DE2233337A1 - Polymers of substd (meth)acrylamides - for use as flocculants - Google Patents

Abstract

(Co)polymers are derived from substd. (meth)acrylamides of formula (I): (where R', R2 and R3 are H or hydrocarbon, and R4 and R5 are hydrocarbons, R6 is -C(R7)=CH2 where R7 is H or lower alkyl, and R8 (sic) is hydrocarbon, Y is -NZ'Z2 or - circled positive NZ'Z2Z3X circled negative X is a salt-forming anion, Z' is H or hydrocarbon, and Z2 is H or (cyclo)alkyl, or -NZ'Z2 may be a heterocycle, and Z3 is H or lower alkyl), e.g. N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide.

Description

"Polymers of amides and their use as flocculants" The invention relates to polymers of amides of the general formula I. in which R1, R2 and R3 are each a hydrogen atom or a hydrocarbon radical and R4 and R5 are each a hydrocarbon radical, R6 is the group means a hydrogen atom or a lower alkyl radical and R8 is a hydrocarbon radical, Y is the group or denotes, x is a salt-forming anion, Z1 is a hydrogen atom or a carbon atom, an hydrogen radical and Z2 is a hydrogen atom or an alkyl or cycloalkyl radical or the group denotes a heterocyclic radical and Z3 is a hydrogen atom or a lower alkyl radical, optionally with a polymerizable vinyl monomer.

The term hydrocarbon radical means alkyl, cycloalkyl, Aryl, aralkyl and alkaryl radicals. Furthermore, the term means hydrocarbon radical those radicals which also contain other substituents, e.g. ether, ester or Nitro groups or halogen atoms, provided that these substituents have the character or the Do not significantly change the reactivity of the hydrocarbon residue. The expression "1 lower alkyl" means radicals having 1 to about 10 carbon atoms.

In the preferred compounds of the invention, the radicals R2, R2 and R3 are hydrogen atoms or lower alkyl radicals or aromatic radicals with 6 to 15 carbon atoms, the radicals R4 and R5 are lower alkyl radicals, cycloalkyl radicals with 3 to 8 carbon atoms or aromatic radicals with 6 to 15 carbon atoms, R7 is a hydrogen atom or a methyl group, R8 is a lower alkyl radical or an aromatic radical with 6 to 15 carbon atoms, z1 and z2 are lower alkyl radicals or cycloalkyl radicals with 3 to .8 carbon atoms or the group is a heterocyclic radical such as the pyrrolidino, piperidino or morpholino group and X (if present) is a typical salt-forming anion such as the chloride, bromide, iodide, sulfate, bisulfate, acetate, carbonate or bicarbonate.

Particularly preferred are compounds in which the radicals R12, R2 and R3 hydrogen atoms or lower alkyl radicals, R4 and R5 lower alkyl radicals, R7 Hydrogen atom, R8 a lower alkyl radical, Z1 and Z2 lower alkyl radicals and Z3 (if present) mean a methyl group.

Specific examples of basic building blocks of the polymers of the invention are: N- ((1-Dimethyl-3-dimethylami noTerot) acrylamide N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide Dimethyl-3- (1-acrylamido-1, 1-dimethylpropyl) ammonium chloride Trimethyl-3- (1-acrylamido-1,1-dimethylbutyl) ammonium iodide N- (1-methyl-1,3-diphenyl-3-diethylaminopropyl) methacrylamide N- [1-methyl-1,3- (p -chlorophenyl) -3-pyrollidinopropyl] acrylamide The monomeric amides of the general formula I can be prepared from the corresponding compounds in which R6 represents the group means. These compounds, also referred to below as "oxy compounds", can be prepared by reacting an oxypropionamide of the general formula II with an Ami1; the general formula in the presence of a.

Reducing agent are produced. Oxypropionamides in general Formula II can be made by reacting a hydroxy compound (alcohol or phenol, preferably an alcohol) with an N-3-oxo-hydrocarbon-substituted acrylamide of in of the USA. - Patent 3 277 056 and 3 415 942 type described.

The reaction of the oxypropionamide with the amine is generally referred to as reductive amination. A typical example of such a reaction is the Leuckart reaction, in which an oxo compound is present with an amine is reacted with formic acid or with an amine formate. Here is the carbonyl carbon atom aminated, and carbon dioxide and water are produced as by-products.

