US2719156A

US2719156A - Methylolated quaternary ammonium compounds

Info

Publication number: US2719156A
Application number: US396306A
Authority: US
Inventors: Benneville Peter L De; Leo S Luskin
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1953-12-04
Filing date: 1953-12-04
Publication date: 1955-09-27
Anticipated expiration: 1972-09-27
Also published as: NL90411C; GB763323A; DE1032259B; FR1117217A

Description

METHYLOLATED QUATERNARY AMMONIUM 'COMPOUNDS Peter L. de Bonneville and Leo S. 'Luskin, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware A plication De em e ,1953, 1 Serial N 0. 396,306

7 Claims. '(Cl. "260 249-19) N9 D awing- This invention relates ,to methylolated quaternary ammonium compounds, particularly in the form of salts,

which serve as anti-static agents on textiles, particularly 1".

on synthetic ffibers whichare prone .to develop and retain a static charge. .These compounds may be assigned the seneralstructure n R3 ,RliNX (EH2 o N/ BUNK-4) dl NHCHrOR as typical thereof. In this formula R represents hydrogen or an alkyl group up to four carbon atoms, preferably -the-methylgroup, R represents hydrogen or an ROCH2- group, R and R represent alkyl groups individually or when taken together represent a saturated divalent aliphatic chain which forms a five.- 'to six-sided heterocycle with the nitrogen, as in morpholine, t'hiamorpholine, 3,5-dimethylrnorpholine, pyrrolidine, piperidine, or N- methylpiperazine, R represents an aliphatic hydrocarbon group, including alkyl, *alkenyl, and ar-allgyl groups, X represents an anion, and R and together may represent a propio'betaine radical, CH 2C H2 CO:6..

"There have long been sought materials which could be applied to textilefibers, particularlyrto synthetic fibers,

including those from cellulose acetat nylon, polye ter con nsate pclmcrylonitr'ile, and otherpolumeri fib rf rming materials t serve asantitati agents which would hav s me re i tance to normal cleaning pr cesses and which would not cause objectionable changes-in the character of these fibers. A,group of compound m ting this challenge hasrnowbecn discov red. Thes n w compounds have the property of imparting acharge or conducting layer on fibers, yarns, and fabrics treated therewith and apparently thus dissipate static charges or prevent the accumulationcf static .ch rge .therec These compounds might e expected to form insoluble resins- Yet they do not appear to ,do so. Rather theyappearto react with the fibers. At'least resinificationpi the compounds has not been iorced beyondthe water-soluble stage. Yet these novel-compounds-are sufliciently-retained .on yarns and fabrics after these are washed-to continue to-exert anti s tatic action.

Various aminoacetoguauamiues are .lkJJOWD of the .formula 2,719,156 Patented Sept. 27, 1955 These are conveniently prepared by reacting together in the presence of an alkaline reagent dicyandiamide and a tert-aminoacetonitrile NGHzCN Such compounds are known in which 'R and R are alkyl, ara'lkyl, cycloalkyl, alkenyl, and phenyl. The two R groups may be the same or may be diiferent. The two R groups may also be part of a saturated divalent chain, such as --CH2CH2CH2CH2.,

to form ,a heterocycle with the amino nitrogen. These aminoacetonitriles are formed in the same way as ,those from other secondary amines, such as dimethylamine, diethylamine, di'butylamjine, dodecylmethylamine, and the like. Secondary amine, formaldehyde, and hydrogen cyanide are brought together in any convenient order and reacted. "The tert-am'inoacetonitrile is collected as. a residue or is puritied'by a conventional step, such as distillation.

it"is, reacted with dicyandiamide in the presence of an alkaline catalyst, such as sodium or potassium hydroxide, benzyltrimethylammonium or dibenzyldimethylammo- ,nium hydroxide, choline, or a quaternary ammonium alkoxide, .such as choliue methoxide .or benzyltrimethylammonium butox'ide. A volatile, inert organic solvent may be used and the reaction accomplished by heating under reflux. The prod ct may be collected as a residue and purified byextraction, charcoaling, crystallizing, or similar conventional step. 7

