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US3925009A - Fatty group containing methylolated, polyoxyalkylene carbamates and textile materials softened by treatment therewith - Google Patents

Fatty group containing methylolated, polyoxyalkylene carbamates and textile materials softened by treatment therewith Download PDF

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Publication number
US3925009A
US3925009A US831756A US83175669A US3925009A US 3925009 A US3925009 A US 3925009A US 831756 A US831756 A US 831756A US 83175669 A US83175669 A US 83175669A US 3925009 A US3925009 A US 3925009A
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Prior art keywords
carbamate
carbon atoms
carbamic acid
group
carbamates
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US831756A
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Thomas F Rutledge
John D Zech
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Zeneca Inc
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ICI Americas Inc
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Priority to US831756A priority Critical patent/US3925009A/en
Priority to US831770A priority patent/US3897208A/en
Priority to JP4862270A priority patent/JPS4948295B1/ja
Priority to GB2749770A priority patent/GB1318564A/en
Priority to DE19702028115 priority patent/DE2028115A1/en
Priority to DE19702028352 priority patent/DE2028352A1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04—Polyester fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon

Definitions

  • the carbamates contain at 1,959,930 5/1934 Schmidt et al 260/404 least one oxyethylene group, at least one fatty group 97 573 3/1934 s u et 260/404 and at least one carbamate group.
  • the carbamates are 2,002,613 5/1935 Orthner et 1, 260/404 useful as textile treating agents or as intermediates for 2,157,362 5/1939 Valrich et a1.
  • 260/482 C the preparation of textile treating agents.
  • novel carbamates of this invention are carbamates of an ethylene oxide adduct selected from the group consisting of 1. an ethylene oxide adduct of a fatty acid containing from 12 to 28 carbon atoms,
  • a preferred class of carbamates of this invention are carbamates of ethylene oxide adduct selected from the group consisting of (5) and (6).
  • the carbamates of this invention contain at least one oxyethylene group, at least one fatty group containing from 12 to 28 carbon atoms, and at least one group wherein R and/or R, are hydrogen or methylol. Accordingly, the carbamates of this invention may be described as esters of carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and the above defined ethylene oxide adducts.
  • the carbamates wherein R, to R, are both hydrogen are useful as intermediates for the preparation of textile treating agents by reacting the carbamate with formaldehyde to introduce one or more methylol groups.
  • the carbamates of this invention wherein R and/or R are methylol are useful as textile treating agents which impart a durable and permanent softness to textile materials when applied thereto.
  • the carbamates of this invention may be prepared by reacting one or more of the ethylene oxide adducts described herein with urea or with an alkyl carbamate such as ethyl or methyl carbamate.
  • the reactions are illustrated by the following equations:
  • the reaction may be carried out by heating a mixture of urea or alkyl carbamate and an ethylene oxide adduct to a temperature in the range of from about 1 10C. to about 200C.
  • Catalysts such as heavy metal salts of weak organic acids, zinc chloride, cobalt chloride, lead acetate, cupric acetate, boron trifluoride, aluminum isopropoxide, dibutyltin dilaurate, and dibutyltin oxide may be used to shorten the reaction time and increase the yield.
  • the degree of carbamylation may be controlled by varying the amounts of ethylene oxide adduct and carbamylating agent used. For example, the reaction of three mols of urea with one mol of an ethylene oxide adduct containing six hydroxyl groups will result in the formation of a carbamate containing an average of three carbamate groups.
  • the carbamates of this invention may also be prepared by reacting an ethylene oxide adduct described herein with phosgene to form a chloroformic ester which then may be reacted with ammonia to give the carbamate.
  • Other methods for preparing the carbamates of this invention will be readily apparent to one skilled in the art.
  • the methylolated carbamates of this invention may be prepared by reacting the carbamate with formaldehyde, paraformaldehyde, or other convenient source of formaldehyde.
  • the ethylene oxide adducts which may be used to prepare the carbamates of this invention are known compounds.
  • the ethylene oxide adducts may be prepared by reacting ethylene oxide with the appropriate fatty alcohol, fatty acid, fatty amine, fatty amide, or ester of fatty acid and a polyol or by reacting a fatty acid with an ether of ethylene oxide and a polyol.
  • a preferred group of fatty alcoals may be represented by the formula ROH wherein is an alkyl group or an alkenyl group containing from Z to 28 carbon atoms.
