1.ApplicationNumber: US-9188749-A
1.PublishNumber: US-2581392-A
2.Date Publish: 19520108
3.Inventor: GROOTE MELVIN DE
KEISER BERNHARD

4.Inventor Harmonized: DE GROOTE MELVIN()
BERNHARD KEISER()

5.Country: US
6.Claims:

7.Description:
(en)Patented Jan. 8, 1952 'QUA'PERNARY DERIVATIVES or JGHLOROXY $3" PROPYIIATED .ci'ifoxYALKY-L- 4*; ."ATED fRHENOE-FALDEHYDE: RESINS- 1. iMelvifi D61fimotliUnivei-sitii:Cithahd Bernhard Keisei-i'webstef Groves, Mouassignors toBetrolitflorpofiatioii'yLtd, -WilmingtoxiiDelr, aicorporation of Delaware The present-invention is concernedwithcertain new chemicalproducts compounds or com- -positions which have useful application in'warious arts. These compoundsaw -quaternary ammonium compounds '-prepa-red" iri the wma-n-ner hereinafter described.
Our invention includes -meth'ods or :procedu-res *for manufacturing s'aid 'new chemical-products, ----compounds, or compositions asetvellras the products, compounds, or compdsitionsthem selves. Said new compounds or compositions are quaternary :ammonium *compounds derived by reaction between 'fill' achloro-oxypropylated derivative of hydroph-ile"hydroxylated synthetic -.products; said hydrophile synthetic products 'being oxyalkylationproductsbf (A) An alpha-beta alkylene oxide having not more than 4 carbon 'atomsand selected from the class consisting: ofcrethylenes-:-oxide,;;2propylene oxide; =butylenetoxide;'.:glycidezandi and (B)" An z,oxyalkylationesusceptiblei msiblewor- ,yganicsolvent-soluble; waters-'insolubl henolaldehyde resin said tresin-:beinaaderivednbyereaction between a vdifunctionalimonoh'ydric. phe- 1 nol and.an;aldehydevhavingrmotnover. ltz carbon :atoms and reactive. -tow.ard.::said t'rnhenoly usaid resin being formed: :izrathe'" substantialnabsence of, trifunctional phenolsxasaidr phenol being-50f the formula:
in which R is a hydrocarbon radical havingnt 'least 4 and not morethan "12 :carbon atoms and substituted in the 2,4,6 positionssaid-oxyalkylated resin being characterizedbyzrthekintroduction into the resin molecule of a plurality tof divalentradicals having the formula (R10). nfilill which Rlsis a member selected from theiiclas's consisting of ethylene radicals, propylene eradicals, butylene radicals, hydroxypropylene 'iadicals, and .ihydroxybutylene:radicals;.:and ngisxa numeral-varying from 1 156120; witli'fdzhe proviso that at least 2 moles of alkylene oxide be intro- ..duced foreach-phenolicnucleus isaid chlorooxypropylated compounds being obtained by -reaction with epichlorohydrin; and (2) a ibasic tertiary amine having not over'50 c'arbon'atoms. ...-.-A1though the--:herein':'idescribed productsahave av number of industrial gapplicationsgrtheysareZof .;particular value for resolvingqietroleumeeeniul-' sions of the water=in oil'typetliatare commonly l methylglyci'de 1 (Cl. zeosssz) 1?"!2 referred to as cut oil," roily oil, emulsified -':oil,-: *etc.-,= and which comprise "fine droplets of naturally-occurring waters or' brines dispersed in a more or -less permanent state throughout 5 tnwmewnmnconstitutes the continuous phase ftcthe eniulsion. This specific application is escribed and claimed in --our "co-pending appliati01i'-=Serla1 -No? 9l'j886j filed" May 6, 1949; now atent 2';542,0l1, -granted *February -20, 1 1951. See also our co-peiiding';application*Seria1 'No.
4i'469i-fll-ed December 10,-1-948.
whet-new products-"are'useful" as1 wetting, detergenteand leveling -agents,, in'-'th'er laundryy'texleahd' dyeing industries; "as wetting'agents "and "16 =detergents z-in the acid washing 'of buildingstone e aiid bricka as wetting agents and Spreaders in ".rtheuapplication or asphaltdn' road building. and ..th e like;; 848 a 'flotation"reagent in the; flotation egatively charged" particles'tsuch as ewagercoah washing -wasterwater, and various rade:=wastes '-and thelikey'awgermicides; inecticideaeniulsifying agents, as, :for: example, or-cosmeticsr spray"oilspwater-repellent textile M2 finishes; a's lubricantsfetc.