A preferred method for the reductive amination of the oxypropionamides consists in the 'reaction with the amine in the presence of hydrogen and a hydrogenation catalyst, such as platinum / platinum oxide, palladium, copper chromite or Raney nickel. From these catalysts platinum / platinum oxide (Ädams catalyst) is preferred. This catalyst is used as Platinum / platinum oxide catalyst called because it is usually used as an oxide, however, in contact with abrasive material, it is immediately reduced to elemental platinum. In practice, a mixture of the oxropionamide and the amine with a low Amount of the hydrogenation catalyst added. Then water fabric is up to a pressure of at least about 3.5 kg / cm2. The mixture is stirred and generally heated to temperatures of about 25 to 1000C, from time to time hydrogen is nachge pressed until the hydrogen uptake ceases. The reductive Amination can be carried out in the presence of a suitable solvent such as an alcohol or ether. However, such a solvent is often not necessary. It was also found that in the presence of a small amount, usually about 0.1 to 5.0 percent by weight, based on the reaction milk, of an acid, the speed of reaction increases.

Typical acids that can be used for this are aromatic Sulphonic acids, mineral acids, perchloric acid and their amine salts The molar ratio from amine to oxypropionamide in the reaction mixture should be at least 1: 1. in the generally the molar ratio is higher and can be up to about 5: 1. Molar ratios from about 1.25: 1 to 3: 1 are preferred.

After the reductive amination has ended, the product can be used in the usual way Way to be isolated and purified.

1 to 10 The examples explain the preparation of the "oxy compounds".

Parts and percentages are by weight unless nothing other is indicated.

B e i s p i e l 1 A mixture of 201 parts (1 mol) of N (1,1-dinethyl-3-oxobutyl) 3-methoxypropionamide and 91 parts (2 moles) of dimethylamine are mixed with 0.5 parts of platinum oxide and 3 parts of p-toluenesulfonic acid are added. The liquid mixture is poured into a hydrogenation vessel poured, the vessel is purged with hydrogen and hydrogen is poured up to a pressure of 4.85 kg / cm2. The hydration is carried out for about 12 hours. As soon as the hydrogen pressure has dropped to 1.9 kg / cm2, it becomes hydrogen again pressed up to a pressure of 4.9 kg / cm. Then the mixture is in one Rotary evaporator evaporated and the remaining yellow liquid is in 16 percent Dissolved hydrochloric acid and extracted it with four 100 ml portions of chloroform. After that, will the aqueous solution by adding a solution of 30 parts of sodium hydroxide in 75 Divide the water made alkaline and reapply the alkaline solution with four 100 ml Portions of chloroform extracted. The chloroform extracts are evaporated and the Distilled residue. The H- (1,1-dimethyl-3-dimethylaminobutyl) -3-methoxypropionamide is obtained from the boiling point 87 to 950C / 0.5 Torr. The compound contains 12.1 percent nitrogen.

The theoretical nitrogen value is 12.2 percent.

EXAMPLE 2 According to Example 1, 263 parts (1 mol) of N- (1,1-dimethyl-3 oxobutyl) -3-phenoxypropionamide with 95 parts (2.11 mol) of dimethylamine in the presence of 1.75 parts of 70 percent aqueous perchloric acid and 0.5 parts of platinum oxide. The N- (1,1-dimethyl-3-dimethylaminobutyl) -3-phenoxypropionamide is obtained.

Example 3 The procedure of Example 2 is repeated, however 216 parts (1 mol) of N- (1,1-dimethyl-3-oxobutyl) -3-methoxy-1-methylpropionamide are used. The N- (1,1-dimethyl-3-dimethylaminobutyl) -3-methoxy-1-methylpropionamide is obtained.

Example 4 A 3.75 liter pressure autoclave is used with 1684 parts (8.38 moles) N- (1,1-dimethyl-3-oxobutyl) -3-methoxypropionamide, 762 parts (16.9 moles) Dimethylamine, 1.5 parts of platinum oxide and 15 parts of dimethylammonium perchlorate charged. Hydrogen is injected into the autoclave up to a pressure of 52.7 kg / cm2, and stirring is started. The hydrogen pressure is restored at time intervals set to a pressure of 59 to 63 kg / cm2. Stirring continues until until the hydrogen uptake has subsided. Thereafter, the mixture is 10 parts Sodium bicarbonate added and evaporated. The residue is acidified with chloroform extracted and made alkaline according to Example 1 and extracted again with chloroform. The chloroform extract of the alkaline solution is evaporated and distilled. The boiling point N- (1,1-dimethyl-3-dimethylaminobutyl) -3-methoxypropionamide is obtained 1080C / 0. -9 torr. Yield 1418.6 parts (73.6 percent of theory).

