JP2002167368A - Alkyl group-substituted dendrimer and method for preparing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkyl group-substituted dendrimer which is an amphiphilc molecule and is suitable as an coating agent for modifying the surface of material having polar functional groups. SOLUTION: This alkyl group-substituted dendrimer is represented by the general formulas (Ia) or (Ib), (wherein, R means the general formula (II); n is an integer of 2 to 20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to novel alkyl-substituted dendrimers. The alkyl-substituted dendrimer of the present invention is an amphipathic molecule and can be used as a coating agent or the like for modifying the surface of a material having a polar functional group.

[0002] Dendrimers are polymers having a highly branched three-dimensional structure, and can be imparted with various functions by modifying the terminal with a functional low-molecular-weight compound. It is thought to have. The alkyl-substituted dendrimer of the present invention is an amphipathic molecule in which the core portion and the substituent portion are incompatible, and the positional relationship between these portions is different from the corresponding linear polymer. The alkyl-substituted dendrimer of the present invention can be used as a surface treatment agent. The function of the surface treatment mainly comes from the structure of the alkyl group portion, and for example, a water repellent function and a liquid crystal alignment function can be obtained. The function as a surface treatment agent is characteristic of the shape of the dendrimer molecule. For example, when a dendrimer derivative, a linear derivative (poly (ethylene imine) derivative), and a low molecular weight derivative are compared, only the dendrimer derivative shows the function of the liquid crystal alignment treatment agent.

An example of an alkyl-substituted dendrimer in which an alkyl substituent is bonded to the terminal of a poly (propylene imine) dendrimer is disclosed by Meijer et al., Which uses amide condensation to form a bond between the substituent and the dendrimer. . In contrast, the present invention uses a Michael reaction to obtain non-amide type alkyl-substituted dendrimers.

[0004]

SUMMARY OF THE INVENTION That is, the present invention provides a compound represented by the following formula:

Embedded image

[0005] or

Embedded image

(Where R is

Embedded image And n is an integer of 2 to 20. ) Is provided.

Further, the present invention provides the following formula:

Embedded image

[0008] or

Embedded image

A polyfunctional amine compound represented by the following formula:

Embedded image Wherein n is the same as defined above, wherein the alkyl-substituted acrylate derivative is reacted in an organic solvent in the presence or absence of a catalyst. About.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The alkyl-substituted dendrimers of the present invention are based on a polyfunctional amine compound. Such cores include polypropylene imine dendrimer DAB-A
m-4, poly (propylene imine) dendrimer first generation
(Poly (propyleneimine) Dendrimer, Generation1.0)
(IIIa)), DAB-Am-8, poly (propyleneimine) dendrimer second generation (Poly (propyleneimine) Dendrimer, G
eneration 2.0) (formula (IIIb)) (all manufactured by DSM) can be used. These compounds can also be synthesized using ethylenediamine and acrylonitrile as starting materials.

The terminal of the polypropyleneimine dendrimer, which is a polyfunctional amine compound, is modified with an alkyl-substituted acrylate derivative. As the alkyl-substituted acrylate derivative, a compound represented by the above formula (IV) is used. Here, n is 2 to 20, preferably 6
-20. Specific compounds include octadecyl acrylate, dodecyl acrylate, octadecyl methacrylate, dodecyl methacrylate, and the like. These acrylates can be used alone or as a mixture.

The alkyl-substituted dendrimer of the present invention is obtained by reacting the polyfunctional amine compound with an alkyl-substituted acrylate derivative in an organic solvent. The amount of the acrylate used is 16 to 80 mol, preferably 16 to 20 mol, DAB-Am-, in the case of DAB-Am-8, relative to 1 mol of the polyfunctional amine [or poly (propylene imine) dendrimer]. 8 to 4 for 4
0 mol, preferably 8 to 10 mol, or 2 to 10 equivalents, more preferably 2 to 2.5 equivalents (Am-
8, and Am-4).

As the reaction solvent, any of those conventionally known as these solvents may be used. Specifically, halogenated hydrocarbons such as tetrachloroethylene, 1,2-dichloroethane, and chloroform; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ether solvents such as tetrahydrofuran and dioxane; and toluene and xylene Aromatic hydrocarbon solvents; N-methyl-2-pyrrolidone, N,
An aprotic polar solvent such as N-dimethylformamide and N, N-dimethylacetamide can be used.
These may be used alone or as a mixture of two or more.