@The i-nstant"ammoniumwompounds are of articular value"'ffor 'various purposes [where uatemary. 'ammo'nium nomp'ounds'L. have? found pcificaapplication.
, i heoxyalkylated resinsp us'ed as' intermediates toeproduce the *products "i'ofthis applica- Ion-ware described in *our Patents" '2 9199,37 0, grantei March 7 1950; and 2542,011; granted bruaryi20j l95l=randreferenceis made'toi these :rrsins used to produce the alcoholic products. PEor speific-rexamples ,of these resins, reference 'sissmademo ltxamples 1a through 103a of Patent 212,499,370. For examples of oxyalkylated prod- .wgucts derived from these resins, reference is made ito'ithe tables in columns 31 throu h 46 of Patent "JIhe reaction ofiepichlorohydrin is, in essence, continuation of'thereaction involving ethylene 45 ICbiide, propylene soxidepror the like. The same .requivalentzcan -beaused;;.but it is desirable to make ai'slight :c'hange inflthe matter of catalyst. The .-usual catalyst in the "oxyalkylation of a material :when neither reactanta'contains chloride, is an 50 .ialkali such as been pointed out previously. Howeveri eithervreacta'nt contains chlorine, another 2 -type ofireactant canbe employed advantageously, tosvit on o'ii-themetallic chlorides such as ferric chloride 1n'f"chlofide;-.etc. At times it is sub- "stantially necessary to use such a catalyst, for
the reason that if an alkali is used, it reacts with a labile chlorine and the catalyst is lost. Our preferred procedure then is to add a slight amount of para -to1uene sulfonic acid to the intermediate products so as to neutralize any residual alkalinity. We havethen added small amounts of stannic chloride as a catalyst, so as to accelerate the reaction with epichlorohydrin.
The-* amount used is less than one-half of 1%, based j on the weight of the material, andusuallyone or two grams of stannic chloride are sufiicient in a reaction involving 300 to 600 grams of reactants. Due to the higher boiling point of epichlorohydrin, as compared with ethylene oxide,
for example, one can use identically the same equipment as employed in the manufacture of resins, as described in Example 1a. of Patent 2,499,370. In fact, it is our preference to use this particular equipment on a laboratory scale. 1
Example 10 The equipment employed was specifically that described in Example 16 of Patent 2,499,370. The resin solution employed was that described as 105D of Patent 2,542,011. instance, and in all subsequent examples, just sufficient para-toluene sulfonic acid was added in each case, if required to bringthe product. to substantially a neutral state, i. e., neutral or very faintly acid to methyl orange indicator. 554 grams of the oxyethylated resin solution were used, and to this there was added 1.6 grams of stannic' chloride. The mixture was stirred. and heated to 95 C. The above amount represented .8 of a mole per phenolic hydroxyl, based on the original phenol employed. The amount of epichlorohydrin added was just sufficient to react with all the phenolic hydroxyls, to wit, .8 of a mole, or 73.6 grams. The epichlorohydrin was added drop-wise with stirring and all oi it a temperature of 130 C. was reached. At this point some of the liquid started to;;refiux at about 125 to 130 C., with a thermometer in the vapor reading 127 C. No reactant passed into the condenser. This indicated that -the epichlorohydrin must have reacted completely at the end of this period, for the reason that it boilsat 117 C. The yield was 520 grams which contained approximately xylene. all istabulatedinthe table below.
Note that in this cosity perhaps a trifle, at the most, but definitely does reduce'water-solubility. Our preference in all instances was to obtain materials, which, after treatment, with epiehlorohydrin, showed -water-solubility at least equal to that described as desirable in connection with the oxyalkylated resin prior to treatment with epichlorohydrin. Stated another way, such material should meet the emulsification test, using xylene, as previously described.