3 e i s p i e 1 5 The procedure of Example 4 is repeated, however 325 parts (1 mol) of N- (1,3-diphenyl-1-mothyl-3-oxopropyl) -3-mothoxypropionamide are obtained used. The N- (1,3-diphenyl-1-methyl-3-dimethylaminobutyl) -3-methoxypropionamide is obtained.

3 e i s p i e 1 6 A solution of 20.1 g (0.1 mol) of N- (1,1-dimethyl-3-oxobutyl) -3-methoxypropionamide and 10 g (0.137 mol) of diethylamine in 100 ml of methanol is mixed with 0.25 g of Raney nickel offset. The mixture is poured into a hydrogenation tank and hydrogen is pressed on up to a pressure of 18.3 kg / cm2. The hydrogenation is carried out at 50.degree carried out until the hydrogen uptake is complete. After that the product isolated according to example 1. N- (1,1-dimethyl-3-diethylaminobutyl) -3-methoxypropionamide is obtained.

Example 7 According to Example 4, a mixture of 201 parts (1 mol) N- (1,1-dimethyl-3-oxobutyl) -3-methoxypropionami.dj 170 parts (2 mol) of piperidine, 0.5 part of platinum oxide and 1 part of dimethylammonium perchlorate at an initial rate Hydrogen pressure of 4.9 kg / cm2 hydrogenated. As soon as the hydrogen pressure is at 2.74 kg / cl.n.2 has dropped, hydrogen is injected again. After working up according to the example, the N- (1,1-dimethyl-3-piperidinobutyl) "3-methoxypropionamide obtained from boiling point 112 to 115 ° C / 0.25 Torr.

EXAMPLE 8 According to Example 1, 20.1 g (0.1 mol) of N- (1,1-dimethyl-3-oxobutyl) -3-methoxypropionamide are obtained with 10 g (0.14 mol) of pyrrolidine in the presence of 0.3 g of platinum oxide and 100 ml of methanol implemented.

After the uptake of water has ended, the methanol is distilled off and the N- (1,1-dimethyl-3-pyrrolidylbutyl) -3-methoxypropionamide formed according to Example 1 isolated.

Example 9 According to Example 1, N- (1,1-dimethyl-3-morpholinobutyl) -3-methoxypropionamide is used by reacting 201 parts (1 mol) of N- (1,1-dimethyl-3-oxobutyl) -3-methoxypropionamide with 174 parts (2 moles) of morpholine in the presence of 0.5 part of platinum oxide and 1 part Dimethylammonium perchlorate produced.

B e i s p i e 1 10 As in Example 4, but using 1810 parts (16.9 mol) of methylaniline become N- (1,1-dimethyl-3-methylanilinobutyl) -3-methoxypropionamide manufactured.

general formula I The amides of / in which R6 is the group denotes, which are also referred to below as acrylamido compounds, can be prepared from the above-described oxy compounds by eliminating R8OH by methods known per se. Typical methods are described by PF Butskus et al., Russian Chemical Reviews, Vol. 35 (1966), p. 39. The preferred method is pyrolysis in the presence of a base, usually a strong base such as solid sodium hydroxide, at temperatures from about 70 to 1500C. This reaction is preferably carried out under reduced pressure.

Another process for the preparation of the acrylamido compounds consists in the reaction of a nitrile of the general formula common form with an o:, ß-unsaturated amine of the all- in the presence of sulfuric acid. Unsaturated amines of the general formula III can be obtained by reacting a compound of the general formula with a 1,3-diene, usually in the presence of a strongly alkaline catalyst such as sodium metal. This reaction is a typical 1,4-addition reaction.

When reacting the unsaturated amine with the nitrile, preference is given to at least about 1.5 moles, generally about 1.9 to 3.0 moles of the nitrile per mole of the unsaturated amine is used. The concentration of sulfuric acid should be at least c about 90 percent, preferably about 96 to 98 percent. The molar ratio from sulfuric acid to amine should be at least about 1: 1, preferably from about 1.1 : 1 to 2: 1. Solution agents are usually not required, it can however, a small amount of a polymerization inhibitor such as Add hydroquinone or a sterically hindered phenol. After completion of the implementation can the product through thin and neutralize the mixture and separating off the unsaturated amide by customary methods.

The preparation of the acrylamido compounds is carried out by the following Examples 11-17 illustrated.