The tert-aminoacetoguanamine which is thus formed to reacted with ,an alkylating agent to form a quaternary amm iu al ypical yl ngagent includ methyl iodide, methyl bromide, ethyl bromide, ethyl chloride, methyl sulfate, .butyl bromide, octyl bromide, dodecyl bromide, ,cctadecyl bromide, .allyl chloride, methallyl chloride, crotyl chloride, idodecenyl chloride, benzyl chloride/or bromide, methylbenzyl chloride, butylbenzyl chloride, .octylbenzyl chloride, dodecylbenzyl chloride,

:methyldodecylbenzylchloride, pentadecylbenzyl chloride,

etc. -ln place of ,oneor more of the above alkylating a n s oil-th more usual type :ther-emay be used 8-p rop,io

l c one.

w' ihc;crtenkaminoacetoguanamine and alkylating agent .tmaycbc mixed and heated together directly or, preferably,

through metathesis .or through known procedures for replacing anions of quaternary ammonium salts. Thus there may appear as an nion not only h common halide or methyl sulfate ions, but also sulfate, acetate, formate, nitrate, phosphate, and other anions.

On the other hand there may in effect be introduced directly a kind of organic ion by reacting the tert-aminoacetoguanamine with fl-propiolactone. This reaction gives propiobetaines,

Solvent is usually driven off from the reaction mixture to give a solid, which is essentially the desired quaternary ammonium salt.

This may be used as obtained or may be purified, if desired, by extraction or crystallization. These salts have fairly good anti-bacterial properties. For example, the lauryldimethylguanaminomethylammonium bromide has a phenol coeflicient of 85 against Micrococcus pyogenes, while substitution of the methyldodecylbenzyl group for the lauryl group gives a salt having a coefficient of 125.

The quaternary salts are reacted with formaldehyde to give N-hydroxymethyl derivatives. The formaldehyde may be supplied from the usual aqueous formaldehyde solutions of commerce, from a revertible polymer, or from alcoholic solutions. One or both of the NH2 groups of the quaternary compound may be reacted and suflicient formaldehyde is supplied to accomplish the desired degree of methylolation. The methylolation reaction is best carried out at a pH between 7 and 10. Temperatures between 40 and 100 C. may be used. The reaction products are soluble, particularly in water. The solutions can be evaporated to give solid products which have the characterizing group NHCH2OH. From one to two such groups may be introduced. There is some evidence that more than two groups may be introduced on average.

This group may be converted to an ether group by reacting the methylol derivatives with an alcohol. This is done by heating the methylol compound with an alcohol under acidic conditions, usually at a pH of to 3, most conveniently under reflux conditions with separation of water. The resulting ROCHzNI-I- derivative is obtained as a solution, from which it may be obtained as a solid by evaporating the solvent, usually here an excess of the alcohol used, such as methyl, ethyl, or butyl alcohol.

Typical preparations of compounds of this invention are described in the following illustrative examples, wherein parts are by weight unless otherwise designated.

Example 1 (a) A mixture of 55.4 parts of dimethylaminoacetonitrile, 50.4 parts of dicyandiamide, and 80 parts of isopropanol is stirred and heated under reflux (about 87 0.). Over a 45 minute period there are added to this mixture 32.3 parts of a 47% choline methoxide solution in methanol in 43.7 parts of isopropanol. The resulting mixture is stirred and heated under reflux for five hours. It is then cooled. The guanamine thus formed is filtered off and dried in an amount of 77 parts. It may be purified with charcoal in boiling water and recrystallized therefrom. It then melts at 235 -238 C. and contains by analysis 49.9% of nitrogen (theory 500% Repetition of the above procedure with use of sodium hydroxide, potassium hydroxide, choline, or benzyltrimethylammonium hydroxide as catalyst leads to the same product in a like degree of purity.

