JPS5834495B2 - A new polymer with hydroquinone as its main chain and its production method - Google Patents

Description

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

More specifically, the present invention relates to a novel polymerization quenching containing a quaternary ammonium polycation and a hydroquinone residue in the main chain, and a method for producing the same. It is a substance used as a dispersant, flocculant, etc.

Until now, polymers containing quaternary ammonium groups have
Ionene CJ-Polym, Sci, obtained from the reaction of a quaternized product of poly-vinylpyridine, a difunctional tertiary amine, and an α,ω-dihalogen compound.

Polym-Iett, Ed 6.159 (1968)
] Polycatic obtained from the reaction of bis-chloroacetate and a difunctional tertiary amine [Journal of Organic Synthesis Chemistry, 31, 703 (1973)] is known.

However, each of these polymers is insoluble in water depending on the degree of quaternization, becomes insoluble in water when a large hydrophobic group is introduced into the circulating unit, and is particularly susceptible to hydration of the ester group in the main chain. There were drawbacks such as a depolymerization reaction caused by a decomposition 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 inventors of the present invention discovered the following formula: The polymer consisting of a cyclic unit represented by a linked cyclic hydrocarbon group, R' is a polymethylene group or xylylene group, and They found that it is stable and came up with the present invention.

Until now, the hydrochloride salt of a polymer obtained from the reaction with hydroquinone, piperazine, and formaldehyde, i.e., the polymer represented by In contrast, the polymer of the present invention is water-soluble even in the presence of a low concentration of acid, alkali, etc., and is different from the polymer of formula (II) in terms of wood quality.

This substance shows that the polymers according to the invention can be used as flocculants under various conditions (see Comparative Examples).

A polymer having a circulating unit of the general formula (I) is a compound represented by C (R' has the same meaning as above) and a compound represented by C (R' has the same meaning as above). It can be produced by reacting in a polar solvent.

The hydroquinone compound (IID) used as one of the starting materials for this method can be easily synthesized from hydroquinone formalin and the corresponding secondary amine.

Examples of the compound of general formula (III) obtained in this way include 2,5-bis(dimethylaminomethyl)hydroquinone, 2,5-bis(dibutylaminomethyl)hydroquinone, 2,5-bis(dipropylaminomethyl) ) Hydroquinone, 2,5-bis(dibutylaminomethyl)
Hydroquinone, 2,5-bis(dibiperidylmethyl)
I can give you hydroquinone.

Further, as an example of the compound represented by the general formula (5), 1
．． 9-Dichlorononane, ■, 6-dichlorohexane, ortho-xylylene chloride, meta-xylylene chloride, para-xylylene chloride, 4,6-dimethyl-methaxylylene chloride and the corresponding dipro □ compound or 1 , 6-hexamethylene ditosylate, para-xylylene ditosylate and the corresponding dimesylate.

In the general formula (5), each X does not necessarily have to be the same, and may be different, and may be a combination selected from halogen and disulfonate.

The hydroquinone compound of the above general formula (song) and the above general formula (
For the reaction with the compound in 5), dissolve both in a polar solvent,
The reaction is carried out by raising the temperature from room temperature to 80°C and stirring for 2 to 8 hours.

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

Suitable polar solvents include dialkyl oxides such as dimethylformamide, diethylacetamide, 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 21
It is a powder at 0°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 invention will be explained in more detail with reference to examples.

Example 1 1.2361 g of 1,6-dipromohexane (5,06
7X10-3 mol) and 2,5-bisdimethylaminomethylnohydroquinone 1.1368S' (1,136
2me dimethyl sulfoxide (DMSO) was added to 8×10 3 mol) and heated at 5000 to 70° C. for 3 hours to perform a polymerization reaction.

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

The obtained polymer had a softening point of 200'C and a reduced viscosity of 0.
249 (polymer concentration = 0, 233'?/dl H2
O) is a pale yellow powder that can be mixed with water, methanol, DMSO
, soluble in dimethylformamide (DMF).

Example 2 Meta-xylylene chloride 1.3211f and 2,5-bis(dimethylaminomethyl)hydroquino 71.122
When 37 nl of DMSO was added to No. 51 and stirred, heat was generated and an increase in viscosity was observed.

When the heat generation subsided, 1 rnl of DMSO was further added and the reaction was carried out at 50'C for 14 hours.

After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was washed with ether to obtain the polymer.

The obtained polymer had a softening point of 205°C and a reduced viscosity of 0.274.
(polymer concentration = 0.282 g/dlH20), and is soluble in water, methanol, and DMSO.