3 e i s p i e 11 A mixture of 144.7 parts (0.63 mol) of N- (1,1-dimethyl-3 dimethylaminobutyl) -3-methoxypropionamide, 1 part solid sodium hydroxide and 1 part Hydroquinone is placed in a reaction vessel equipped with a condenser with a by means of dry ice cooled template, an agitator and a device for control the temperature is equipped. The pressure in the container is reduced to less than 5 Torr is reduced and the flask is heated to 8,000. It sets off a violent response on, and a liquid condenses in the template. After about 30 minutes the temperature is increased to 906C and held at this value for 3 hours. That N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide formed boils at 80 to 9,100 / 0.3 to 0.4 torr.

Yield 109.1 parts (87.4 percent of theory). The compound contains 14.1 percent nitrogen.

EXAMPLE 1 e 12 to 14 The procedure of Example 11 is repeated, but using N- (1,3-diphenyl-1-methyl-3-dimethylaminopropyl) -3-methoxypropionamide, N- (1,1-dimethyl-3-piperidinobutyl) -3-methoxypropionamide and N- (1,1-dimethyl-3-methylanilinobutyl) -3-methoxypropionamide. The corresponding acrylamides are obtained.

3 e i s p i e 1 15 A mixture of 273 parts (4 mol) of isoprene and 2 parts (0.087 mol) sodium metal is at 00C within a period of 180 parts (4 mol) of dimethylamine are added for 1 hour. The temperature is through cooling with a cooling coil filled with dry ice and isopropanol on one Value kept below 120C. When the addition of the dimethylamine is complete, the mixture becomes Stirred and keft for another 3 1/2 hours.

Then 6 parts of methanol are added to dissolve the sodium, and the mixture is distilled. The fraction boiling at 117.5 to 119.5 ° C is 1-dimethylamino-3-methyl-2-butene.

A container made of a plastic is cooled to OOC and with 450 g (8.5 moles) of acrylonitrile, 1020 g (10 moles) of sulfuric acid and 37 g of water are charged. This mixture is then mixed with 475 g (4.2 mol) of the 1-diinethylamino-3-methyl-2-butene obtained and 8.5 g of 2,6-di-tert-butyl-p-cresol are added. The mixture is about 1 hour stirred at 680C and then neutralized with about 30 percent sodium hydroxide solution. the Organic layer is separated, diluted with 2050 ml of methanol and made with ammonia neutralized. 1000 ml of methanol are then added and the solution is filtered. The methanol is distilled off from the filtrate and the residue is reduced under reduced pressure Distilled pressure. There are 400 g (64.5 percent of theory) N- (1,1-dimethyl-3-dimethylaminopropyl) -acrylamide obtained from boiling point 75 to 920C / 0.25 to 0.9 torr. The product contains 15.4 percent nitrogen, the theoretical value is 15.2 percent.

The amino compounds prepared in the manner described above can by reaction with a suitable acid in an amine salt or by reaction e.g. converted into the quarterly ammonium salts with an alkyl halide or sulfate will. This is illustrated in the following examples.

3 e i s p i e 1 16 2.8 g (0.0197 mol) of methyl iodide become one Solution of 3.6 g (0.0182 mol) of N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide in Given 10 ml of benzene. An exothermic reaction sets in and the temperature of the The mixture is kept at 25 to 30 ° C. by external cooling. After 16 to 18 hours A greasy solid separates out with stirring. This solid is separated off and recrystallized from a mixture of methanol and benzene. Yield 4.7g Trimethyl-3 (1-acrylamido-1,1-dimethylbutyl) ammonium iodide.

3 e i s p i e 1 17 In a solution of 5 g of N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide hydrogen chloride gas is passed in benzene. The dimethyl-3- (1-acrylamido) -1,1-dimethylpropyl) ammonium chloride formed precipitates and is filtered off.

The acrylamido compounds can be used either alone or with others polymerize polymerizable monomers. The term "polymer" means homopolymers, Copolymers, terpolymers and other interpolymers.

The polymers of the invention are generally by free radical Polymerization obtained. The polymerization can be in bulk, solution, suspension or Emulsion can be carried out, with illan the monomer or monomers with a Polymerization initiator either in the absence or presence of a diluent at temperatures of about 0 to 2000C. Examples of suitable free Free radical polymerization initiators are benzoyl peroxide, tert. -Butyl hydroperoxide, Acetyl peroxide, hydrogen peroxide, azoisobutyric acid dinitrile, sodium persulfate, Ammonium persulfate ~ sodium metabisulfite and chlorate sulfite. The solution polymerization can be used in an organic solvent such as benzene, toluene, cyclohexane, n-hexane, Naphtha, tetrahydrofuran or a mineral oil. The emulsion and suspension polymerization is preferably carried out in water or a mixture of Water carried out with an organic solvent containing hydroxyl groups.

