DE1182826B - Process for the production of cationic polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C08f

Number:
File number:
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German class: 39 c - 25/01

1182 826
B64978IVd / 39c
November 29, 1961
3rd December 1964

It has been found that valuable, cationic polymers are obtained if nitrogen-containing, cyclic compounds of the general formulas I or II alone or together with others, Ethylenically unsaturated monomers polymerized in the usual way.

- (CHR ₂ ) *

CH ₂ = CH

II

Herein, η is either 2 or 3, Ri is a hydrogen atom or an alkyl, aryl or aralkyl process for the preparation of cationic
Polymers

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

ίο Dr. Heinz Pohlemann, Limburgerhof (Palatinate),
Dr. Herbert Spoor, Mutterstadt (Palatinate),
Dr. Otto von Schickh, Ludwigshafen / Rhine

group with 1 to 12 carbon atoms; R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, where in the same molecule R ₂ can have different meanings on different carbon atoms; R ₃ is a hydrogen atom or an optionally substituted or interrupted by heteroatoms aliphatic, aromatic or araliphatic monovalent hydrocarbon radical; A is a monovalent acid

25 anion.

Examples of compounds of the formula I are N - vinylimidazoline, 1 - vinyl - 2 - methylimidazoline, I-vinyl-2-propyl-4-methylimidazoline and N-vinyl tetrahydropyrimidine.

R3 can be, for example, one of the following radicals:

-CH ₃ , -C ₂ H ₅ ,

H ₂ C

The following are, for example, possible acid anions:

Cl ', Br', J ', SO ₃ H', SO ₃ CH ₃ ', CH ₃ COO', SO ₃ '

Compounds of general formula I can, for. B. can be produced as follows:

2-methylimidazoline is dissolved in hot toluene. About 3% potassium is added to the solution and the mixture is mixed with a mixture in the pressure vessel treated from acetylene and nitrogen at about 120 ° C until the acetylene uptake is complete. After the tohiol has been distilled off, 1-vinyl-2-methylimidazoline remains from boiling point 83 to 86 ° C at 20 torr.

The production of these compounds is not claimed here.

The compounds of group II can be selected from those of group I in a simple manner Neutralizing with an inorganic or organic acid, e.g. B. with hydrochloric acid, sulfuric acid, Acetic acid, benzenesulfonic acid or by quaternization according to customary methods with alkylation or aralkylating agents such as dimethyl sulfate, diethyl sulfate, ethyl iodide, benzyl chloride, chloromethylated Furan or thiophene, ethylene oxide or propylene oxide are produced.

The quaternization not claimed here is preferably in a polar solvent such as

409 730/411

3 4

Water, ethanol, acetone, acetonitrile, etc., or in The polymerization temperatures in the general mixtures of those with non-polar, organic mean between room temperature and 120 ⁰ C. Solvents such as benzene, toluene, cyclohexane The molecular weights of the homopolymers are in, etc., made at temperatures below 8O ⁰ C. generally in the order of magnitude of a few The compounds characterized by the above general 5,000, while the copolymers mol formulas can weight te well over 100,000, alone or in a mixture with each other, but preferably the properties of the copolymers depend in a mixture other polymerizable, strongly on the type and amount of comonomers. Ethylenically unsaturated compounds polymerized. Water-soluble, alcohol-insoluble products are obtained. 10 one by copolymerization with up to about 50% ethylenically unsaturated compounds with acrylamide. If the acrylamide content is smaller, then the monomers described are copolymerized, the products are often both water and can be soluble, for example styrene and α-methyl alcohol. The copolymers with hydrostyrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylophobic monomers, such as acrylic esters or vinylamide, methacrylamide, N-substituted acrylic or 15 esters, are generally methacrylamides in organic media, such as N-alkyl or N-methylol soluble, insoluble in water. If larger amounts of crosslinking composite or methacrylic acid, such as methyl, ethyl, propyl, nentene, which have several olefinic double bonds butyl, isobutyl, octyl, dodecyl, Cyclohexyl wear, e.g. B. methylenebisacrylamide or butanediol acrylate or methacrylate, vinyl esters, such as vinyl diacrylate, to obtain completely insoluble products, acetate. Vinyl propionate, vinyl butyrate, vinyl stearate, according to the wide range of possible variations vinyl ethers, such as methyl, ethyl, butyl vinyl ethers, in the preparation of the polymers according to the N-vinyl compounds, such as vinyl pyrrolidone or the invention, products are obtained that are for many purposes vinyl imidazole, also vinyl chloride, vinylidene chloride are suitable. They are used to produce or butadiene. Furthermore, acidic reacting films, fibers, moldings and lacquers can also be used. Ethylenically unsaturated monomers such as acrylic copolymers are acidic for finishing. Methacrylic acid, crotonic acid, vinyl sulfonic acid and impregnation of leather and textiles acid or styrene sulfonic acid, used with polymerized; they improve the dyeability of be. Fibers, films and moldings, especially from The polymerization can be done after the usual 30 acrylonitrile or cellulose acetate-based. Many of the polymers can be used as antistatic agents for polymerization or emulsion polymerization. For treating hydrophobic plastics, such as poly-initiation of the polymerization, olefins, polyesters, polyamides or initiators which give free radicals in cellulose, such as water esters, are used. In a suitable form, they are material peroxide, potassium persulphate, benzoyl peroxide, Cu 35 also suitable for absorbing acid ions from liquid molar hydroperoxide, peracetic acid or azo diisobutter and as anion exchangers. Furthermore, acid nitrile, optionally in combination with them as sedimentation aids, which accelerate the flocculation activators such as ascorbic acid, formaldehyde sulf and settling of finely divided suspensions, oxylate or heavy metal salts, such as. B. copper can be used.

