DE2549840A1 - Acrylamido-alkane-sulphonic acid amine and quat. ammonium salts - and their (co)polymers used as lubricant additives and pesticides - Google Patents

Abstract

The novel amine salts and quat. ammonium salts are of formula CH2:CH1.CO.NH.CR2R3.SO3H (in which R1 is H or lower alkyl. R2-2 are H or hydrocarbyl, >=2 of these being hydrocarbyl). Claims also cover their polymers and copolymers with an unsatd. monomer, esp. an acrylic cpd. The oil-soluble polymers are valuable dispersants, viscosity modifiers and rust inhibitors for lubricants, whilst the polymers are generally useful for their pesticidal and self-quenching properties. Pref. R1 is H or Me, R2 and R3 are hydrocarbyl, esp. lower alkyl and R4 and R5 are H. E.g. an amine salt (m. pt. 136-137 degrees C) was prepd. by reacting CH2:CH.CO.NH.-CMe2.CH2.SO3H with equimolar amt. of t-C8-H17.NH2 at room temp. at 50 degrees C in MeOH.

Description

"Amine salts and quaternary ammonium salts of acrylamido

alkanesulfonic acids and their polymers "The invention relates to the subject matter characterized in the claims.

The term "hydrocarbon radical" means a radical with present hydrocarbon character. Examples of these radicals are given below: (1) Hydrocarbon radicals, namely aliphatic radicals such as alkyl or alkenyl radicals, alicyclic radicals such as cycloalkyl or cycloalkanyl radicals, aromatic radicals, aromatic radicals substituted by aliphatic or alicyclic radicals, aliphatic or substituted by aromatic radicals alicyclic and cyclic radicals in which the ring is completed by another part of the molecule, that is, in which two substituents together form an alicyclic radical. Specific examples of these radicals are ethyl, ethyl, propyl, butyl, hexyl, octyl, decyl, vinyl, allyl, benzyl, cyclohexyl, cyclopentyl, methylcyclopentyl, cyclopentadienyl, vinylphenyl -, isopropenylphenyl, cinnamyl, naphthyl, ethynyl, propargyl, phenyl, tolyl, xylyl, diethylphenyl, dodecylphenyl and p-methylbenzyl groups and the group of the formula (2) Substituted hydrocarbon radicals, namely radicals which have substituents that are not hydrocarbon radicals but do not significantly change the hydrocarbon character of the radicals. Examples of such substituents are halogen atoms, such as fluorine, chlorine, bromine and iodine atoms, hydroxyl groups, alkoxy groups, especially lower alkoxy groups, keto, carboxyl or carbalkoxy groups, especially lower carbalkoxy groups, amide, amino, nitro, cyano , Mercapto or alkylthio groups, especially lower alkylthio groups, alkylsulfoxy or sulfone groups, sulfonic acid ester or sulfonamide groups.

(3) hetero groups, that is, groups which represent the hydrocarbon of the groups character / does not change significantly, and the atoms other than carbon atoms contained in a chain or in a ring system. Specific examples of heteroatoms are nitrogen, oxygen and sulfur atoms.

Generally there will be no more than about 3 substituents or heteroatoms and preferably no more than one heteroatom or substituent per 10 carbon atoms in the hydrocarbon residues.

The term "alkyl" has the same meaning as used above for the hydrocarbon residues was given.

The hydrocarbon radicals in the compounds are preferably Invention free of acetylenic and usually also free of olefinic double bonds and they contain at most about 30, preferably at most about 12 carbon atoms. The radicals are usually hydrocarbon radicals, especially lower hydrocarbon radicals with 1 to 7 carbon atoms. The preferred radicals are lower alkyl or lower Aryl radicals 7, in particular lower alkyl radicals.

The radical R1 in the compounds of the general formula I is a hydrogen atom or a lower alkyl radical, preferably a methyl group. The other radicals R are preferably hydrocarbon radicals, in particular alkyl radicals and especially lower alkyl radicals.

At least two of the radicals R2, R3, R4 and R5 are hydrocarbon radicals. As a rule, the radicals R2 and R3 are hydrocarbon radicals, usually lower ones Alkyl, lower aryl or lower aralkyl radicals, while the radicals R4 and R5 are hydrogen atoms or hydrocarbon radicals, usually lower Alkyl, lower Mean aryl or lower aralkyl radicals.

Specific examples of acrylamidoalkanesulfonic acids of the general Formula I are given below.