The radical polymerization of the monomers can also be called photopolymerization can be performed with UV light, visible light, or ultra-red light. For this Process is the -egemzar-t known suitable initiators and sensitizers necessary.

Suitable emulsifiers for the production of emulsion polymers are cation-active compounds, such as stearyl dimethylbenzylammonium chloride, non-ionic Wetting agents, such as alkylaryl polyether alcohols and: sorbitan monooleate, anion-active Network agent, such as sodium decylbenzenesulfonate, dioctylsodium sulfosuccinate, Sodium salts of alkylaryl polyether sulfates and sodium lauryl sulfate, as well as alkali metal salts of lignosulfonic acid and silica, as well as colloidal substances such as casein, sodium polyacrylate, Carboxymethyl cellulose, hydroxyethyl cellulose, tragacanth, sodium alginate, gelatin Methyl cellulose, gum arabic, dextrins and polyvinyl alcohol.

For the production of copolymers with the amides, the most varied Monomers are used. Usually these monomers are polymerizable vinyl compounds. These include (1) esters of unsaturated alcohols, (2) esters of unsaturated acids, (3) esters of unsaturated polyhydric alcohols (such as butenediol), (4) cyclic vinyl compounds, (5) unsaturated ethers, (6) unsaturated ketones, (7) unsaturated amides, (8) unsaturated aliphatic hydrocarbons, (9) vinyl halides, (10) unsaturated acids, (11) unsaturated acid anhydrides, (12) unsaturated acid chlorides, and (13) unsaturated ones Nitriles Specific examples of these compounds are: 1. Esters unsaturated alcohols: allyl, methallyl, crotyl, 1-chloroallyl, 2-chloroallyl, Cinnamyl, vinyl, methylvinyl, 1-phenallyl and butenyl esters of (a) saturates Acids such as vinegar, propionic, butyric, valeric, caproic and stearic acids; (b) unsaturated Acids, such as acrylic acid, α-substituted acrylic acids, such as alkyl acrylic acids, e.g. methacrylic, ethyl acrylic and propyl acrylic acid, and arylacrylic acids such as phenyl acrylic acid, Cronic, oleic, linoleic and linolenic acids; (C) polybasic acids, such as oxalic, malonic, Amber », glutaric, adipic, pimeline, cork, azealic and sebacic acidy (d) unsaturated polybasic acids, such as maleic, fumaric, citraconic, mesaconic, itaconic and methylenemalonic acid, Acetylenedicarboxylic acid and aconitic acid; (e) aromatic acids such as benzoic, phenylacetic acid, Phthalic, terephthalic and benzoylphthalic acids.

2.-Esters of saturated alcohols, such as methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl or behenyl alcohol, with unsaturated aliphatic monobasic or polybasic carboxylic acids of the aforementioned Art.

3. Esters of unsaturated polyhydric alcohols, such as butenediol, with saturated ones and unsaturated aliphatic and aromatic monobasic and polybasic Acids of the aforementioned type.

4. Cyclic vinyl compounds, e.g.

(a) monovinyl-substituted aromatic hydrocarbons, such as allylbenzene, Styrene, o-, m-, p-chlorostyrenes, -bromostyrenes, -fluorostyrenes, -methylstyrenes, -äthylstyrenes and cyanogen tyrenes; Di-, tri- and tetrachlorostyrenes, -bromostyrenes, -fluorostyrenes, -methylstyrenes, -äthylstyren and -cyanstyrenes; Vinyl naphthalene and vinyl cyclohexane; (b) the corresponding polyvinyl compounds such as divinylbenzene and trivinylbenzene; (c) heterocyclic vinyl compounds, such as inylfuran, vinylpyridine, vinylbenzofuran, N-vinyl carbazole, N-vinyl pyrrolidone, N-vinyl thiopyrrolidone and N-vinyloxazolidone.

5. Unsaturated ethers, such as methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, Octyl vinyl ether, diallyl ether, ethyl methyl ether and allyl ethyl ether.

6. Unsaturated ketones such as methyl vinyl ketone and ethyl vinyl ketone.

7. Unsaturated amides, such as acrylamide, methacrylamide, N-methylacrylamide, N-phenylacrylamide, N-allyl acrylamide, N-methylol acrylamide, N-allyl caprolactam, diacetone acrylamide and N- (1,1-dimethyl-3-hydroxybutyl) acrylamide.

