JPS5834496B2 - Novel polymer with catechol as main chain and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble polymer (ionene) and a method for producing the same.

More specifically, the present invention relates to a novel polymer containing a quaternary ammonium polycation and a catechol residue in its main chain, and a method for producing the same.

Water-soluble polymers, especially cationic polymers, are substances used as dispersants, flocculants, and the like.

Until now, polymers containing quaternary ammonium groups have
Ionene obtained from the reaction of a quaternized product of polyvinylpyridine, a difunctional tertiary amine, and an α,ω-dihalogen compound (Journal of the Society of Organic Synthetic Chemistry).

703 (1973)) is known.

However, these polymers are insoluble in water depending on the degree of quaternization, insoluble in water when large hydrophobic groups are introduced into the circulating units, and hydrolytic reactions of ester groups in the main chain. There were disadvantages such as depolymerization reaction caused by the depolymerization reaction.

As a result of repeated research to develop a new type of water-soluble resin that overcomes the drawbacks of these conventional water-soluble polymers, the present inventors found that the following formula (where R is a lower alkyl group or The polymer consisting of cyclic units represented by linked cyclic hydrocarbon groups, R' is a polymethylene group or xylylene group, and X is an anionic residue) is completely water-soluble, and the aqueous solution of the polymer is free from depolymerization. They found that it is stable and came up with the present invention.

The polymer having the circulating unit of the general formula (1) is prepared by combining a catechol compound represented by (R has the same meaning as above) and a compound represented by (R1' has the same meaning as above) in a polar solvent. It can be produced by reacting in

The catechol compound (n) used as one of the starting materials in this method can be easily synthesized from catechol, formalin, and the corresponding secondary amine.

Examples of the compound of general formula (II) obtained in this manner include 2,5-bis(dimethylaminomethyl)catechol and 2,5-bis(dipiperidylmethyl)catechol.

In addition, as an example of a compound represented by the general formula ([ID,
1.9-dichlorononane, ■, 6-dichlorohexane,
Ortho-xylylene chloride, meta-xylylene chloride, para-xylylene chloride, 4゜6-dimethyl-methaxylylene chloride and corresponding dibromide compounds or 1,6-hexamethylene ditosylate, para-xylylene ditosylate and the corresponding dimesylate.

In the general formula ([Each X in ID does not necessarily have to be the same, each may be different, and may be a combination selected from halogen and sulfonate.

The catechol compound of the general formula (II) and the general formula (
The reaction with compound Ill) is carried out by dissolving both in a polar solvent and reacting at a temperature from room temperature to 80° C. with stirring for 2 to 8 hours.

The ratio of each raw material used at this time is preferably equimolar.

Suitable polar solvents include dialkylamides such as dimethylformamide, dimethylacetamide and diethylacetamide, sulfoxides such as dimethylsulfoxide and sulfolane, and alcohols such as methanol and ethanol.

It is advantageous to use these solvents in such amounts that the concentration of each raw material is as high as possible and the viscosity of the polymerization system does not become extremely high.

After the reaction is complete, the solvent is distilled off from the reaction mixture, and the residue is washed with ether, or an appropriate amount of methanol is added to the reaction mixture, and this solution is reprecipitated in benzene, ether, etc. to obtain the desired product. The polymer is obtained as a pale yellow powder.

The polymer of the present invention has a molecular weight of about 2,000 to 50,000 and a decomposition point of 75
It is a powder with a temperature of ~175°C, and is soluble in solvents such as water and methanol as it is.

This polymer can be used as a flocculant, but since the phenolic hydroxyl group in the main chain can be chemically modified, it can also be used as a material for various functional polycations.

Next, the present description will be explained in further detail with reference to examples.

Example 1 0.2535 g of 1,6-dibromohexane and 3°5-
Add 1rILl of sulfolane to the mixture with bis(dimethylaminomethyl)catechol and react at 50°C for 2 hours.

After the reaction is complete, a small amount of methanol is added to dissolve the precipitated polymer to form a uniform polymer solution.

The polymer is obtained as a pale yellow powder by reprecipitating the polymer solution into ether.

The obtained polymer had a softening point of 145-150°C and a reduced viscosity of -0,099 (polymer concentration = 0.216 g/dl
H2O).

Example 2 DMSO of 1a was added to a mixture of 0.4690 g of 1,9-nonamethylene ditosylate and 0.2242.9 of 3,6-bis(dimethylaminomethyl)catechol, and 5
Heat at 0°C for 2 hours.

After the reaction was completed, the solvent was distilled off and the residue was washed with ether to obtain a hygroscopic powder.

The obtained polymer had a softening point of 75-85°C and a reduced viscosity of 0.
．． 068 (polymer concentration - o, 2o1/dl).

Example 3 2rrLl of dimethylacetamide are charged into a mixture of 0.448'l of 3,6-bis(dimethylaminomethyl)catechol and 0.5287g of meta-xylylene chloride.

The reaction starts spontaneously and is exothermic.

When the heat generation subsides, add 2rrLl of methanol and heat at 50°C for 2 hours.

The polymer can be obtained by adding ether to the reaction solution, stirring it, and filtering the precipitated powder.

The obtained polymer had a softening point of 160 to 175°C, reduced viscosity = 0.112 (polymer concentration = 0.259 g/dd
H20).

Claims (1)

[Claims] 1. A circulating unit represented by the general formula (in which R is a lower alkyl group or a cyclic hydrocarbon group in which R groups are linked together, K is a polymethylene group or xylylene group, and X is an anionic residue) A water-soluble polymer consisting of 2. The water-soluble polymer according to claim 1, wherein R in the general formula is a polymethylene group. 3. The water-soluble polymer according to claim 2, wherein the polymethylene group is a nonamethylene group. 4. The water-soluble polymer according to claim 2, which is a polymethylene group or a hexamethylene group. 5. The water-soluble polymer according to claim 1, wherein R in the general formula is a xylylene group. 6. The water-soluble polymer according to claim 5, wherein the xylylene group is an ortho-xylylene group. 1. The water-soluble polymer according to claim 5, wherein the xylylene group is a meta-xylylene group. 8. The water-soluble polymer according to claim 5, wherein the xylylene group is a 4,6-dimethyl-methaxylylene group. 9. The water-soluble polymer according to claim 5, wherein the xylylene group is a para-xylylene group. 10. The water-soluble polymer according to claim 1, wherein X in the general formula is an ion of chlorine, bromine, P-4 luenesulfonic acid, and mechnesulfonic acid. 11 A catechol compound represented by the general formula (in the formula, R is a lower alkyl group or a cyclic hydrocarbon group in which two R groups are connected), and a catechol compound represented by the general formula (in the formula, " is a polymethylene group or a xylylene group,
is a method for producing a water-soluble polymer comprising a circulating unit by reacting a compound represented by chlorine and bromine atoms or residues of para-toluenesulfonic acid and methanesulfonic acid in a polar solvent. 12. The manufacturing method according to claim 11, wherein the polar solvent is selected from dimethylformamide, dimethylacetamide, diethylacetamide, dimethylsulfoxide (DMSO), sulfolane, methyl alcohol and ethyl alcohol.