  • Illustrative examples of such tty alcohols include dodecanol, dodecenol, tetradec- 1o], tetradecenol, hexadecanol, hexadecenol, octa- :canol, octadecenol, eicosanol, eicosenol, docosanol, )cosenol, tetracosanol, tetracosenol, hexacosanol, :xacosenol, octacosanol, and octacosenol.
  • Fatty acids which may be used to prepare the ethylie oxide adducts include saturated and unsaturated tty acids having from 12 to 28 carbon atoms.
  • a prerred group of fatty acids may be represented by the rmula ROH wherein R is an acyl group containing om 12 to 28 carbon atoms.
  • Illustrative examples of lCh fatty acids include lauric acid, myristic acid, palitic acid, margaric acid, stearic acid, oleic acid, aralldiC acid, behenic acid, lignoceric acid, cerotic acid, ontanic acid, lauroleic acid, myristoleic acid, palmiteic acid, oleic acid, linolenic acid, ricinoleic acid, limic acid, eicosenoic acid, docosenoic acid, and tetcosenoic acid.
  • Fatty amines which may be used to prepare the ethylle oxide adducts include primary or secondary, satuted or unsaturated amines containing at least one tty group having from 12 to 28 carbon atoms.
  • a prerred group of fatty amines may be represented by the rmula R R' NH wherein R is an alkyl or alkenyl group )ntaining from 12 to 28 carbon atoms and R is hydro- :n or an alkyl or alkenyl group containing from 1 to 3 carbon atoms.
  • Illustrative examples of such fatty nines include dodecylamine, hexadecylamine, octa- :cylamine, eicosylamine, pentacosylamine, dodecylamine, dioctadecylamine, N-methyl- )decylamine, N-ethyloctadecylamine, ARMEEN TD, RMEEN SD cocoamine, oleyl amine.
  • Fatty amides which may be used to prepare the ethylie oxide adducts include fatty amides having at least 1e fatty group containing from 12 to 28 carbon atoms.
  • preferred group of fatty amides may be represented the formula RNR'H wherein R is an acyl group con- .ining from l2 to 28 carbon atoms and R is hydrogen an alkyl or alkenyl group containing from 1 to 28 ll'bOI'l atoms.
  • Illustrative examples of such fatty ames include dodecanamide, hexadecanamide, oc- .decanamide, octadecenamide, eicosanamide, pen- .cosanamide, N-methyl-octadecanamide, n-stearyldroxystearamide, dodecenamide, N-oleyl- :tadecanamide, N-oleyl-pentadecenamide, and N uryl-stearamide.
  • Polyols which may be used to prepare the ethylene tide adducts include polyols having from 3 to 6 caran atoms and from 2 to 6 hydroxyl groups.
  • a prerred group of polyols may be represented by the forula R(OH),, wherein R is an aliphatic group having om 3 to 6 carbon atoms and m is from 2 to 6.
  • Illustrave examples of these polyols include propylene glycol, :xamethylene glycol, butanediol, isosorbide, isoman- .de, glycerine, hexanetriol, pentaerythritol, erythritol, )lbilfil'l, mannitan, sorbitol, mannitol, dulcitol, guertol, inositol, and arabitol.
  • novel carbamates of this invention may be char- :terized by a formula selected from the group consistg of the following generalized formulae wherein idencal symbols have identical signification:
  • R is an alkyl group containing from 12 to 28 carbon atoms, an alkenyl group containing from l2 to 28 carbon atoms, an acyl group containing from 12 to 28 carbon atoms, or the group resulting from removing a hydroxyl group from lanolin,
  • R is hydrogen or CH,OH
  • R is hydrogen or -CH OH
  • n is an integer from 1 to 150
  • R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
  • x is an integer from 2 to 6
  • each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from l2 to 28 carbon atoms, acyl groups containing from l2 to 28 carbon atoms,
  • R is hydrogen, an acyl group containing from 12 to 28 carbon atoms, or
  • At least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms
  • at least one A contains a -(-CH,C- H 0) R group
  • at least one A contains R is an alkyl group containing from 12 to 28 carbon atoms, an alkenyl group containing from 12 to 28 carbon atoms, or an acyl group containing from l2 to 28 carbon atoms
  • each B is independently selected from the group consisting of alkyl groups containing from 1 to 28 carbon atoms, alkenyl groups containing from 1 to 28 caratoms, and -(-CH -CH,-O ⁇ ,, R wherein R is hydrogen or with the proviso that at least one B contains a 11 R 5 C N: I group,
  • Example 1 to 25 The following procedure is employed in Example 1 to 25.