8. Unsaturated aliphatic hydrocarbons, such as ethylene, propylene, Butenes, butadiene, isoprene, 2: chlorobutadiene and, more generally, α-olefins.

9. Vinyl halides, such as vinyl fluoride, vinyl chloride, vinyl bromide, Vinylidene chloride, vinylidene bromide, allyl chloride and ailyl bromide.

10. Unsaturated acids of the aforementioned type, such as acrylic, methacrylic and propyl acrylic acid.

11. Unsaturated acid anhydrides, such as maleic, citracon, itacon, cis -4-Cyclohexene-1,2-dicarboxylic acid and bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride.

12. Unsaturated acid halides5 such as cinnamoyl, acrylic, methacrylyl, Crotonyl, 07.eyl and fumaryl chlorides or bromides.

13. Unsaturated nitriles such as AcryInitril-, MetELacryInitril and others substituted acrylonitriles.

The preferred comonomers used are the vinyl esters of carboxylic acids, such as vinyl acetate, the alkyl esters of unsaturated carboxylic acids such as ethyl acrylate, 2-ethyl-ethyl acrylate and methyl methacrylate, unsaturated nitriles such as acrylonitrile, and unsaturated amides, such as acrylamide, N-methylacrylamide and methacrylamide.

The relative proportions of the amides and the comonomers used During the copolymerization depend on the reactivity of these monomers as well the desired properties of the copolymers from Hard copolymers by polymerizing a mixture of monomers with few substituents or relatively short-chain substituents obtain. If polymers To be produced with even greater hardness, a monomer mixture can be used which is incorporated with a small amount of a bifunctional monomer, such as divinylbenzene, which crosslinks the polymer. The polymers can also from polymers of N-3-oxo-hydrocarbon-substituted acrylamides, such as N- (1,1-dimethyl-3-oxobutyl) acrylamide (Diacetone acrylamide), by reductive amination in a similar manner and among similar Conditions prepared as described for the preparation of the oxy compound above are described.

Polymers in which Y is an amino group can be used in the corresponding salts and quaternary ammonium salts are converted in the same way as described for the ionomers. Polymer salts can be obtained from the monomeric salts can be obtained by conventional polymerization.

The preparation of the polymers using the acrylamide do-compounds is illustrated in Examples 18-30.

Example 18 A solution of 10 parts of N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide in 40 parts of benzene is flushed with nitrogen for 10 minutes and then rflit added 0.05 parts of benzoyl peroxide.

The solution is heated to 60 ° to 650 ° C. for 16 hours. After that will be another 0.05 part of benzoyl peroxide entered. The mixture is again 16 hours heated and then the benzene is distilled 2l5. It remains a viscous one Oil that is dissolved in methanol. The solution is poured into water. ISiorboi falls the Polymer of N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide and is on air dried.

For example 19 4 grams (0.202 moles based on monomer) of the polymer from Example 18 are dissolved in 25 ml of methanol and mixed with 2.85 g (0.202 mol) of methyl iodide offset. The solution is heated to 50 to 60 ° C. for 90 minutes. One forms white precipitate The liquid is decanted and the precipitate, the poly [trimethyl-3- (1-acrylamido-1, 1-dimethylbutyl) ammonium iodide] is washed with acetone and dried in the air.

For example, 20 parts of a mixture of 20 parts of N- (1,1-dimethyl-3-dimethylaminobuene tyl) acrylamide, 80 parts of water and 0.1 part / sodium lauryl sulfate is 30 minutes Purged with nitrogen and then with a solution of 0.1 part of ammonium persulfate and 1 part water added. During the polymerization, the solution is stirred The mixture is left to stand for 16 to 18 hours and then filtered off. The received Suspension homopolymer is dried on the L B e i s p i e l 21 A solution of 20 parts (0.19 mol) of N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide in 8.5 Parts of water are flushed with nitrogen and, with 0.5 parts of ammonium persulfate The mixture is stirred for about 90 minutes. During this time, the Polymerization. Then 175 parts of water and then 13.7 parts (0.109 mol) Dimethyl sulfate added. An exothermic reaction sets in. The mixture will 16 to Stirred for 18 hours. An aqueous solution of the quaternized is obtained Homopolymer from which the water is reduced by evaporation and drying Pressure is removed.

EXAMPLE 22 The procedure of Example 18 is repeated again however, N- (1,3-diphenyl-1-methyl-3-dimethylaminopropyl) acrylamide is used as the monomer used on the same weight basis. A similar homopolymer is obtained.