2-acrvlamido-2-methYlpropanesulfonic acid 2-methacrylamido-2-methylbutanesulfonic acid 2-acrylamido-2-phenylpropanesulfonic acid 2-Acrylamido-2-methyl-2- (4-chlorhenyl) propane sulfonic acid 2-acrylamido-2-methyl-2- (4-tert-butylphenyl) propane sulfonic acid 3-acrylamido-2-butanesulfonic acid 3-methacrylamido-3-methyl-2-butanesulfonic acid 4-methacrylamido-4-methyl-3-pentanesulfonic acid 3-acrylamido-3-methyl-2- (4-chlorophenyl) -2-butanesulfonic acid In the particularly preferred sulfonic acids of general formula 1, R2 is a lower alkyl, lower aryl or lower aralkyl radical, in particular a lower alkyl radical, R3 is a lower alkyl radical and R4 and R5 are hydrogen atoms. 2-Acrylamido-2-methylpropanesulfonic acid is particularly preferred.

The amines, of which the salts of the compounds of general Derive formula I can be primary, secondary or tertiary amines. Specific Examples are aliphatic amines, such as methylamine, dimethylamine, diethylamine, diethylamine, Triethanolamine, Butylamine, Hexylamine, Octylamine, Dodecylamine, Isopropyl-dodecylamine and octadecylamine, alicyclic amines such as cyclopentylamine, cyclohexylamine, dicyclop entylamine, dicyclohexylamine and N-methyl-N-cyclohexylamine, aromatic amines, such as Aniline, methylaniline, dimethylaniline, 4-dodecylaniline and N-dodecylaniline, or heterocyclic amines, such as aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, Imidazoles, indoles, piperazines, isoindoles, purines, morpholino, thiamorpholines, N-aminoalkylmorpholines, N-Aminoalkylthiamorpholine, Azepine, Azocine, Azonine, Azecine and Tetra, Di and Perhydro derivatives of the aforementioned compounds. Amines can also be substituted with Hydrocarbon radicals of the aforementioned type and polyamines, such as alkylene polyamines, with 2 to 10 amino groups and 2 to 7 carbon atoms in the alkylene radicals, in particular the ethylene polyamines, as well as p-phenylenediamine and aminopropylmorpholine are used will. Preferably the amines contain at least 6, usually at least 10 carbon atoms. The aliphatic monoamines are particularly preferred, in particular the primary monoamines with about 10 to 40, especially about 10 to 20 carbon atoms.

The salts of the compounds of the invention can be prepared according to known per se Methods are made. For example, the amine salts are made by reacting of the free amine with the free sulfonic acid. Mixtures can also be used of amines are used for salt formation. The implementation is usually at Temperatures of about 10 to 75 ° CS, preferably about 20 to 50 ° C., in a diluent such as water, an alcohol, an aromatic hydrocarbon, a chlorinated one Hydrocarbon or an ether. Generally the amine and the sulfonic acid used in approximately equimolar amounts. The amine salt is after known methods isolated and purified. Generally the solvent will distilled off and the residue uriçristallisiert.

The quaternary ammonium salts of the compounds of the general formula I can by reacting a tertiary amine with an ester of sulfonic acid, preferably a vicinal hydroxyalkyl ester. These esters are made by Implementation of the acid free with an epoxide, such as ethylene oxide or propylene oxide, manufactured.

The preparation of the salts of the compounds of the general formula I will be explained below.

Example 1 e 1 to 16 Different acrylamidoalkanesulfonic acids of the general formula are reacted with equimolar amounts of various amines in diluents at temperatures from room temperature to about 50 ° C. In Example 1, the reaction temperature is 60 to 650C. After a short reaction time, the solvent is distilled off. The corresponding amine salt remains, which is recrystallized and dried in some cases.

The amines and sulfonic acids used and other details the implementation are summarized in Table 1. The percentages in Table I. refer to the volume. Table I Ex. R2 Amine Diluent Solvent F., ° C for limcrystallization 1 CH3 trimethylamine methanol - -2 CH3 Pyridine methanol - -3 CH3 tri-n-butylamine methanol - -4 CH3 tert-octylamine methanol Acetonitrile 136-137 5 CH3 2-nonyl-2-methanol * 81.5-84 imidazoline 6 CH3 dodecylamine Methanol acetonitrile 56-59 7 CH3 isopropyl- methanol dodecylamine - -8 CH3 N-dodecylaniline Methanol (28%), benzene (72%) - -9 CH3 laurylamine methanol acetonitrile -10 CH3 dilaurylamine Methanol acetonitrile 49-55 11 CH3 octadecylamine methanol ** acetonitrile 80-82 12 CH3 N-Octadecylglycine Methanol Acetonitrile 85-88 13 CH3 Oleylamine Benzene - -14 CH3 Soyaamine methanol - -15 CH3 N-oleyl-B-amino-methanol - -butyric acid 16 C6H5 octadecylamine Methanol (67%), benzene (33%) acetone (90%) 99-101 methanol (10%) * product with acetone washed ** When cooling to 0 ° C, the product precipitates from methanol.

