JPH0376707A - Production of functional polymer - Google Patents

Abstract

PURPOSE:To prepare a hydrophilic polymer having an unsatd. fatty acid deriv. group in its side chain by reacting a (co)polymer having an arom. sulfonic ester group in its side chain with an unsatd. fatty acid deriv. having an aliph. tertiary amino group. CONSTITUTION:An arom. sulfonic ester obtd. by reacting toluenesulfonyl chloride with an alcohol [e.g. hydroxy (meth)acrylamide] is, if necessary together with a monomer copolymerizable with the sulfonic ester (e.g. styrene), (co)polymerized to give a (co)polymer having an arom. sulfonic ester group in its side chain. The resulting (co)polymer is reacted with an unsatd. fatty acid deriv. having an aliph. tertiary amino group (e.g. dimethylaminoethyl cinnamate).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a method for producing functional polymers, particularly hydrophilic polymers having unsaturated fatty acid derivatives in their side chains.

(Prior art) There are various methods for producing hydrophilic polymers, and there are many examples of studies that have carboxy groups, sulfo groups, or quaternary salts in the side chains.For example, JP-A No. 49-98490.4
9-111991.49-85822.53-6394
．． 59-79246 for details.

However, these conventional production methods have some problems when it comes to producing polymers, especially polymers with functional groups such as unsaturated fatty acid derivatives. For example, the reactivity is low, the introduction rate of functional groups is not increased, side reactions are likely to occur, gelation is likely to occur, raw materials are expensive, etc.

The inventors of the present invention have developed a new manufacturing method by paying attention to these ingredients.

(Object of the Invention) The object of the present invention is to provide a method for producing a functional polymer by skillfully using easily available and highly reactive compounds.

(Gutter Bottom of the Invention) The purpose of the present invention is to provide a function characterized by reacting a homopolymer or a copolymer having an aromatic sulfonic acid ester group in the side chain with an unsaturated fatty acid derivative having an aliphatic tertiary amino group. This achievement was achieved by developing a method for producing synthetic polymers.

In the present invention, aromatic refers to aryl which may have a substituent, and the substituent is selected from alkyl, halogen, alkoxy, substituted alkyl, and the like. Benzene or toluene is preferred from the viewpoint of manpower and reactivity. In particular, toluene sulfonic acid ester is better.

A divalent group having 20 or less carbon atoms selected from amides, esters, ethers, aromatic rings, etc. may be present between the main chain and the ester. Aromatic sulfonic acid esters can be easily obtained by reacting toluenesulfonyl chloride with alcohol. The alcohol moiety is obtained by saponification of vinyl acetate alone or a copolymer, (meth)acrylate or (meth)acrylamide alone or copolymer having a hydroxy group, hydroxymethylstyrene alone or a copolymer, hydroxyethyl There are vinyl ether homopolymers or copolymers. Please refer to the patents mentioned above for details on this subject. As monomers for copolymerization, styrene, (
Examples include meth)acrylate and acrylamide. Another example is one in which a monomer having an aromatic sulfonic acid ester is monopolymerized or copolymerized. for example,
Toluenesulfonyloxytyl (meth)acrylate, toluenesulfonyloxypropyl (meth)acrylamide, toluenesulfonyloxymethylstyrene, etc. are advantageously used in the present invention. These have already been proposed by the present inventors.

Regarding the polymerization method, please refer to the bottom of this page for details.

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e Methods of PolymerCh
emistry”, J-Brandrup Polyme
r Handbook"Wiley&5ons
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Homopolymers or copolymers are generally obtained by radical polymerization reactions. Preferred examples include azo compounds, peroxides, and redox compounds.

Unsaturated fatty acid derivatives containing aliphatic tertiary amino groups will be described.

The aliphatic tertiary amino group refers to a tertiary amine consisting of two selected from alkyl or aralkyl and an alkyl substituted with at least one unsaturated fatty acid.

Alkyl or aralkyl may have an unsaturated fatty acid derivative, an unsaturated bond, etc. as a substituent. Dimethylamino, diethylamino, dibutylamino, methylbenzylamino, ethylpropargylamino, diallylamino, allylethylamino, dibenzylamino, N-hydroxypropylethylamino, N-acryloxyethylamino, dihydroxyethylamino, morpholino, piperazino, etc. Preferred as a tertiary amine residue.