This polymer can also be synthesized using DMF as a solvent.

Example 3 Para-xylylene dichloride 1.7511S' and 2.5
-bis(dimethylaminomethyl)hydroquinone 2.2
107 to 4401! of DMSO was added thereto, and the mixture was stirred and reacted with 500C1.

The reaction solution became cloudy after about 10 minutes, and a polymer precipitated.

After 2 hours, about 307 nl of methanol was added and left to stir to form a methanol solution.

The polymer was obtained by reprecipitating this methanol solution into benzene.

The obtained polymer has a softening point of 210°C and a decomposition point of 215°.
C1 reduced viscosity 2.93 (polymer concentration = 0.306 g/
d/1H20) as a pale yellow powder and was soluble in water and methanol.

Example 4 4.6-dimethyl-mecuxylylene dichloride 1.3
10-methanol was added to 1.4829f of 4211 and 2,5-bis(dimethylaminomethyl)hydroquinone, and the mixture was reacted at 50°C for 12 hours.

After the reaction was completed, the solvent was distilled off and washed with dry ether, thereby making it possible to quantitatively obtain a polymer.

The obtained polymer had a softening point of 200 to 205°C and a reduced viscosity of 0.237 (polymer concentration = 0.106 L?/dl).
powder.

Example 5 1.6-nonamethyleneside sylate 0.4687f and 2
,5-bis(dimethylaminomethyl)hydroquino 70
．． 2248f? Add 1.5 ml of DMSO to the
C Heat the reaction for 13 hours.

After the reaction is complete, the solvent is distilled off, ether is added to the residue, and the mixture is stirred.

The precipitated polymer was a pale yellow powder with a reduced viscosity of 20.0642 (polymer concentration = 0.211 g/7H20).

Example 6 Para-xylylene dichloride 0.8771 f and 2,5
-bis(dipiperidylmethyl)hydroquinone 1.52
Add 3-DMSO and 2-ethanol to 521,
React at 0-80°C for 13 hours.

After the reaction was completed, the polymer precipitated and became cloudy, but the polymerization solution was directly poured into ether to perform reprecipitation.

The obtained polymer had a softening point of 120-140' C1 reduced viscosity = 0.060 (polymer concentration = 0.226 g/diH
20) is a pale yellow powder and is soluble in water and methanol.

Comparative Example Take 9 ml of 1000pp solution of methyl orange and put into two measuring cylinders.

Into this solution were added the polymers of the invention (Example 3) and (I).
An aqueous solution of a polymer of formula (2X 10'&ol
/rnl) in 1 rnl each, and incubate overnight.

In the case of the polymer of the present invention, methyl orange precipitates together with the polymer, but the polymer of formula (II) only produces turbidity and does not have the ability to precipitate the dye.

Furthermore, in order to compare the precipitation/sedimentation ability in the presence of alkali, the above-mentioned mixed solution was mixed with sodium carbonate at pH=1.
0, and the amount of dye remaining in the aqueous solution without precipitation or sedimentation is measured using a visible absorption spectrum, (II)
The amount of residual dye in the polymer of formula (In) was about three times that of the polymer of the present invention, and it was found that the polymer of formula (In) had a poorer precipitation/sedimentation effect on the dye than the polymer of the present invention.

Claims (1)

[Claims] 1. A cyclic unit 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, R' 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 Water-soluble polymer according to claim 2, in which the polymethylene group is a nonamethylene group 4 R' in the general formula 5, water-soluble polymer according to claim 2, in which polymethylene group or hexamethylene group The water-soluble polymer according to claim 1, wherein is a xylylene group. 6. The water-soluble polymer according to claim 5, wherein the xylylene group is an ortho-xylylene group. 7. Water-soluble polymerization according to claim 5, in which the xylylene group is a meta-xylylene group. 8. Water-soluble polymerization according to claim 5, in which the xylylene group is a 4,6-dimethyl-meta-xylylene group. Polymer. 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-)luenesulfonic acid, and methanesulfonic acid. 11 A hydroquinone compound represented by the general formula (R in the formula is a lower alkyl group or a cyclic hydrocarbon group in which R's are connected to each other) and the general formula (R' in the formula is a polymethylene group or a xylylene group,
X is a chlorine or bromine atom or a para-toluenesulfonic acid or methanesulfonic acid residue) is reacted in a polar solvent. manufacturing method. Claim 11 wherein the polar solvent is selected from dimethylformamide, dimethylacetamide, diethylacetamide, dimethyl sulfoxide, sulfolane methyl alcohol a) and ethyl alcohol.
Manufacturing method described in section.