JPH0559023A - Compound having plural terminal 2-oxooxazolidin-5-ylmethyl groups - Google Patents

Abstract

PURPOSE:To provide a pew compound capable of giving an one pack type coating material free from a thermally evaporatable component and useful as a new polymer raw material (monomer) of addition polymerization type. CONSTITUTION:A poly (2-oxooxazolidin-2-ylmethyl) ester of polycarboxylic acid of formula I (X is ester bond, ether bond; A is polycarboxylic acid residue forming the ester bond, aliphatic polyol residue forming the ether bond; n is the valency of the polycarboxylic acid or polyol), and a poly (2-oxooxazolidin-5- ylmethyl) ether of aliphatic polyol, e.g. ethylene glycol-1,2-bis(2-oxooxazolidin- ylmethyl) ether. The compound can be synthesized by reacting a compound of formula II with a compound of formula III (R is monohydric alcohol residue). The compound forms a new type linear or three-dimensional network polymer by an addition polymerization reaction with a polyamine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 2-oxooxazolidin-5-ylmethyl ethers of polycarboxylic acids or 2-oxooxazolidin-5-ylmethyl ethers of aliphatic polyols. These compounds are new compounds and form a new type of linear or three-dimensional network polymer by addition polymerization reaction with polyamine.

[0002]

BACKGROUND ART As is well known, a polyurea resin is produced by an addition polymerization reaction of a polyisocyanate compound and a polyamine. The polyisocyanate compound, which is one of the raw materials, is highly reactive and reacts with active hydrogen-containing compounds such as water, alcohol and amine even at room temperature. Therefore, in order to prepare a composition containing a polyisocyanate compound as a two-part composition, or in order to form a one-part composition, the isocyanate group must be blocked with a blocking agent such as a secondary alcohol which is volatilized by heating.

[0003] The present invention is a novel addition polymerization type polymer raw material (monomer) which can be made into a one-liquid type, for example, when it is used as a paint and does not contain a component volatilized by heating.
I will provide a.

[0004]

DISCLOSURE OF THE INVENTION The compounds of the present invention have the formula I

[Chemical 2] Can be represented by In the formula, X is an ester bond or an ether bond, A is a polycarboxylic acid residue or an aliphatic polyol residue forming the ester bond or an ether bond, and n is a valence of the polycarboxylic acid or polyol. is there.

[0005]

DETAILED DESCRIPTION The compounds of the present invention have the formula II

[Chemical 3] (Wherein X, A and n are the same as above), or a polyglycidyl ether of an aliphatic polyether, and a compound of formula III

[Chemical 4] It can be synthesized by reacting with a carbamic acid ester represented by (wherein R is a monovalent alcohol residue).

Examples of the polycarboxylic acid polyglycidyl ester of the formula II include polyglycidyl of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, succinic acid and adipic acid. Esters can be mentioned.

Examples of the polyglycidyl ether of the aliphatic polyol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and other aliphatic polyol polyglycidyl ethers, and polyethylene glycol. Examples thereof include polyglycidyl ethers of polyether polyols such as polypropylene glycol and polytetramethylene glycol.

The ester residue R of the carbamate of formula III is optional as it is not a residual group. However, it is generally selected from aliphatic hydrocarbon radicals having up to 10 carbon atoms, aromatic or araliphatic hydrocarbon radicals. These hydrocarbon groups may have a substituent such as a hydroxyl group. Specific examples of the ester residue include methyl, ethyl, isopropyl, butyl, benzyl, phenyl, 2-hydroxyethyl and the like, and methyl ester, ethyl ester or 2-hydroxyethyl ester are easily available and preferred.

The reaction is generally carried out by heating the starting compound in an equivalent ratio in the absence of solvent. At that time, an alcohol corresponding to the ester residue of carbamic acid is produced as a by-product, and the alcohol is distilled off. The reaction can also be carried out using a solvent that can be distilled off at the same time as the by-produced alcohol.

The reaction of the glycidyl ester or glycidyl ether of formula II with the carbamate of formula III can use a tertiary amine or tin compound or mixtures thereof as a catalyst.