Unsaturated fatty acids include beta-naphthyl acrylic acid, acrylic acid, methacrylic acid, cinnamic acid, thienyl acrylic acid, furyl acrylic acid, p-ethoxycarbonyl cinnamic acid, alpha-cyanocinnamic acid, sorbic acid, crotonic acid, dimethyl maleic anhydride. Examples include maleic anhydride, cinnamylideneacetic acid, and cyanothienylpentadienoic acid.

The bond between the aliphatic tertiary amino group and the unsaturated fatty acid is preferably a divalent group having 12 or less carbon atoms and which may have ether, ester, amide, ureido, urea, etc. Halogen atoms, as long as they do not interfere with the quaternary salt formation reaction.
It may have a hydroxy group, a dialkylaminoaryl group, etc.

From the viewpoint of availability of raw materials, it is preferable to react a halide, preferably a chloride, of an unsaturated fatty acid with an alcohol having the above-mentioned amine residue.

Preferred examples include diethylaminoethanol, dimethylaminoethanol, dihydroxyethylbutylamine, N-hydroxyethylmorpholine, ethylallylamine, diethylpropanolamine, dimethylaminomethylbenzyl alcohol, and diethylaminomethylcinnamyl alcohol. Another production method involves an amidation reaction between the above-mentioned amine having an amine residue and an unsaturated fatty acid, or an ester or chloride thereof.

Preferred examples include aminopropyldiethylamine, aminoethylmorpholine, aminoethyldibutylamine, triethyldiethylamine, dimethylaminomethylaniline, and aminobutyljetanolamine.
In amidation and esterification, it is preferable to use a base as a catalyst. Caustic soda, caustic loading, pyridine, triethylamine and the like are preferred. It is also preferable to use a polar solvent.

Since the functional polymer of the present invention can have one or more unsaturated fatty acid derivatives and quaternary salt moieties per polymerization unit, it has a mordant effect, cures and crosslinks quickly, and is reliably and hydrophilic. It has the advantage that it can be conveniently used for image formation using water treatment, water-containing solvent treatment, etc. Examples of use in such applications are already detailed. J-Kosar''
L1ght 5intensive Systems
Tsunoda "Photosensitive Resin" JP-A-1-105944, etc.

The present invention will be described in detail with reference to Examples below.

Example 1.2 MEKrooml, hydroxyethyl acrylate 0.
Using 1 mol of butyl methacrylate, 0.1 mol of butyl methacrylate, and a catalytic amount of azobisisobutyronitrile, the mixture was heated to 6.5°C from 65°C to 78°C while passing nitrogen gas according to the usual method.
After stirring for a while, a copolymer was obtained. The conversion was almost quantitative. 1.0.1 mol of toluenesulfonyl chloride was added to 50ml of sulfolane and stirred. Next, 0.3 mol of triethylamine was added dropwise at a temperature below 50 degrees. Except for the by-produced hydrochloride, the resulting polymer containing tosyloxy groups was separated using methanol. The reaction rate determined from the dry weight was quantitative.

As a result, a copolymer of toluenesulfonyloxyethyl acrylate and butyl methacrylate was obtained. It is called polymer l.

Weigh and dissolve 4 g of polymer 1 in DMFIQml,
0.01 mol of dimethylaminoethyl cinnamate was added and the mixture was maintained at 60 degrees for 50 minutes.

The resulting quaternary salt polymer was precipitated from ethyl acetate/hexane and isolated. (Example 1) A similar operation as above was performed using diethylaminoprobyl cinnamamide. (Example 2) (Reference example) Each of the functional polymers having an unsaturated fatty acid derivative moiety and a quaternary ring moiety in the side chain obtained in Examples 1 and 2 contained 8
% sensitizer (N-methylbenzoylnaphthothiazoline) was added and dissolved in DMF. This was dip-coated onto an electrolytically treated aluminum plate so that the thickness after drying was 2 microns. Irradiation was performed for 2 minutes from a distance of 30 cm using a 400W high-pressure mercury lamp. The exposed areas did not come off even after rinsing with solvent.

Claims (1)

[Claims] A method for producing a functional polymer characterized by reacting a single or copolymer having an aromatic sulfonic acid ester group in its side chain with an unsaturated fatty acid derivative having an aliphatic tertiary amino group.