sulfate or ferric chloride. In many cases 4 ° N-vinyl-substituted N-heterocycles and their

polymerization, including by irradiation with polymers, are already known. The known

high-energy rays or by simple Er compounds, such as 2-vinylbenzimide

heat. It can also, especially azole or alkyl-substituted N-vinylimidazoles, ent-

for homopolymerization of the imidazoline derivatives, hold at least two double bonds in the ring

Friedel-Crafts catalysts such as boron fluoride or 45 and therefore have an aromatic character. the

Aluminum chloride can be used. compounds to be polymerized according to the invention

If the polymerization is carried out in emulsion, on the other hand, there is only one double bond in the ring

Cationic ones are expediently used and are therefore like those made from them

or non-ionic emulsifiers. As emulsifiers, polymers are more basic than nitrogen-containing aromatic

suitable are e.g. B. salts of higher fatty amines, 50 see ring systems.

such as octadecylamine sulfate, quaternary ammonium The parts mentioned in the following examples compounds, such as cetylpyridinium methosulfate, or are parts by weight, triethanolamine _R quaternized with dimethyl sulfate. . . . tristearate, furthermore oxyethylated octylphenol, which contains e 1 s ρ 1 e about 10 to 50 moles of added ethylene oxide. 25 parts of vinyl are contained in a reaction vessel. The emulsifiers can also be dissolved in a combination of methylimidazoline in 300 parts of water. It is neutralized with cationic or nonionic protective collo- ses with concentrated hydrochloric acid and ides, such as polyvinylimidazolinium salts, polyvinyl 75 parts of acrylamide are added. After dissolving the acrylic alcohol or polyvinylpyrrolidone can be applied. amide, a temperature of 20 ⁰ C is set, depending on the type of polymerization to give the 60 and 0.2 part of potassium persulfate and 0.1 part form polymers in solid form, in the form of more or aldehydsulfoxylat are stirred into the solution less viscous solutions or as dispersions. After a few minutes, the temperature rises. The polymerization of the monomers can also take place at 55 ^° C., and a tough, highly viscous mixture is obtained in the presence of substrates, e.g. B. textiles or solution from which the solid product fillers are made after cooling, whereby one is precipitated by adding 1000 parts of methanol with particularly good absorption of the polymer while stirring. The precipitate is washed after fiber or thorough mixing with the filler with methanol and achieved at 50 ⁰ C im. Vacuum dried. The product is in water

easily soluble and has a relative viscosity in 0.1% aqueous solution of 5.12 (i.e., the The transit time through the viscometer is 5.12 times as long for the solution as for pure water).

The product is suitable as a flocculant 5 for cellulose-containing, aqueous suspensions. For testing add 100 g of a 0.2% cloudy suspension of finely ground sulfite pulp (pH = 5) in three glass tubes and stir in the first 1 ml of a 0.1% solution of the prepared according to this example Product one, in the second 1 ml of a 0.1% solution of pure polyacrylamide analog Viscosity and lets the third stand without any additive. You can see that in the first tube after a few Seconds of large, quickly settling flakes are formed, which leave a clear, protruding solution. In the second tube, flake formation begins after about 2 minutes and the solution remains cloudy, while in the third tube the suspension is still practically unchanged after 30 minutes.

Example 2

6 parts of acrylamide and 4 parts of vinylmethylimidazoline are dissolved in 100 parts of ethyl acetate. Are then also 0.1 part of azodiisobutyronitrile are added and heated with stirring at 6O ⁰ C. It separates a precipitate. After cooling, filtering and drying, 9 parts of a colorless, pulverulent polymer are obtained, which dissolves in water with a strongly basic reaction. It has a relative viscosity in 0.1% strength aqueous solution of 1.15.

