in 1.69 g (4.37 mmol) cholesterol and 0.47 g (4.04 mmol) trimethylethylenediamine. The solution dissolved in 25 ml was added dropwise for 0.5 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 1.5 hours to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was subjected to liquid chromatography with toluene: THF = 1: 1, and then the solvent was distilled off to obtain 0.70 g (0.43 mmol, 31.52%) of a colorless translucent gel product.

Example 9

Molecular Formula 9

In a solution of 0.63 g (1.10 mmol) of product G2P-3Cl obtained in Example 4 in 10 m of toluene, a solution of 0.73 g (5.32 mmol) 4-pyridine propanol and 0.64 g (5.20 mmol) trimethylethylenediamine in 25 ml of toluene was prepared. Dropwise addition for 0.5 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 2 hours to confirm the completion of the reaction in the ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was subjected to liquid chromatography with THF: CHCl ₃ = 3: 7 solution, and then the solvent was distilled off to obtain 0.46 g (0.53 mmol, 48.18%) of a colorless translucent gel product. there was.

Example 10

Molecular Formula 10

0.75 g (1.36 mmol) of the product G2P-3Cl obtained in Example 4 was dissolved in a solution of 10 m of toluene in a vacuum for 10 minutes in 0.45 g (3.66 mmol) p-pyridine aldoxin and 0.51 g (4.39 mmol) trimethylethylene A solution of diamine in 25 ml of toluene was added dropwise for 0.5 hour.

After stirring for 1 hour at room temperature and warmed to 50 ℃ for 2 hours to confirm the completion of the reaction by ¹ H-nuclear magnetic resonance spectrum.

The resulting salt was filtered with toluene, and the product was chromatographed with a THF: toluene = 3: 7 solution, and then the solvent was distilled off to obtain 0.43 g (0.55 mmol, 21.65%) of a colorless semitransparent gel product. .

The polysiloxane dendrimer obtained by the present invention is a material having a cylindrical structure having a highly branched structure shown in Figure 3 by dendrimerized development by using Si-H functional group of the polysiloxane as a core material. Their high-density structure is expected to play the role of nanotubes with excellent commercial applications.

Claims (4)

Desalination in the presence of trimethylethylenediamine by addition reaction with triclovinylsilane and allyl alcohol and reaction of chlorine atoms on terminal silicon atoms in the compound using the reactivity of a number of functional Si-H bonded to the polysiloxane linear structure Polysiloxane Dendrimer of Formula 1 Obtained by Substitution Reaction with Wherein R ¹ is allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, and n is 1 to 70, wherein the cylindrical polysiloxane dendrimer. The method of claim 1, A reaction obtained through the addition of Si-H in the presence of a platinum catalyst to an unsaturated functional group present at the terminal to control the branching unit (branch) using the reactivity of the unsaturated functional group of the material corresponding to R of the formula (1) Polysiloxane Dendrimer of Formula 2 as Product Wherein a is 1 to 2 and n is 1 to 70, wherein the cylindrical polysiloxane dendrimer is used. The method of claim 2, Polysiloxane dendrimer of Formula 3 obtained by substitution reaction by desalting in the presence of trimethylethylenediamine by reacting chlorine atom on terminal silicon atom of compound by using reactivity of chlorine bonded to silicon atom of Formula 2 Wherein R ² is an allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, b is 1 to 2, n is 1 to 70, the cylindrical polysiloxane dendrimer. The method of claim 2, In the structure defined in Chemical Formula 2, commercial application is possible by performing a substitution reaction by desalting in the presence of trimethylethylenediamine by using a chlorine atom as a reactive group on a terminal silicon atom among compounds having a 2 and Cl number 1 Polysiloxane dendrimers of Formula 4 obtained by substituting organofunctional groups 8-hydroxyquinoline, 5- (2-hydroxyethyl) -4-methylthiazole, p-pyridinepropanol, p-pyridinealdoxime, and cholresterol with various possible hydroxyl groups Wherein R ³ is allyl, alkyl, aryl, pyridine derivative, bicomponent aryl group, and n is 1 to 70, wherein the cylindrical polysiloxane dendrimer.