  • the indicated amounts of urea and ethylene oxide adduct are charged to a three-necked flask and the contents of the flask heated to the indicated temperature for the indicated length of time.
  • the reaction product is filtered to remove any unreacted urea.
  • the filtrate is the carbamate of the starting ethylene oxide adduct.
  • the recovered carbamate is then mixed with a 37% aqueous solution of formaldehyde and heated to about 50C. for 10 to 12 hours to form the methylolated carbamate.
  • Examples 1 to 25 is followed in Examples 26 to 29 except that the indicated amount of ethyl carbamate is used instead of urea and a toluene azetrope is used to remove the liberated ethanol. grams of the indicated ethylene oxide adduct are employed in each example.
  • droxyl groups from an adduct of ethylene oxide and a partial fatty acid ester of a polyol having from 65 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from 12 to 28 carbon atoms.
  • the carbamates containing at least one methylol group may be used to treat textile material to impart thereto improved physical characteristics such as softness. It has been found that if the methylolated carbamates of the resent invention are applied to textile material along ith a textile resin catalyst for the methylolated carbaate and the textile material heated to an elevated mperature, the methylolated carbamate will be atmay be dipped into the liquid and the excess liquid extracted by centrifugation. In the spraying method of application, the fabrics are simply sprayed with an aqueous solution or dispersion of the carbamate and then .ched to the fiber so that the softening properties imdried by any suitable means.
  • methylolated carbamates applied to ashing or drycleaning.
  • the methylolated carbamates the textile material may vary over a wide range and will the present invention have been found to work well depend, mainly, on the degree of softness desired. Prefi cellulosic fibers. Although this invention is in no erably, the methylolated carbamates are applied to tex- :nse limited by theoretical considerations, the methyltile fabrics in amounts within the range of about 0.1% ated carbamates of the present invention are believed to about 5% by weight based on the dry weight of the I react with the treated cellulosic fibers during the fabric.
  • the heat cure of the textile fabric treated with the :tween the methylol groups of the carbamate and the methylolated carbamates may be effective at tempera ydroxyl groups of the cellulose.
  • the methyll5 tures from about 300F. to 350F. and in periods of ated carbamates are believed to react with the amino time ranging from about 10 to about minutes at the pups or the carboxyl groups present in wool, with the lower temperature to about 2 to 3 minutes at the higher rminal amino or carboxyl groups in nylon or the temperature.
  • the reaction may take place at lower nide groups therein having active hydrogen atoms, or temperatures if the curing time is extended.
  • the textile resin catalysts for the methylolated carbacation of two preferred methylolated carbamates of the ate may be any of the catalysts known in the art for present invention to fabric materials. It is understood, italyzing the reaction of methylol groups with active of course, that other methylolated carbamates may be ydrogen atoms of textile materials.
  • a preferred class readily substituted for those employed in the following :catalyst is the acid or latent acid catalysts. By latent examples.
  • :id catalysts is meant substances which develop acid- The following procedure is employed in Examples yduring the curing step. Particularly suitable catalysts and 31. Swatches of cotton poplin fabric are treated clude metal salts of strong acids such as magnesium with the indicated treating solution at 80% pickup on iloride, magnesium sulfate, zinc nitrate, and alumi- 30 the Butterworth Pad. The treated swatches contains 1% JlTl sulfate; ammonium salts such as ammonium chloof the indicated methylolated carbamate and 0.1% of de, ammonium dihydrogen phosphate, and ammothe zinc catalyst. The swatches are air dried at 200F.
  • the methylol- ;ed carbamates are applied to textile materials in the irm of aqueous dispersions thereof by conventional ethods.
  • the curing catalyst may be applied to the texle material along with the carbamate or from a sepaite bath.
  • the textile material may be treated with an queous dispersion of the carbamate by immersion ierein or by spraying.
  • the textile material may either be run through padding machine wherein the textile material is first ipped into the aqueous dispersion or solution of the arbamate and then squeezed, or the textile materials
  • this invention has been described with reference to specific reactant materials, including specific ethylene oxide adducts, carbamate agents, and methylolating agents, it will be apparent that still other different and equivalent materials may be substituted for those described.