The compound thus prepared corresponds in composition to dimethylaminoacetoguanamine, which may be represented In the same way diethylaminoacetonitrile can be converted to diethylaminoacetoguanamine. Neither of these tert-aminoacetoguanamines is effective as an anti-static agent; nor are methylol derivatives thereof.

(b) There are mixed 29.6 parts of dimethylaminoacetoguanamine, 22.3 parts of benzyl chloride, and 680 parts of methanol. The mixture is heated under reflux for about 12 hours with formation of the quaternary salt, which separates when the mixture is cooled. This salt is filtered 01?. Additional product is obtained from the filtrate when it is concentrated. There is thus obtained in about 75% yield the quaternary salt,

This salt is sparingly soluble in water and is more soluble in aqueous dilute acid solutions. It is a white solid, melting at 251-253 C.

Reaction of diethylaminoacetoguanamine with benzyl chloride in the same way leads to the diethyl benzyl acetoguanamino quaternary chloride which is essentially like the dimethyl derivative described above.

(c) A portion of 44 parts of this quaternary salt is treated with 38 parts of an aqueous 36.5% formaldehyde solution which has been brought to a pH of 9.3 by addition of 10% sodium carbonate solution. The mixture is slowly heated to about C. with solution of the salt within 10 minutes to give a clear, orange-colored, viscous solution. Evaporation of this solution under reduced pressure at 45 C. gives a hygroscopic solid which by analysis contains 1.85 hydroxymethyl groups per molecule. This product is extremely water-soluble. This compound is fairly effective as a corrosion inhibitor. Rate of corrosion of a 10% sulfuric acid solution on an iron plate is reduced from over 0.25 lb./sq. ft./day to about 0.05 lb./sq. ft./day.

Methylolation of the diethyl compound gives a very similar product.

The above procedure is followed using 44 parts of the above quaternary salt and 20 parts of the aqueous 36.5% formaldehyde solution adjusted to a pH of about 9.2. The solid obtained on evaporation shows on analysis about one methylol group per molecule.

(d) A solution is prepared from 8.3 parts of the above benzyl chloride quaternary salt of dimethylaminoacetoguanamine in 12 parts of methanol. Thereto is added a solution of 3.1 parts of methyl hemiformal in 5 parts of methanol which has been adjusted to a pH of 8.5. The resulting mixture is heated under reflux for about an hour, at which time the solution has become homogeneous. It is then cooled and brought to a pH of 3.5 by adding dilute acid. The acid solution is heated under reflux for 20 minutes, is then cooled, is neutralized, and is evaporated to incipient precipitation. The concentrate is diluted with 70 parts of water to give a solution containing 14% of the dimethoxymethylated quaternary salt.

When nylon clothis passedthrough adilutesolution of .this salt and is dried, no statfic chargeis "built up :thereon. If thecloth is now washed withsoap' and soda alkoxymethyl derivatives.

Example 2 (a) A mixture of 40 parts of dimethylaminoacetoguanamine, 59 parts of dodecenyl chloride and 1000 par-ts of methanol isheated under reflux for five hours. The solution is then concentrated and cooled. There separates a white .so1idin..:an amount .Of .84 parts. It has a melting point of 249 C. and contains by analysis 9.62% of chlorine. It corresponds in composition to the dodecenyl chloride quaternary sallt of dimethylaminoguanamine. The theoreticalhchlorine content of this salt is 9.57%.

(b) There are mixed 57 parts of this salt and 35 parts of formaldehyde in an aqueous 37% solution which has been adjusted with sodium carbonate to a pH of 9.5. The mixture is heated to about 80 C. for minutes and treated with 800 parts of benzene. Benzene and water are distilled off to give a clear solution. fhe'resulting solution is evaporated totgive a slightly colored solid which is the di-hydroxyme hyl .derivative. It is freely soluble in water and quite surface active. Applied to synthetic fabrics, it prevents accumulation of a static charge. It reacts with cellulosic fabrics to supply quaternary groups thereon.