' V Example 20 The same procedure was followed as in Example 1c, preceding, except that the oxyalkylated resin solution employed was that previously described under the leading 11% of Patent 2,542,011. The reactants employed were as follows: 645 grams of the resin solution; 55 grams of epichlorohydrin, and 1.2 grams of stannic 15 minutes.
chloride. The catalyst and the oxyalkylated resin solution were mixed together, as in Example 1c, and the epichlorohydrin added in a 10-minute period without any temperature rise. The temperature was then raised to 135 to 140 0.. As the temperature moved upward, there was a certain amount of refluxing which took place at 127 C. This reflux appeared for only a short period of time, and then the temperature rose rather rapidly to the predetermined point of 135 to 140 C. It was held at this temperature for one hour. At the end of this time, the reaction was complete. The final yield was approximately 700 grams containing about 20% xylene. 7 Example 3c The same procedure was followed as in Example 1c, preceding, except that the resin solution employed was that described as 123?) of Patent 2,542,011. The amount of this resin solution employed was 779 grams. The amount of catalyst employed was 1.2 grams. The amount 'of epichlorohydrin employed was 55.2 grams. The'resin, plus the catalyst, was heated to about C. and then the epichlorohydrin added in The temperature remained at 110 to C. for a short period of time and then was raised to 140 C. and stirred for 30 minutes. The yield was about 850 grams, containing about 17% xylene.
The same procedure was followed in a number of similar products and the data for this series Epichlo Solv. Pres Ex ox ai k Altount m rog a m gnOli gg g ig ff gield m 11151 esm o rams se rams rams r0 ,P r
Grams Temp. 0. hours Cent 1 Ex. No. of Patent 2,542,011.
1 In these experiments apparently some of the epichloroliydrin was lost through the condenser. The amount which combined is definitely less than the initial amount, in view of the lower final yield.
5 In this case an unoxyethylated resin was dissolved with enough added xylene to give a solution containing 40% xylene and 60% solvent.
The ultimate product was diluted with enough additional xylene so that the final product contained 30% and 70% resin which had been treated with eplchlorohydrin.
The chloro-oxypropylated compounds previously described have been prepared in pres-.- ence of a slight amount of solvent, such as xylene. This xylene usually was residual from the preparation of the ester and carried through the oxyalkylation stage and into the final stage. We have found this purely as a matter of convenience, particularly since solvent may be present for subsequent use, i. e., demulsification, or for the preparation of more complex derivatives. Needless to say, the solvent can be removed. In other words, the solvent, such as'xylene, can be distilled out and particularly employing a vacuum of about 20 to 40 mm. of mercury or thereabouts, and a temperature of 130 Q.
As previously pointed out, having obtained compounds in which there is a labile chlorine atom present, such as those described above, such products are then used as intermediates for further reaction with tertiary amines, particularly basic tertiary amines, to produce quaternary ammonium compounds. We have employed a large number of tertiary amines. In numerous cases these tertiary amines can be purchased in the open market. In other instances they can be prepared from primary or secondary amines by procedures which convert such amines into tertiary amines, for example, treatment with a methylating agent, such as dimethylsulfate, or an alkylene oxide, such as ethylene oxide, propylene oxide, styrene oxide, etc.
The alkylamines are best prepared from higher fatty acid amines, such as the primary fatty acid amines and secondary fatty amines listed in Armeen Price List No. 10, dated August 30, 1948, issued by Armour 8: Company, Chicago, Illinois. Rosin amines can be employed and are obtainable from Hercules Powder Company, Wilmington, Delaware. In a general way, the upper carbon atom limit in such amines is approximately 50, as, for example, a dialkyl fatty amine obtained from fatty acids having 22 carbon atoms, which is then treated with dimethylsulfate, styrene oxide, etc., or treated with ethylene oxide or propylene oxide, particularly repetitiously. One example of such amine would be di-octadecylamine, which was subsequently treated with 2 to 4 moles of propylene oxide.
Other suitable amines are the ester type, such as triethanolamine or triethanolamine which has been treated with 3 moles of ethylene oxide. followed by esterification with a higher fatty acid. Similar basic esters are obtainable from tertiary amines, such as diethylethanolamine. For instance, We have employde diethylethanolamine stearate as prepared by Carbide 8: Carbon Chemicals Corporation, New York city, N. Y., and designated for trade purposes as Amine ES.
One is not limited to monoamines but polyamines also can be employed. In the treatment of polyamines one can add enough of the chlorinecontaining reactant to combine with one or more of the basic nitrogen atoms present. Purely by way of examples, the following reactants are suggested.
R=alkyl or alkanol. R1=a1kyl from R100, the acyl radical of a higher fatty acid, or the like.