  • application processes and reaction steps thereof may be modified within the spirit and scope of this invention.
  • R is an acyl group containing from 12 to 28 carbon atoms or the group resulting from removing a hydroxyl group from lanolin
  • R is hydrogen or CH OH
  • R is CH OH
  • n is an integer from 1 to 150
  • R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
  • x is an integer from 2 to 6
  • each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from 12 to 28 carbon atoms, acyl groups containing from 12 to 28 carbon atoms,
  • R is hydrogen, an acyl group containing from l2 to 28 carbon atoms, or
  • At least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms, at least one A contains a ⁇ CH CH 0- ⁇ , R, group, and at least one A contains a N group,
  • At least one B contains a group R is H or with the proviso that at least one R is y is a number from I to 5, and D is the group remain ing after removing all the hydroxyl groups from an adduct of ethylene oxide and a partial fatty acid ester ofa polyol having from 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from l2 to 28 carbon atoms.
  • a carbamate of claim 5 having the formula wherein R is an acyl group containing from 12 to 28 carbon atoms, n is an integer from l to 150, R is hydrogen or methylol, and R is methylol.
  • a carbamate of claim 5 having the formula wherein R is an alkyl group containing from 12 to 28 carbon atoms or an alkenyl group containing from l2 to 28 carbon atoms,
  • each B is independently selected from the group consisting of alkyl groups containing from 1 to 28 carbon atoms, alkenyl groups containing from I to 28 carbon atoms, and ⁇ Cl-l Cl-l O-,, R wherein R is hydrogen or 0 I ate Z,
  • a carbamate of claim 5 having the formula (R ,D wherein R is H or with the proviso that at least one R is y is a number from 1 to 5,
  • D is the group remaining after removing all the hydroxyl groups from an adduct of ethylene oxide and a partial fatty acid ester of a polyol having from 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from 12 to 28 carbon atoms, R is hydrogen or methylol, and R is methylol.
  • a carbamate of claim 5 having the formula R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
  • x is an integer from 2 to 6
  • each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from 12 to 28 carbon atoms, acyl groups containing from 12 to 28 carbon atoms,
  • N/ l 12 with the proviso that at least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms, at least one A contains a CHgC' fi -0 ⁇ R group, and at least one A contains a I -E-N group,
  • R is hydrogen or methylol, and R is methylol.
  • a carbamate of claim 9 having the formula R (OA) wherein R is the group remaining after removing all the hydroxyl groups from sorbitol, A is independently selected from the group consisting of hydrogen,
  • R is hydrogen, an acyl group containing from 12 to 28 carbon atoms, or
  • a process of treating textile material containing cotton and nylon which comprises depositing a carbamate of claim 5 and an acidic textile resin catalyst on the surface of the textile material and thereafter curing by heating the textile material to an elevated temperature.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Carbamates are disclosed which are esters of carbamic acid, Nmethylol carbamic acid, or N,N-dimethylol carbamic acid and an ethylene oxide adduct of a fatty acid, fatty alcohol, fatty acid ester of a polyol, fatty amine, or fatty acid amide. The carbamates contain at least one oxyethylene group, at least one fatty group, and at least one carbamate group. The carbamates are useful as textile treating agents or as intermediates for the preparation of textile treating agents. Process of treating textiles and textiles having improved properties are disclosed.

Description

United States Patent 1191 Rutledge et a1. 1 1 Dec. 9, 1975 15 FATTY GROUP CONTAINING 2,518,267 8/1950 Baird 6161. 260/4045 METHYLOLATED POLYOXYALKYLENE 2,585,826 2/1952 Olsen 260/482 13 44 1961 s 1., 260/482 (3 CARBAMATES AND TEXTILE MATERIALS 2/1969 40:1 :31.? 1 1 1 260/4045 SOFTENED BY TREATMENT THEREWITH 3,524,876 8/1970 Gregson 8/187 [75] Inventors: Thomas Rutledge; JOhII D. Zech, both of Wilmington, Del.