EXAMPLES 17 to 23 According to Examples 2 to 16, the amine salts listed in Table II are obtained from acrylamidoalkanesulfonic acids of the general formula manufactured.

Table II Ex. R1 R2 R3 R4 R5 Amine 17 H CH3 C2H5 H H Pyridine 18 CH3 CH3 CH3 CH3 H isoindole 19 CH3 C6H5 CH3 CH3 H diethylamine 20 H CH3 H CH3 H aniline 21 H CH3 CH3 C2H5 H methylaniline 22 H CH3 H C2H5 CH3 octadecylamine 23 H p-C6H4Cl H CH3 CH3 Dodecylamine Example 24 By reacting 1 mol of 2-acrylamino-2-methylpropanesulfonic acid the 2-hydroxyethyl ester is prepared with 20 moles of ethylene oxide under reflux. Excess ethylene oxide is then distilled off. A solution of 1 mole of the Ester in methanol is refluxed with 1 mol of triethylamine.

The methanol is then distilled off. The triethylammonium salt remains of 2-acrylamido-2-methylpropanesulfonic acid 2-hydroxyethyl ester.

The salts of the compounds of general formula 1 can according to a radical mechanism either alone or in the presence of other polymerizable Monomers are polymerized. The term "polymer" means homopolymers, Copolymers, terpolymers and other copolymers.

The radical polymerization can take place in bulk, solution, suspension or emulsion. The monomer or monomer mixture is with a Polymerization initiator and optionally in the presence of a diluent brought together at temperatures of about 0 to 2000C. Examples of usable Polymerization initiators are benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide, Hydrogen peroxide, azobisisobutyronitrile, persulfate bisulite, persulfate sodium formaldehyde sulfoxylate and chlorate sulfite.

Examples of emulsifiers which can be used for the production of emulsion polymers are cation-active compounds, such as stearyldimethylbenzylammonium chloride, non-ionic Compounds such as alkylaryl polyether alcohols and sorbitan monooleate are anion-active Compounds such as sodium decylbenzenesulfonate, dioctylsodium sulfosuccinate, sodium salts of alkylaryl polyether sulfates and sodium lauryl sulfate, alkali salts of lignosulfonic acids and silicas, colloidal substances such as casein, sodium polyacrylate, carboxymethyl cellulose, Hydroxyethyl cellulose, tragacanth, sodium alginate, gelatin, methyl cellulose, gum arabic, dextrins and polyvinyl alcohol.

A wide variety of polymerizable materials can be used to produce copolymers Unsaturated compounds are used, for example (1) esters of unsaturated Alcohols, (2) esters of unsaturated acids, (3) esters of unsaturated polyhydric alcohols, (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 nitriles.

Specific examples of these compounds are given below: 1. Unsaturated alcohols and their esters: allyl, methallyl, crotyl, 1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, 1-phenylallyl, and butenyl alcohol as well as their esters with saturated acids, such as acetic acid, propionic acid, butyric acid, Valeric acid, caproic acid and stearic acid, or with unsaturated acids such as Acrylic acid, α-substituted acrylic acids, including alkyl acrylic acids, ltie Methacrylic acid, ethyl acrylic acid and propyl acrylic acid, and arylacrylic acids, such as Phenylacrylic acid, Crotonic acid, oleic acid, linoleic acid and linolenic acid, with polybasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, with unsaturated polybasic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, Itaconic acid, methylenemalonic acid, acetylenedicarboxylic acid and aconitic acid, and with aromatic acids such as benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid and benzene phthalic acid.

2. Esters of saturated alcohols, such as methanol, ethanol, propanol, isopropanol, Butanol, isobutanol, sec. -Butanol, tert-butanol, 2-ethylhexyl alcohol, cyclohexyl alcohol or behenyl alcohol, with unsaturated aliphatic monohydric or polyhydric Carboxylic acids of the aforementioned type.

3. Esters of unsaturated polyhydric alcohols, such as butenediol, with saturated ones or unsaturated aliphatic, aromatic monobasic or polybasic carboxylic acids of the aforementioned Art.