[0014] The reaction temperature is -50 to 150 ° C, preferably 25 to 80 ° C. If the reaction temperature is lower than −50 ° C., the reaction rate is remarkably reduced, which is not preferable. 150 ° C
If the reaction temperature exceeds, the stability of the polyfunctional amine compound or the alkyl-substituted acrylate derivative is not preferred.

The reaction time is 2 to 200 hours, preferably
18-90 hours. If the reaction time is shorter than this, the reaction does not proceed completely, which is not preferable. After completion of the reaction, the target alkyl-substituted dendrimer can be obtained by concentrating and removing the solvent. Alternatively, purification may be performed by adding a poor solvent such as methanol, ethanol, isopropyl alcohol, hexane, and toluene, heating the mixture, and removing the supernatant.

[0016]

The present invention will be described more specifically with reference to examples and comparative examples. All syntheses were performed under a stream of nitrogen. The properties of the resulting alkyl-substituted dendrimer were measured as follows.

[0017] ¹ H NMR  Measured using JNM-LA300 (manufactured by JEOL Ltd.)
Was.IR  Measured using FT / IR-230 (manufactured by JASCO Corporation)
Was.

Example 1 Synthesis of Octadecyl-Substituted First-Generation Propyleneimine Dendrimer (n = 17) Octadecyl acrylate (0.1%) was placed in a 20 mL reaction vessel.
88 mmol, 285.6 mg), poly (propylene imine) dendrimer DAB-Am-4 (0.10 mmol, 3
1.6 mg), add 2.0 ml of dichloromethane,
Stirred at 40 ° C. for 18 hours. After cooling to room temperature, this solution was dropped into toluene with vigorous stirring, and the resulting precipitate was collected to purify the target product. This was dried under reduced pressure to give 151 mg of a crystalline white solid in a yield of 5 mg.
Obtained at 2%. Consumption of acrylic double bond by ¹ HNMR
(5.87, 6.20, 6.48 ppm) and the formation of methylene chains at the α and β positions of the ester (2.47, 2.75 ppm) were observed. By IR, 1727.9 cm ^-1 (CO)
Characteristic absorption was observed.

Example 2 Synthesis of Octadecyl-Substituted Second-Generation Propyleneimine Dendrimer (n = 17) Synthesis was carried out in the same manner as in Example 1 using octadecylacrylate and poly (propyleneimine) dendrimer DAB-Am-8. 488 mg of a crystalline white solid was obtained in a yield of 8
Obtained at 2%. Consumption of acrylic double bond by ¹ HNMR
(5.87, 6.20, 6.48 ppm) and the formation of methylene chains at the α and β positions of the ester (2.47, 2.75 ppm) were observed. By IR, 1727.8 cm ^-1 (CO)
Characteristic absorption was observed.

[0020]

As described above, the substituted dendrimer of the present invention is an amphipathic molecule, and the feature of the dendrimer structure restricts the positional relationship between the incompatible partial structures, and thus can function as a coating agent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA02 AB68 AB80 AB99 AC52 BB11 BB12 BB16 BB20 BB24 BB25 4H020 BA02

Claims (4)

[Claims] 1. The following formula: (Wherein R is And n is an integer of 2 to 20. An alkyl-substituted dendrimer represented by). 2. The following formula: And a polyfunctional amine compound represented by the following formula: (Wherein n represents an integer of 2 to 20), wherein the alkyl-substituted acrylate derivative is reacted in an organic solvent in the presence or absence of a catalyst. Item 10. A process for producing an alkyl-substituted dendrimer according to item 1. 3. The following formula: (Wherein R is And n is an integer of 2 to 20. An alkyl-substituted dendrimer represented by). 4. The following formula: And a polyfunctional amine compound represented by the following formula: (Wherein, n represents an integer of 2 to 20), wherein the alkyl-substituted acrylate derivative is reacted in an organic solvent in the presence or absence of a catalyst. Method for producing dendrimers.