697,315 9/1953 United Kingdom [73} Assignee: lCl United States, lnc., Wilmington, 1,123,677 8/1968 United Kingdom 8/1163 Del. 1,128,812 10/1968 United Kingdom 610,393 12/1960 Canada [22] Filed: June 9, 1969 O R PUBLICATIONS THE [21] Appl. No.: 831,756
Marsh, Crease Resisting Fabrics, Reinhold, New York, 1962, p. 135. [52] [1.5. CI. 8/l15.7; 8/1155; 8/115.6', Robinette American Dyestufl Reporter, December,
260/482 C 4 g 51 Int. 01. ..C07C125/04;C07C 125/06; 57'1"" fgT"f DO6M 5/54; DO6M 3H6 sslsmn .ram1mr.. annon [58] Field of Search 8/115.5, 115.6, 116.3, 1 1 ABSTRACT 8/1276, 128 R, 115.7; 260/294 R, 40 Carbamates are disclosed which are esters of carbamic 482 B, 432 C acid, N-methylol carbamic acid, or N,N-dimethy1o1 carbamic acid and an ethylene oxide adduct of a fatty References Cited acid, fatty alcohol, fatty acid ester of a polyol, fatty UNlTED STATES PATENTS amine, or fatty acid amide. The carbamates contain at 1,959,930 5/1934 Schmidt et al 260/404 least one oxyethylene group, at least one fatty group 97 573 3/1934 s u et 260/404 and at least one carbamate group. The carbamates are 2,002,613 5/1935 Orthner et 1, 260/404 useful as textile treating agents or as intermediates for 2,157,362 5/1939 Valrich et a1. 260/482 C the preparation of textile treating agents. Process of 2.184.003 12/1939 D k y a1 y y y 4 0/ C treating textiles and textiles having improved proper- 2,197,479 4/1940 Meigs 260/482 0 ties are disclosed 2,218,939 10/1940 Steindorf 1 260/482 C 2,477,346 7/1949 Pikl 260/482 C 12 Claims, N0 Drawings FATTY GROUP CONTAINING METHYLOLATED, POLYOXYALKYLENE CARBAMATES AND TEXTILE MATERIALS SOFTENED BY TREATMENT THEREWITH This invention relates to novel carbamates. More particularly, this invention relates to novel carbamates which are useful as textile treating agents or as intermediates for the preparation of textile treating agents. This invention further relates to a process of treating textile material and to textile material having improved properties.
It is an object of this invention to provide novel carbamates.
It is another object of this invention to provide carbamates which are useful as intermediates for the preparation of textile treating agents.
It is another object of this invention to provide carbamates which are useful as textile treating agents.
It is another object of this invention to provide carbamates for application to textile materials to impart softness thereto, which will adhere to the textile materials through numerous subsequent laundering, drycleaning or similar operations and maintain a relatively high degree of softness in such materials without reapplication thereto.
It is another object of this invention to provide a process of treating textile materials.
It is another object of this invention to provide textile material having improved properties.
Other objects and advantages of this invention will be apparent from the following description and appended claims.
The novel carbamates of this invention are carbamates of an ethylene oxide adduct selected from the group consisting of 1. an ethylene oxide adduct of a fatty acid containing from 12 to 28 carbon atoms,
2. an ethylene oxide adduct of a fatty alcohol containing from 12 to 28 carbon atoms,
3. an ethylene oxide adduct of a fatty amine containing from 12 to 28 carbon atoms,
4. an ethylene oxide adduct of an amide of a fatty acid containing from 12 to 28 carbon atoms,
5. an ethylene oxide adduct of a partial fatty acid ester of a polyhydric alcohol containing from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups, said fatty acid containing from 12 to 28 carbon atoms, and
6. a partial ester of a fatty acid containing from 12 to 28 carbon atoms and an adduct of ethylene oxide and a polyhydric alcohol containing from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups.
A preferred class of carbamates of this invention are carbamates of ethylene oxide adduct selected from the group consisting of (5) and (6).
The carbamates of this invention contain at least one oxyethylene group, at least one fatty group containing from 12 to 28 carbon atoms, and at least one group wherein R and/or R, are hydrogen or methylol. Accordingly, the carbamates of this invention may be described as esters of carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and the above defined ethylene oxide adducts. The carbamates wherein R, to R, are both hydrogen are useful as intermediates for the preparation of textile treating agents by reacting the carbamate with formaldehyde to introduce one or more methylol groups. The carbamates of this invention wherein R and/or R are methylol are useful as textile treating agents which impart a durable and permanent softness to textile materials when applied thereto.