4. Cyclic vinyl compounds, such as styrene, o-, m- or p-chlorostyrene, Bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes and cyanostyrenes, di-, tri- and tetrachlorostyrene, bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes, cyanostyrenes, Vinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene and allylbenzene, and heterocycles, such as vinyl furan, vinyl pyridine, vinylbenzofuran, N-vinylcarbazole, N-vinyl pyrrolidone and N-vinyloxazolidone.

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

6. Unsaturated ketones such as ethyl 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 hydroxymethylated diacetone acrylamide.

8. Unsaturated aliphatic hydrocarbons, such as ethylene, propylene, Butenes, butadiene, isoprene, 2-chlorobutadiene and, more generally, a-oleline.

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

10. Unsaturated carboxylic acids such as acrylic acid, methacrylic acid and Propyl acrylic acid.

11. Unsaturated acid anhydrides, such as maleic anhydride, citraconic anhydride, Itaconic anhydride, cis -4-cyclohexene-1,2-dicarboxylic anhydride, and bicyolo [2,2,1] -5-heptane-2,3-dicarboxylic anhydride.

12. Unsaturated acid halides, such as cinnamoyl, acrylyl, methacrylyl, Grotonyl, oleyl and fumaric chloride or bromide.

13. Unsaturated nitriles such as acrylonitrile, methacrylonitrile and others substituted acrylonitriles.

Particularly preferred comonomers are the monomeric acrylic compounds, including acrylonitrile, methacrylonitrile, acrylic acid amide, substituted acrylic acid amides, including diacetone acrylamide and water soluble hydroxymethylation products of these compounds, acrylic acid and methacrylic acid and their esters.

The preparation of polymers is explained below.

Parts and percentages relate to weight, unless nothing other is indicated.

Examples of 25 to 44 copolymers are taken in solution Nitrogen as a protective gas and produced with benzoyl peroxide as a polymerization initiator. After the polymerization has ended, the polymers are poured into the solution precipitated in methanol, filtered off, washed with methanol and hot water and dried under reduced pressure. The process conditions are given in Table III summarized.

Table III Ex. Mono-Comonomer% Solvent Polymerimer Sation Ex. temp "C 25 4 dodecyl methacrylate 65.5 benzene (877 '? 70 methyl methacrylate 25.8 ethanol (13% 26 6 dodecyl methacrylate 88.5 benzene 70 27 6 dodecyl methacrylate 90.7 benzene 70 28 6 lauryl methacrylate 81.4 benzene * 60 29 7 dodecyl methacrylate 64.0 benzene 70 riethyl methacrylate 25.2 30 8 dodecyl methacrylate 85.2 benzene 70 31 11 dodecyl methacrylate 72.7 benzene 60 32 11 dodecyl methacrylate 78.0 benzene 60 33 11 dodecyl methacrylate 84.2 benzene 60 34 11 dodecyl methacrylate 72.2 benzene 70 methyl methacrylate 14.2 35 11 stearyl methacrylate 88.1 benzene ** 65 36 11 lauryl methacrylate 80.0 benzene 70 37 12 dodecyl methacrylate 82.6 benzene 70 38 12 dodecyl methacrylate 62.3 benzene 70 methyl methacrylate 24.5 39 10 dodecyl methacrylate 82.0 benzene 70 40 10 dodecyl methacrylate 62.0 benzene 70 methyl methacrylate 24.4 41 13 dodecyl methacrylate 84.1 benzene 70 42 14 dodecyl methacrylate 84.5 benzene 70 43 14 dodecyl methacrylate 63.4 benzene 70 methyl methacrylate 25.0 44 15 dodecyl methacrylate 61.8 benzene (80%) 70 methyl methacrylate 24.4 ethanol (20% * For precipitation, the ethanol solution of the polymer is mixed with water.

** The precipitated polymer is dissolved in methylene chloride.

Example 1 45 A mixture of 5 parts of the product of Example 9, 35 parts of acrylonitrile and 150 parts of water is flushed with nitrogen and mixed with 0.08 part of benzoyl peroxide. The mixture is stirred for 16 hours heated to 60 ° C. The resulting polymer precipitates and is filtered off with Washed water, dissolved in dimethylformamide and poured into methanol again failed. The polymer is then filtered off and reduced at 70 ° C. for hours Print dried.