The tertiary amine used as a catalyst includes aliphatic amines, aromatic amines, nitrogen-containing heterocycles, N, N-dimethylbenzylamine, N, N-dimethylaniline, triethylamine, N. , N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N-methylmorpholine, 1,4
-Diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine, quinoline, imidazole and the like are used.

As the tin compound, di-n-butyltin dilaurate, stannous chloride, tin octenoate,
Dibutyltin oxide, dioctyltin oxide, 1,
3-diacetoxy tetrabutyl distannoxane, 1,3
-Dichloro tetrabutyl distannoxane, dibutyl dibutoxy tin, etc. are mentioned.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 Ethylene glycol-1,2-bis (2-oxooxa)
Zolidine-5-ylmethyl) ether Ethylene glycol diglycidyl ether 8.7 g to ethyl carbamate 8.9 g, N, N-dimethylbenzylamine 0.3 g and dibutyltin dilaurate 0.3 g
Was heated for 2 hours at 140 ° C. while distilling off by-produced ethanol. The reaction product was cooled and then purified by silica gel column chromatography (developing solution, ethyl acetate / methanol = 4/1) to obtain 11.7 g (yield 90%) of the title compound as white crystals. Melting point: 90-95 ° C ¹ H-NMR (DMSO, δ) 3.10-3.75.
(M, 12H), 4.55-4.81 (m, 2H),
7.47 (bs, 2H)

Example 2 1,4-Butanediol bis (2-oxooxazolidi)
(N-5-ylmethyl) ether 1,4-butanediol diglycidyl ether 5.1 g
4.5 g ethyl carbamate, 0.2 g N, N-dimethylbenzylamine and dibutyltin dilaurate.
Add 2 g and distill off the ethanol produced as a by-product.
Heated at 0 ° C. for 2 hours. After cooling the reaction product, silica gel column chromatography (developing solution, ethyl acetate /
Purification by methanol = 4/1) gave the title compound (6.7 g, yield 92%) as white crystals. Melting point: 80-85 ° C ¹ H-NMR (DMSO, δ) 1.38-1.70.
(M, 4H), 3.05-3.62 (m, 12H),
4.51-4.85 (m, 2H), 7.52 (bs, 2)
H)

Example 3 Bis (2-oxooxazolidine hexahydrophthalate
-5-ylmethyl) ester diglycidyl ester of hexahydrophthalic acid 8.0 g
4.5 g ethyl carbamate, 0.3 g N, N-dimethylbenzylamine and dibutyltin dilaurate.
Store 3 g and distill off the by-product ethanol, 1
Heated at 50 ° C. for 2 hours. After cooling the reaction product, silica gel column chromatography (developing solution, methanol)
Was purified by the above method to give the title compound (8.2 g) as a yellow candy-like solid.
(Yield 80%) was obtained. ¹ H-NMR (DMSO, δ) 0.90-2.10
(M, 8H), 2.90 (m, 2H), 3.22 (d
d, 2H), 3.58 (t, 2H), 4.18 (d, 4)
H), 4.78 (m, 2H), 6.50 (bs, 2H)

In the same manner as in Examples 1 to 3, the following compounds were synthesized by reacting the corresponding polyol polyglycidyl ether or polycarboxylic acid polyglycidyl ester with carbamic acid ester.

1,6-hexanediol bis (2-oxooxazolidin-5-ylmethyl) ether trimethylolpropane tris (2-oxooxazolidin-5-ylmethyl) ether pentaerythritol tetrakis (2-oxooxazolidin-5-ylmethyl) ether Polyethylene glycol bis (2-oxooxazolidin-5-ylmethyl) ether Polypropylene glycol bis (2-oxooxazolidin-5-ylmethyl) ether Phthalic acid bis (2-oxooxazolidin-5-ylmethyl) ester Tetrahydrophthalic acid bis (2-oxo Oxazolidin-5-ylmethyl) ester

Claims (1)

[Claims] 1. The formula: The compound represented by. In the formula, X is an ester bond or an ether bond, A is a polycarboxylic acid residue forming an ester bond or an aliphatic polyol residue forming an ether bond, and n is a valence of the polycarboxylic acid or polyol.