EXAMPLE 23 The procedure of Example 18 is repeated, however, the monomer is replaced by the N- (1,1-dimethyl-3-methylanilinobutyl) acrylamide used on an equal weight basis. A similar homopolymer is obtained.

Example 24 A solution of 1 part of N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide in 5 parts of water with 0.1 part of methylene blue and a solution of 0.2 parts Triethanolamine added in 10 parts of water. The solution is made with an ultra-red heat lamp irradiated. The polymerization begins after about 5 seconds, which is reflected in the Disappearance of the blue color in the solution and the formation of a cloudy precipitate shows.

3 e T 5 p i e 1 e 25 to 27 copolymers of acrylonitrile with N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide are made from 49.5 parts of acrylonitrile and 0.5 parts of acrylamide, 47.5 parts of acrylonitrile and 2.5 parts of the acrylamide or 45 parts of acrylonitrile and 5 parts of the acrylamide manufactured. In either case, the monomers are in 600 parts Dissolved water, the aqueous solution is flushed with nitrogen and with a solution of 0.25 parts of ammonium persulfate. added to 1 part of water. Once the precipitation of the copolymer is complete, it is filtered off, washed with water and dried in a vacuum oven.

Example 28 2503 parts of dimethyl sulfate are added to a solution of 2.97 parts of N (1,1-dimethyl-3-dimethylaminopropyl) acrylamide in 225 parts of water given with stirring. One takes place over a period of about 30 minutes exothermic reaction. Then 15 parts of acrylamide are added and the solution becomes purged with nitrogen. About 0.5 g of ammonium persulfate are then added. The polymerization takes place over a period of 4 hours. After this Time 200 parts of water are added and stirring is continued. It will obtained a homogeneous mixture, which with water to an iprozentigen solution of the quaternized copolymer is diluted.

Example 29 A mixture of 40 parts of vinyl acetate, 10 parts N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide, 0.5 part sodium lauryl sulfate and 450 parts of distilled water is purged with nitrogen and with a solution 0.25 parts of ammonium persulfate in 1 part of water are added. After that, the mixture heated to> 5 ° C for 1 hour while stirring. The product is an emulsion of the formed Copolymer.

Example 30 According to Examples 25 to 27, a copolymer of 30 Parts of ethyl acrylate, 20 parts of N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide, 450 parts of water, 0.5 part of sodium lauryl sulfate and a solution of 0.25 part Ammonium persulfate made in 1 part water. That obtained by coagulating The polymer is filtered off and dried in a vacuum oven.

Through the incorporation of the acrylamide bonds, nitrile-polyamine is obtained their dyeability is improved. This is shown by an experiment in which the foils in the Examples 25 to 27 copolymers produced with a polyacrylonitrile film be colored with the dye Orange II. The slides are 90 minutes in one 0.05 percent aqueous solution of Orange II suspended at 80 to 980C, then washed with distilled water and dried. The 1'olyacrylonitrilfoli e is not colored, while the color of the films of the polymers of Examples 25 to 27 with increasing content of N- (1,1-dimethyl-3-dimethylam.inobutyl) -acrylamide in Copolymer increases.

The dyeability of polypropylene is also increased by treatment with the polymers of the invention improved. This is shown by an experiment in which 2.5 g, 5.0 g or 7.5 g of an N- (1,1-dimethyl-3-dimethylaminobutyl) acrylamide homopolymer similar to that of Example 20 is added to 50 g samples of polypropylene. The polypropylene is overlaid with a sufficient amount of methanol, and the mixtures are Shaken for 1 minute and 40 minutes left in closed bottles. Then the bottles are opened and the methanol is initially at room temperature temperature and finally evaporated in a vacuum oven at 48 to 50 0C. Foils from the modified polypropylene samples obtained are in 2 1/4 hours in the above-described solution of the dye Orange II suspended at 60 to 90 ° C.

After that, the slides are removed from the solution with distilled Water washed and dried. All foils are colored by the dye.

The polymers obtained from the acrylamido compounds are also valuable for improving the dry strength and wet strength of paper. the Improvement in dry strength is shown in an experiment on the strip of filter paper with a percent solution of the polymer of Example 20 in methanol saturated and dried by hanging for two hours at room temperature. The average tear strength of the treated paper strips, determined on an Instron tester using a crosshead speed of 5.08 mm / minute at a temperature of 220C is 9.79 kg / 25.4 mm width in comparison 6.26 kg / 25.4 mm width for an untreated sample.

The quaternized polymers are valuable as flocculants to precipitate a wide variety of substances from water.

