JPS62458A - Fluorine-containing urethane - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing urethane expressed by formula I [Rf is 1-20C polyfluoroalkyl; X is -R1-, -CON(R2)-R3- or -SO2N(R2)-R3- (R1 and R3 are bifunctional organic group; R2 is H or monofunctional organic group); R is formula II; A is residue obtained by removing active hydrogen from monohydric alcohol or blocking agent capable of liberating isocyanate group by heat treatment; n is an integer 1-3]. USE:A textile treating agent and nonblocking agent for imparting water and oil repellency (with a low viscosity and high fluorine content). PREPARATION:One mol 1,8-diisocyanato-4-isocyanatomethyloctane expressed by formula II is reacted with n mol fluoroalcohol and (3-n) mol active hydrogencontaining compound in an inert solvent, as necessary, in the presence of a catalyst added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel fluorine-containing urethane used for imparting water and oil repellency to carpets, fibers, etc.

(Prior art) It has been discovered that fluorine-containing urethane, which is synthesized from incyanate having three or more isocyanate groups and alcohol having a fluoroalkyl group, is a compound useful as a stain-proofing agent for carpets, etc. (%
(Japanese Patent Publication No. 59-31751, Japanese Patent Application Publication No. 59-33315)
.

(Problems to be Solved by the Invention) Conventionally, the polyisocyanate used as a raw material for the above-mentioned fluorine-containing urethane is an adduct of diinocyanate,
In terms of weather resistance and non-yellowing properties, for example, water adducts of aliphatic or cycloaliphatic diisocyanates, trimethylolpropane adducts, or incyanas, such as hexamethylene diinocyanate or inphorone diisocyanate. fluorine-containing urethanes synthesized using these polyisocyanates.

They have high viscosity and are difficult to handle, and generally have low fluorine content, and do not have sufficient water and oil repellency.
It was not always satisfactory as an antifouling agent.

(Means for Solving the Problems) As a result of repeated research in order to solve the above problems, the present inventors have discovered that specific triisocyanyl octane 1,8-diisocyanato-4-incyanatomethyloctane 0 and b. By using NART, compared to conventional products, it maintains its weather resistance and non-yellowing properties, has a low viscosity, and has a high fluorine content.
The present inventors have discovered that it is possible to obtain an unprecedented fluorine-containing urethane that is useful as a processing agent for imparting water and oil repellency, and have completed the present invention.

OCN -CH, CH, CH, CHCH, CM, CH,
CH, -NGOC-NCO ■ The fluorine-containing urethane of the present invention can be synthesized by the reaction described below.

First, 1,8-diisocyanato-4-incyanatomethyloctane (IF) Fi, for example, JP-A-56-1273
As shown in No. 41, it can be obtained by reacting 1,8-diamino-4-7minomethyloctane or a salt thereof with phosgene.

For 01 mol of triisocyanate thus obtained,
Fluoroalcohol (LID f1 mol and active hydrogen compound (IV) in an inert solvent with addition of catalyst if necessary)
The fluorine-containing urethane (I) of the present invention can be obtained by reacting 3 to 11 moles simultaneously or stepwise (n is an integer of 1 to 3).

Rf X-0H (lIL) -H (IV) (wherein R (,

CFs(CFz)nCHtOH, CFs(CFt)nS
Those in which R( is a perfluoroalkyl group, such as OtN(CtHs)CHtCHtOH (n is an integer of 5 to 10), and those in which the terminal is substituted with an atom other than F, such as H(CFt)ecHtOH, may also be used. These can be used alone or in an appropriate mixed form.

As the active hydrogen compound (IV), lower alkyl alcohols such as methanol and ethanol, functional groups such as glycidol, furfuryl alcohol, and benzyl alcohol,
Examples include alcohols having aroma H1, phenols, oximes, incyanate blocking agents such as C-caglolactam, methyl acetoacetate, and imidazole.

As an inert solvent, 1,1.1-)lichloroethane,
Halogenated carbons such as trichloroethylene, chloroform, trichlorotrifluoroethane (hydrogens, benzene,
Hydrocarbons such as toluene and hexane, ethers such as dimethoxyethane, diethylene glycol dimethyl ether, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate can be used. .

As the catalyst, tertiary amines such as triethylamine and triethylene diamine, tin catalysts such as diptyltin dilaurate, etc. are usually used in an amount of 0.01 to 1.0% by weight based on (1).

The temperature at the back end is 40-100C, and the reaction time is Vi.
The reaction proceeds smoothly in about 1 to 4 hours.

(Effects of the Invention) The fluorine-containing urethane of the present invention thus obtained has a lower viscosity and a higher fluorine content than conventional products.

It can be used for various purposes in the form of an organic solvent or an aqueous suspension, and is particularly useful as a fiber processing agent and non-adhesive agent that utilizes its water-repellent and oil-based properties.

(Example) Example 1 1 dimethoxyethane 20 mm was placed in a 50 mm four-bottle flask equipped with a stirrer, a dropping funnel, a thermometer, and a condenser tube.
% triisocyanate ([) 4.192 and 4.2 mg of diptyltin dilaurate were charged. In this,
At 60 t:', CF, CH, OH5,0Of were added dropwise using a dropping funnel over 2 hours, and stirring was continued for 2 hours.

The completion of the reaction was confirmed by IR when the absorption of NCO groups disappeared. The reaction solution was concentrated under reduced pressure using an evaporator to obtain fluorine-containing urethane as a colorless and transparent liquid. The IR spectrum of this fluorine-containing urethane liquid film is shown in FIG.

Example 2 Dimethoxyethane 2QtRt was added to the same apparatus as in Example 1.
,) Liisocyaner) (II) 1. a 9 y and diptyltin dilaure) 1,9# were charged. H(CFt)scH,OH5,0OS' was added dropwise into the mixture using a dropping funnel over 2 hours at 60C, and stirring was continued for 1 hour. After confirming that the fluoroalcohol was consumed by thin layer chromatography, 0.241 ri of methanol was added dropwise to the reaction solution lowered to 40C, and stirring was continued for an additional hour. Confirmation of the completion of the reaction and post-treatment of the reaction solution were carried out in Example 1.
I did the same thing. The desired product was obtained as a colorless transparent liquid.

The IR spectrum of this target product in a liquid film is shown in FIG.

Comparative Example 1 Tri-inocyanate (II) was replaced with a water adduct of hexamethylene diisocyanate (Asahi Kasei).

Duranate 24A-100)9. Synthesis was carried out under the same conditions as in Example 1 using IQf and adding 9,1 da of diptyltin dilauret. The fluorine-containing urethane was obtained as a translucent viscous liquid. The IR spectrum of this fluorine-containing urethane liquid film is shown in FIG.

The properties of the fluorine-containing urethanes synthesized in Examples and Comparative Examples are shown in the table below, and the fluorine-containing urethanes of the present invention have lower viscosity and higher fluorine content than conventional products.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 show IR spectra of liquid films of fluorine-containing urethanes synthesized in Example 11, Example 2, and Comparative Example 1, respectively.

Claims (1)

[Claims] A fluorine-containing urethane represented by the general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, R_f is a polyfluoroalkyl group having 1 to 20 carbon atoms, and X is -R_1-, -CON(R_2)-R_3-
or one of -SO_2N(R_2)-R_3-(R_
1, R_3 is a divalent organic group, R_2 is a hydrogen atom or a monovalent organic group), A is a monovalent alcohol or a residue obtained by removing active hydrogen from a blocking agent that releases isocyanate groups by heat treatment, n is 1 It is an integer of ~3.