The following examples and the table illustrate specific preparations:
Example 1d 65 grams of the chlorinated derivative identified as Example 1c were mixed with 21.3 grams of dimethyldodecylamine. The temperature rose to 28 C. and then 33 C. The mixture was held. at this temperature for 20 minutes and then allowed to stand overnight. It was then heated to 140 C. for 6 hours. At the end of this time the reaction was complete.
Example 2d The same chlorinated derivative was used as in Example 1d. The particular tertiary amine employed was benzyldimethylamine. The amounts employed were 130 grams of the chlori; nated derivative identified as 10, and 27 grams of benzyldimethylamine. The maximum temperature employed was 140 C. and the reaction mass was held at this temperature for a period of 5 hours. The final product was particularly soluble in water.
Example. 3d
The same procedure was employed as in the preceding examples and the same chlorinated derivative employed. 65 gramsof the compound identified as Example 10 were mixed with 32 grams of octylphenoxyethoxyethyl dimethylamine. The material was heated to to C. for approximately 3 hours. The product obtained was comparatively clear and the reac-- tion appeared to go more rapidly than in Example 1d, preceding.
Example 4d The procedure of the preceding example was employed and also the same chlorinated reactant. 65 grams of the material identified as 10 were mixed with 8 grams of pyridine. The mixture was heated at 110 to C. for approximately 5 hours. The reaction with pyridine takes place rather rapidly, although the products do not seem to be quite as soluble as in some other instances, as hereinafter noted.
Example 503 The same procedure was followed as in Example 4d, preceding, except that the 8 grams of pyridine were replaced by 18.5 grams of tri-N- butylamine. The product was heated at 120 C. for 8 hours. At the end of this time a slight odor of butylamine persisted in the sample, in-, dicating that there was still a very small proportion of unreacted amine present. The above experiments and additional experiments are summarized in the following table.
Ex Epichloro.- Amt. Amt. Time of Deriv. Used Tertiary Amine Used Used gg Reaction Ex. No. Grams Grams so Hours 1c W 65 Dimethyldodecylamine 21. 3 140 6 1c 1 130 Benzyldimethylamine 27. 140 1c 65 32. 0 110 3% 1c 65 8. 0 120 5 1c 65 18. 5 120 8 146 26. 6 110 7 20 146 17. 0 100 1 2c 58 6. 0 120 2 2c 58 Pyridine 39. 0 100 4 2c 58 Tri-N-butylamlne 9. 3 100 3% 3c 142 Dodecyl dimethylamine. 21. 3 140 4% 31: 142 Benzyldimethylamine. 13. 5 120 3 142 Alpha picoliue 9. 3 120 2 30 142 Opeedma 1 32. 1 100 6% 30 142 Dietliylcyclohexylamine. l5. 5 100 5% 4: 129 9-Octadecenyldimethylaminc 29. 5 100 8 40 129 Pyridine 7. 9 135 3 4c 129 Benzyldimethylmnine... 13. 5 150 3 do 129 Dimethylaniiine 12. l 150 6 is 129 Methyl morpholine 13. 8 130 1 5c 82 Pyridine 2. 4 130 5c 82 4. 7 130 1 5c 82 11. 9 130 1 5c 82 27. 8 120 3% 5c 82 Dodecyldimethyiamiue 32. 0 155 3% 6!: 95.8 Pyrid ne 2. 4 130 1% 6c 95.8 Pyridine. 4. 74 135 1 6c 95. 8 Pyridine. 23. 7 130 1% 6c 95. 8 Opeedma 38. 4 110 2% 6c 95. 8 Dimcthyl Aniline 15. 5 150 6% 7c 129 Pyridine 7. 9 130 4 108. 5 Pyridine l l 4. 9 145 1 8c 108. 5 Benzyldimethylamine. 8. 4 135 1% 8c 1118. 5 Tri-N-butylamine 11. 6 120 3% 80 108. 5 N methyl Morpholine. 9. 8 140 2 8c 91 Opeedma 1 l. 17. 7 140 5% 9:: 101 Pyridin I 8. 7 100 1 9a 101 N-methyl Morpholin l1. 1 80 1 9a 101 4. 0 120 8% 101 35.0 140 1 10!: 107 7. 9 130 5 10c 107 21. 0 130 7 10 107 85. 3 125 4 107 26. 9 100 2 101 40. 0 130 3 110 101 9. 9 135, 2 110 101 19. 4 140 i 8% 11 101 12. 6 140 5 lie 101 1. 6 140 3% 108 Opeedma 46. 0 140 5% 13 110 Opeedma es 4% 130 110 Amine ES 76. 7 140 4% 140 116 Opeedma l v 96. 0 7 151: 118 N -methy1 Morpholine 20. 2 120 3 V 1 Opeedma-Octylpheuoxyethoxyethyl Dimethylaminc.