The effectiveness of these polymers as flocculants for precipitation of kaolin shows an experiment in which 1 part of kaolin is suspended in 100 parts of water will. Also add about 0.1 part of a 20 percent aqueous solution of the polymer of example 19 added. The suspension will last about 30 seconds shaken and then left to stand. A flaky one forms immediately Precipitation. In a control sample that was not made with the homopolymer from Example 19 is added, the kaolin remains suspended.

The effectiveness of the quaternized polymers as flocculants For raw wastewater, an experiment shows that '600 ml of wastewater in a beaker are given. With rapid stirring, an aqueous solution of the quaternized Polymeri sats added. Rapid stirring is continued for 3 minutes, after which time is Stirred slowly for 12 minutes. Finally the mixture is allowed to settle. from A 50 ml aliquot is removed from the upper 12.7 mm of the mixture and its turbidity is determined with a Boyce-Phoenix light scattering photometer. The results are compiled in the table below.

Flocculant concentration table, ppm. Haze homopolymer of Ex. 21 1 2.57 2 2.03 -4 0.931 8 0.400 10 0.152 12 0.112 13 O, O9O copolymer of Ex. 28 1 1.39 2 0.570 4 0.306 8 0.136 10 0.067 As the acrylamido compounds Can be polymerized by photopolymerization, they are also suitable for Light printing fins (photo engravings) and photographic methods.

You can also use crosslinkers, such as divinylbenzene, in the presence of Suspending agents, such as bentonite, copolymerized to form cation resin exchangers will.

Claims (16)

P a t e n t a n s p r ü c h e 1. Polymers of amides of the general formula I in which R1, R2 and R3 are each a hydrogen atom or a hydrocarbon radical and R4 and R5 are each a hydrocarbon radical, R6 is the group means R7 is a hydrogen atom or a lower alkyl radical and R8 is a hydrocarbon radical, Y is the group means X is a salt-forming anion, Z1 is a hydrogen atom or a hydrocarbon radical and Z2 is a hydrogen atom or an alkyl or cycloalkyl radical, or the group denotes a heterocyclic radical and Z3 is a hydrogen atom or a lower alkyl radical, optionally with a polymerizable vinyl monomer. 2. Polymers of amides according to Claim 1, in which R7 is a hydrogen atom or the methyl group and. R8 denotes a lower alkyl radical. 3. Polymers of amides according to claim 2, in which Y is the group means. 4. Polymers of amides according to Claim 3, in which R1, R2 and R3 each represents a hydrogen atom or a lower alkyl radical, R4 and R5 each represent a lower one Alkyl radical, R7 is a hydrogen atom and Z1 and Z2 are lower alkyl radicals. 5. Polymers of amides according to Claim 4, in which R1 is a hydrogen atom or a methyl group, R2, R3 and R7 are hydrogen atoms, R4r, R5 and R8 are methyl groups and Y represents the dimethylamino group. 6. Polymers of amides according to Claim 2, in which Y is the group means. 7. polymers of amides according to claim 6, in which R1, R2 and R3 Hydrogen atoms or lower alkyl radicals, R4 and R5 lower alkyl radicals, R7 a hydrogen atom and Z1 and Z2 represent lower alkyl radicals. 8. Polymers of amides according to Claim 7, in which R1 is a hydrogen atom or a methyl group, R2, R3 and R7 hydrogen atoms, R4, R5 and methyl groups and Y is the group 0+ N (CH3) 3x. 9. Polymers of amides according to Claim 1, in which R7 is a hydrogen atom or a methyl group. 10. Polymers of amides according to claim 9, in which Y is the group means. 11. Polymers of amides according to claim 10, in which R1, R2 and R3 hydrogen atoms or lower alkyl radicals, R4 and R5 lower alkyl radicals, R7 Hydrogen atom and Z1 and Z2 mean lower alkyl radicals. 12. Polymers of amides according to Claim 11, in which R1 is a hydrogen atom or a methyl group, R2, R3 and R7 hydrogen atoms, R4 and R5 methyl groups and Y represents the dimethylamino group. 13. Polymers of amides according to claim 9, in which Y is the group means. 14. Polymers of amides according to claim 13, in which R1, R2 and R3 hydrogen atoms or lower alkyl radicals, R4 and R5 lower alkyl radicals, R7 Hydrogen atom and z1 and z2 mean lower alkyl radicals. 15. Polymers of amides according to claim 14, in which R1 is a hydrogen atom or a methyl group, R2, R3 and R7 hydrogen atoms, R4 and R5 methyl groups and Y is the group N (CH3) 3xe. 16. Use of the polymers according to claim 1 as flocculants.