Example 46 A mixture of 5 g of the product of Example 9, 15 g of acrylonitrile and 80 g of water are mixed with 6 ml each of a 0.075 molar solution of sodium metabisulfite and a 0.15 to 5 molar solution of ammonium persulfate The mixture is added under nitrogen as a protective gas for 5 1/2 hours at room temperature touched. During this time, the resulting copolymer precipitates. The copolymer is filtered off, washed with water, dissolved in dimethylformamide and poured in reprecipitated in methanol.

3 e i s p i e 1 47 According to Example 46, a homopolymer is made from 25 g of the product of Example 9 made in 100 g of water. The polymer will dissolved in methanol and reprecipitated by pouring the solution into water.

For example, 48 to 50 copolymers of various amine salts of the compounds of general formula I are in benzene solution and with azobisisobutyronitrile produced as a polymerization initiator. The polymerization takes place in pressure bottles carried out at 600C.

The polymer is precipitated by pouring it into methanol, then washed with methanol and hot water and dried.

The monomers, the proportions and other reaction conditions are summarized in Table IV.

Table IV Ex. Monomer Comonomer Ex.

48 5 dodecyl methacrylate 57.9 methyl methacrylate 22.8 49 11 isodecyl acrylate 51.9 methyl methacrylate 30.6 50 11 tert-octyl acrylamide 85.5 B e i s p i e 1 51 es a mixture of 50.8 g of dodecyl methacrylate, 20 g of methyl methacrylate, 9.5 g of des Product of Example 11 and a solution of 5 g of hydroxymethylated diacetone acrylamide (produced by reacting diacetone acrylamide with formaldehyde in the molar ratio of about 1: 7 in aqueous solution and in the presence of a small amount of potassium hydroxide) prepared in 150 ml of methyl ethyl ketone and 10 ml of methanol. The mixture is with 0.15 g of azobisisobutyronitrile and 1 g of a mixture of C10 12-mercaptans were added. The mixture is then rinsed with stick material and filled into a pressure bottle and 24 hours shaken at 600C. After that, the obtained Tetrapolymer by pouring it into methanol, washing the precipitate with methanol and hot Water and drying isolated.

The polymers of the invention are suitable as paints Metal surfaces for rust protection. For this purpose, the polymer is generally used mixed in a solvent, optionally together with a pigment, and applied to the metal by dipping, brushing, spraying or applying with a roller. For example, the polymers of Examples 34, 40, 41 or 51 can be used in xylene or in a mixture of xylene and methyl isobutyl ketone in a volume ratio of 2: 1 be solved. The solution is then applied to a metal surface and allowed to evaporate the solvent. A rust protection coating remains behind a thickness of about 0.025 mm.

Oil-soluble polymers of the invention are valuable dispersants, Viscosity modifiers and rust inhibitors for lubricants. The polymers are generally useful due to their pesticidal and self-extinguishing properties.

Claims (14)

Claims (# Amine salts and quaternary ammonium salts of acrylamidoalkanesulfonic acids of the general formula I in which R1 is a hydrogen atom or a lower alkyl radical and the radicals R2, R3, R4 and R5 are hydrogen atoms or hydrocarbon radicals and at least two of the radicals R2, R3, R4 and R5 are hydrocarbon radicals. 2. Compounds according to claim 1 of the general formula I, in which R2 and R³ represent hydrocarbon radicals. 3. Compounds according to claim 2 of general formula 1, in which R1 represents a hydrogen atom or an ethyl group, R2 and R3 are lower alkyl, lower Aryl or lower aralkyl radicals and R4 and R5 hydrogen atoms or lower alkyl, mean lower aryl or lower aralkyl radicals. 4. Compounds according to claim 3 of the general formula I, in which R2 and R3 are lower alkyl radicals and R4 and R5 are hydrogen atoms. 5. Compounds according to claim 4 of the general formula I, characterized characterized in that the amine salts differ from aliphatic I; ionoamines with at least Derive 6 carbon atoms. 6. Amine salt of 2-acrylamido-2-methylpropanesulfonic acid. 7. Dodecylamine salt of 2-acrylamido-2-methylpropanesulfonic acid. 8. Octadecylamine salt of 2-acrylamido-2-methylpropanesulfonic acid. 9. Polymer of a salt of acrylamidoalkansullonic acid according to claim 1. 10. Polymer of a salt of a compound according to Claim 3. Polymer of an amine salt of a compound according to Claim 5. 12. Polymer of an amine salt of a compound according to claim 6. 13. Copolymer of an amine salt of a compound according to claim 6 with a polymerizable unsaturated monomer. 14. Copolymer according to claim 13, characterized in that the polymerizable unsaturated monomers is an asryl compound.