such solvent can be eliminated in the customary 59 manner by distillation, and particularly vacuum distillation, under approximately 20 to 40 mm. of mercury at 130 to C. Our experience has been that reaction of a tertiary amine generally gives the product a reddish tint; in other words, the final product is apt to be reddishblack, deep red, or reddish-amber. The viscosity of the final product is apt to be greater than the initial materials from which it is obtained,
and it is apt to be a solid, or a sticky or tacky solid. These properties, of course, return to the product in absence of any solvent. We prefer, as a matter of convenience, to have enough solvent present or to add enough, so as to obtain a liquid material which can be handled easily. By and large, we prefer that the original resin be treated with ethylene oxide, rather than propylene oxide, or some other oxide, and we also prefer that at least 5 moles of ethylene oxide be introduced for each original phenolic nucleus. We have found that N-methyl morpholine and octylphenoxyethcxyethyl dimethylamine are particularly desirable reactants.
Pyridine and pyridine homologuesreact rapidly,
but our preference, when using these materials,
is to have at least 10 moles of ethylene oxide present per initial phenolic hydroxyl. As is noted, the products readily give water-soluble or water-dispersible compounds, for reasons which need not be enumerated, but particularly in light of the co-valency which appears between the quaternary nitrogen compound or radical and the chlorine atom or ion.
Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:
1. A quaternary ammonium compound derived by reaction between (1) a chloro-oxypropylat- 1 ed derivative-oi hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a diiunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionin which R is a hydrocarbon radicalhaving at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin'molecule at the phenolic hydroxyls of a pluralityof divalent radicals having the formula (R1O)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radi cals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; said chlorooxypropylated compounds being obtained by reaction with epichlorohydrin; and (2) a basic tertiary amine having not over 50- carbon atoms.
2. A quaternary ammonium compound derived by reaction between (1) a chloro-oxypropylated derivative of hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and (B) an oxyalkylation susceptible, fusible, organic solventsoluble, water-insoluble, phenol-aldehyde resin;
said resin bein derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula:
in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (R) n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to with the proviso that at least 2 ,functional group reactive toward said phenol;
said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula:
in which R is a hydrocarbonradical having at least 4 and not'more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxylakylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)n, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for eaciz phenolic nucleus; said chloro-oxypropylated compounds being obtained by reaction with epichlorohydrin; and with the further proviso that the hydrophile properties of the chloro-oxypropylated derivative, as well as the oxyethylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water; and (2) a basic tertiary monoamine having not over 50 carbon atoms.
4. A quaternary ammonium compound derived by reaction between (1) a chloro-oxypropylated derivative of hydrophide hydroxylated synthetic products; said hydrophile synthetic products being oxyethylation products of an oxyethylatiom susceptible, fusible, organic solvent-soluble water-insoluble; phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula:
in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H4O)n; and n is a numeral varying from 1 to 20; with the proviso that more than 4 moles of ethylene oxide be introduced for each phenolic nucleus; said chloro-oxypropylated compounds being obtained by reaction with epichlorohydrin on the equimolar basis of one mole of the epoxy compound for each phenolic hydroxyl originally present; and with the further proviso that the hydrophile properties of the chloro-oxypropylated derivative, as well as the oxyethylated resin, in an equal weight of xylene are sufiicient to the produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water; and (2) a basic tertiary monoamine having not over 50 carbon atoms.
5. The product of claim 4, wherein the amine is acyclic.
6. The product of claim 4, wherein the amine is aliphatic and has less than 30 carbon atoms.
7. The product of claim 4, wherein the amine is aliphatic and has less than 30 carbon atoms. and R is substituted in the para position.
8. The product of claim 4, wherein the amine is aliphatic and. has less than 30 carbon atoms, and R is a butyl radical substituted in the para position. v
9. The product of claim 4, wherein the amine is aliphatic and has less than 30 carbon atoms, and R is an amyl radical substituted in the para position.
10. The product of claim 4, wherein the amine is aliphatic and has less than 30 carbon atoms,
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,076,624 De Groote Apr. 13, 1937 2,499,365
De Groote Mar. '7, 1950