Example 3 (a) A mixture of 16.8 parts of dimethylaminoaceto guanamine, 31 parts of dodecyl bromide, and 238 parts of methanol is heated under reflux'afor'20-ihours, =.atwhich time the quaternizationrgis over 90% complete, as shown by titrations for ionizable chlorine. When the reaction mixture is cooled, a solid separates and is filtered ofi. When dried, it melts at 24,3245 C. with decomposition and contains 19.0% of bromine. Evaporation of the filtrate gives an additional crop of solid quaternary salt, bringing the yield to 422 parts. The product is soluble in water and in dilute acids. The solutions are markedly surface active. This salt has a phenol coefficient against .Salmonella typlzasa of 2.5 and agaiustMicmaacizus .pyqgenes var. .aureus of .85.

(b) A portion of 11,6,parts of thissaltistreated with 7 parts of aqueous 36.5% formaldehyde solution .adjusted to pH 9. The mixture is heated to about 75 C. and treated with 160 parts of benzene. Heating is continued with azeotropic-memoval of water. Evaporation leaves 10.5 parts of a tan solid, which is the polymethylol V derivative, containing by analysis 15.6% of bromine.

This compound is converted to the methoxymethyl derivative by treating with methanol acidified to a pH of 3.5 and heating with toluen Ihiscompound is also efiective in dissipating electric charges on synthetic yarns and fabrics.

Example :4

and 3.5 parts of aqueous 36% formaldehydesolution which has been adjusted to a pH of 9.13 with soda 'ash.

6 The mixture is heated and about 80.parts of benzene added. The mixture is heated under reflux and then water and benzene are taken ofi .to give a solid residue which is soluble in water, the dimethylolated derivative.

The alkoxymethyl derivatives are formed by reacting the methylo'l compound as above on the acid side with an alkanol.

Example 5 (a) There are mixed 16.8 parts of dimethy-laminoacetoguanamine, 36.7 parts of -11-.octa d ecyl .bromidaand 317 parts of methanol. The mixture is heated under During this time the initial slurry becomes homogeneous and then deposits awhite -;S 0l:id. The reaction mixture is cooled .to-give a white, waxy solid, which is filtered off, washed with ether, and dried in a yield .of about 33 parts by weight. It contains by analysis 15.3% of bromineandcorresponds to the octadecyl bromide quaternary ammonium salt, for which the theoretical bromine ,content is 15.9%. The compound melts at 242-244 C.

(b) There are mixed 25 parts of the above Quaternary ammonium salt, 17 parts of aqueous 36% formaldehyde solution which 'has been adjusted to pH .9 with soda ash solution,.,and 30.0 parts of toluene. The mixture is heated under reflux and is then distilled. The residual solution is evaporated under reduced pressure to a tan solid. It is somewhat soluble in water and imparts surface activity to its solutions.

Example 6 (1a) A solutionof 2-3.5 parts of dimethylaminoaceto- --,g-uanamin e in 250 parts of water is added to 7.2 parts-of tB-propiolactone.

A clear solution results. It is stirred and heated at 2C. for five hours. ltsis-evaporatedto dryness to give a white solid which is soluble in dimethyl- Lforrna-mide or ether.

The solid melts at 21--8 -222 C. with decomposition. By-nitrogen analysis it contains ,9'1 :of the quaternary salt, gnanaminomethyl dimethylpropiobetaine.

,(b) A mixture of 12 parts of this product, .56 'parts cofimethanol, $5.16 parts of a 59% formaldehyde solution in methanol, and 2.5 parts of water is adjusted to a pH Qf'Y8.JO .8-'S .with aqueous 50% sodium hydroxidesolution.

' This mixture is heated under reflux for .30 minutes, aciditied, and heated for 2.0 minutes under reflux. -It is neutralized-cooled, and filtered. The filtrate is evaporated :;to dryness to give 2155 parts of solid product, the dismethoxymethyl derivative of the above quaternary compound. It is dissolved in water to give a"15% solution. This solution :is added to a treating bath through which a fabric, of synthetic fiber from polyacrylonitrile is passed to @give. a i'finish which prevents accumulation .of static charges.