Example 3

55 parts of vinylmethylimidazoline are dissolved in 200 parts of water. Then allowed to 63 parts of dimethyl sulfate was gradually added dropwise into the solution to give prevented by cooling from the outside, that the temperature exceeds 50 ⁰ C. A 38.5% solution of the quaternary salt is obtained.

58 parts of this solution are mixed with 260 parts of water and 90 parts of acrylamide and polymerized by adding 0.5 part of potassium persulfate and 0.2 part of sodium hyposulfite, wherein the temperature rises from 20 to 55 ° C. The 29% strength solution of the cationic polymer obtained an excess of acetone is added, the product precipitating in solid form. It will filtered off and dried. The relative viscosity of the 0.1% strength aqueous solution is 2.58.

The product is suitable as a fiber flocculant for pulp suspensions and as a thickener for cationic polymer dispersions.

Example 4

350 parts of water, 28 parts of butyl acrylate, 88 parts of tert-butyl acrylate, 6.3 parts of vinylmethylimidazoline and 5 parts of an attachment

55 Product of about 5 moles of ethylene oxide in 1 mole of oleylamine, which quaternizes by means of dimethyl sulfate are mixed, and the resulting aqueous emulsion is treated with concentrated hydrochloric acid pH 5 set.

20% of the emulsion are placed in a reaction vessel, 0.5 parts of potassium persulfate are added and the mixture is heated to 75.degree. The remainder of the emulsion is added to the reaction solution over the course of an hour. This gives a polymer dispersion with 25% solids content, stable on storage, even at elevated temperature (7O ⁰ C), and after repeated cooling to - can be thawed unchanged 20 ⁰ C. The Fikentscher K value is 68, measured in cyclohexanone.

The polymer dispersion obtained is suitable for the production of tack-free protective coatings on wood, paper or plaster that is resistant to water and weak alkalis (soaps).

Example 5

49 parts acrylamide and 1 part of N-Vinyltetrahydropyrimidin, bp. 91 ⁰ C at 17 Torr, are dissolved in 200 parts of water and the solution with sulfuric acid to pH 5. 0.2 part of potassium persulfate and 0.05 part of formaldehyde sulfoxylate are then added. After a few minutes, polymerization begins and the temperature rises from 25 to 48 ⁰ C. The mixture is maintained for 30 minutes at the same temperature and then cooled, the solid product precipitated with methanol and dried. It has a relative viscosity (0.1% in water) of 1.54 and is particularly suitable for precipitating solids from finely divided suspensions, e.g. B. coal or ore slurries.

The following test is used to test the sedimentation effect: 40 g of finely powdered kaolin are suspended in 11 water and each 275 ecm of this suspension in two glass tubes of 2.1 cm Given diameter. The height of the liquid is 75 cm. 8.3 ecm of a solution are added to tube 2 of 824 mg in 1 liter of water. The suspensions in the two tubes are now through ten times Shaking moved within a minute and then left to stand vertically. The suspended Substances settle when standing still. There is a clear dividing line between an upper clearing part of the liquid and a lower, cloudy part, which contains the suspended matter contains. The height of the clear liquid layer is now measured at different time intervals. It is a simple measure of the sedimentation effect of the polymer compared to the settling rate the additive-free suspension. The following table shows the heights of the clear zones according to different Times indicated.

Sedimentation of a kaolin suspension (40 parts of kaolin in 1000 parts of water)

additive 1 minute Clear zone of the I.
2 minutes liquid after
3 minutes 5 minutes protruding
solution Without 0 cm
8 cm 0.5
20th 1
30th 2
42 cloudy
clear 0.0025% of the polymer

Claims (1)

Claim: Process for the production of cationic polymers, characterized thereby (CHR ₂ ) " CH ₂ = CH-N N I wherein Ri is a hydrogen atom or an alkyl, aryl or aralkyl group with 1 to 12 carbon atoms, R _{2 is} a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, where in the same molecule R ₂ can have different meanings on different carbon atoms, R3 is a hydrogen atom or an optionally substituted or interrupted by heteroatoms aliphatic, aromatic or araliphatic monovalent hydrocarbon radical, net that nitrogen-containing cyclic compounds of the general formulas I or II - (CHR ₂ ) _n II A is an acid anion and η is either 2 or 3, alone or in a mixture with other, ethylenically unsaturated monomers polymerized in the usual way. Considered publications:
German Patent Nos. 847 347, 911017, 504;
U.S. Patent No. 2,606,175. 409 730/411 11.64 © Bundesdruckerei Berlin