.sessed definite ion exchange properties with capacities'for vafious samples ranging from 3' '10" to "10- milliequiv- ,alents per square centimeter. Some samples were treated with benzyl chloride. They then had capacities of 4 10- and 9 10 milliequivalents per square centimeter. The ion exchange compounds formed by reaction of the methoxymethyl derivatives and cellulose were found regenerable. The treated fabrics withstood attack by alkali whereas untreated samples of the same fabric were markedly deteriorated by this treatment. The treated fabrics are of interest in filter cloths, conveyor belts, and the like for handling pulps and slurries from which small amounts of acid are to be removed.

Cellophane sheets were treated as above to give films having ion exchange action with a moderate degree of permselectivity.

Example 7 (a) To a solution of 179 parts of morpholine in 174 parts of water are added 20 parts of concentrated hydrochloric acid, and then at 1520 C. 163 parts of a 37% solution of formaldehyde in water. Following this there is introduced 54 parts of anhydrous hydrogen cyanide at 1520 C. and the mixture stirred for two to three hours at 20 C. The resulting crystalline product is recrystallized from ethanol to yield 63 parts of morpholinoacetonitrile, melting at 59 61.5 C.

(b) When 63 parts of this aminonitrile, 37.8 parts of dicyandiamide and 85 parts of isopropyl alcohol are heated under reflux, and a solution of 14 g. of potassium hydroxide in 50 ml. of isopropyl alcohol is added to this over a period of one hour, the solution darkens and the dicyandiamide dissolves. After refluxing for five hours and cooling, the dark red product is collected on a filter, washed with small amounts of hot water and dried. The tan solid so obtained is high-melting and corresponds in analysis to morpholinoacetoguanamine.

(c) A mixture of 21 parts of the tertiary guanamine and 14 parts of methyl iodide in 100 parts of methanol is heated for three hours. After removal of solvent the water-soluble quaternary salt is obtained in good yield as a solid residue.

(d) To 12 parts of 36.5% formaldehyde solution in water is added sufiicient aqueous sodium carbonate to give a pH of 9.3. When 17.5 parts of the above quaternary salt are added and the mixture is warmed at 80 C. for ten minutes, there results a clear solution of the methylol derivative. The water may be removed by azeotroping with benzene to give the solid methylol derivative, or the solution may be used without isolation. The composition of the product corresponds to about three methylol groups per mol of quaternary guanamine.

In a similar way, from N-cyanomethylpyrrolidine, which is obtained as a liquid distilling at 80-83 C./ mm., there can be prepared, using essentially the same ratios of reactants, pyrrolidinoacetoguanamine. This can be used in exactly the same way as heretofore described to produce methylolated and methoxymethylated quaternary guanamine salts.

We claim:

1. Compounds of the structure with the indicated nitrogen from the class consisting of 75 morpholinc, thiamorpholine, pyrrolidine, and piperidine, R represents a member of the class consisting of alkyl, alkenyl of at least three carbon atoms, benzyl, and alkyl benzyl groups and jointly with X a propiobetaine radical, and X represents a salt-forming anion.

2. A compound of the formula CH: CHaCcHr,

CHa-N-Cl Hz N N J-NHCH0H N 3. A compound of the formula CH: CHzCnHa CHa-NCl wherein R is a member of the class consisting of hydrogen and the methyl group and X is a member of the class consisting of chlorine and bromine.

6. A compound of the formula 7. A compound of the formula CH3 CHzCH C H3 N 0 0 C H2 ('1 N N HOCHzNH- C-NHCHzOH References Cited in the file of this patent UNITED STATES PATENTS West Dec. 30, 1947 Thurston Jan. 18, 1949

Claims

1. COMPOUNDS OF THE STRUCTURE