The carbamates of this invention may be prepared by reacting one or more of the ethylene oxide adducts described herein with urea or with an alkyl carbamate such as ethyl or methyl carbamate. The reactions are illustrated by the following equations:
o i organic-OH HJVHNH, NH, organic- NH,
These two well-known methods of forming carbamates are described in detail in the article by Adams et al. published in Chemical Reviews, Volume 65, pages 567-602, 1965. The disclosure of this article is hereby incorporated into this application by reference. Briefly, the reaction may be carried out by heating a mixture of urea or alkyl carbamate and an ethylene oxide adduct to a temperature in the range of from about 1 10C. to about 200C. Catalysts, such as heavy metal salts of weak organic acids, zinc chloride, cobalt chloride, lead acetate, cupric acetate, boron trifluoride, aluminum isopropoxide, dibutyltin dilaurate, and dibutyltin oxide may be used to shorten the reaction time and increase the yield. The degree of carbamylation may be controlled by varying the amounts of ethylene oxide adduct and carbamylating agent used. For example, the reaction of three mols of urea with one mol of an ethylene oxide adduct containing six hydroxyl groups will result in the formation of a carbamate containing an average of three carbamate groups. The carbamates of this invention may also be prepared by reacting an ethylene oxide adduct described herein with phosgene to form a chloroformic ester which then may be reacted with ammonia to give the carbamate. Other methods for preparing the carbamates of this invention will be readily apparent to one skilled in the art. The methylolated carbamates of this invention may be prepared by reacting the carbamate with formaldehyde, paraformaldehyde, or other convenient source of formaldehyde.
The ethylene oxide adducts which may be used to prepare the carbamates of this invention are known compounds. U.S. Pat. Nos. 1,959,930; 1,970,578; and 2,002,613, the disclosures of which are hereby incorporated hereinto by reference, disclose the preparation of ethylene oxide adducts which may be used to prepare the carbamates of this invention. Briefly, the ethylene oxide adducts may be prepared by reacting ethylene oxide with the appropriate fatty alcohol, fatty acid, fatty amine, fatty amide, or ester of fatty acid and a polyol or by reacting a fatty acid with an ether of ethylene oxide and a polyol.
Fatty alcohols which may be used to prepare the eth= ylene oxide adducts include saturated or unsaturated straight or branched chain fatty alcohols having frBifl 2 to 28 carbon atoms. A preferred group of fatty alcoals may be represented by the formula ROH wherein is an alkyl group or an alkenyl group containing from Z to 28 carbon atoms. Illustrative examples of such tty alcohols include dodecanol, dodecenol, tetradec- 1o], tetradecenol, hexadecanol, hexadecenol, octa- :canol, octadecenol, eicosanol, eicosenol, docosanol, )cosenol, tetracosanol, tetracosenol, hexacosanol, :xacosenol, octacosanol, and octacosenol.
Fatty acids which may be used to prepare the ethylie oxide adducts include saturated and unsaturated tty acids having from 12 to 28 carbon atoms. A prerred group of fatty acids may be represented by the rmula ROH wherein R is an acyl group containing om 12 to 28 carbon atoms. Illustrative examples of lCh fatty acids include lauric acid, myristic acid, palitic acid, margaric acid, stearic acid, oleic acid, aralldiC acid, behenic acid, lignoceric acid, cerotic acid, ontanic acid, lauroleic acid, myristoleic acid, palmiteic acid, oleic acid, linolenic acid, ricinoleic acid, limic acid, eicosenoic acid, docosenoic acid, and tetcosenoic acid.
Fatty amines which may be used to prepare the ethylle oxide adducts include primary or secondary, satuted or unsaturated amines containing at least one tty group having from 12 to 28 carbon atoms. A prerred group of fatty amines may be represented by the rmula R R' NH wherein R is an alkyl or alkenyl group )ntaining from 12 to 28 carbon atoms and R is hydro- :n or an alkyl or alkenyl group containing from 1 to 3 carbon atoms. Illustrative examples of such fatty nines include dodecylamine, hexadecylamine, octa- :cylamine, eicosylamine, pentacosylamine, dodecylamine, dioctadecylamine, N-methyl- )decylamine, N-ethyloctadecylamine, ARMEEN TD, RMEEN SD cocoamine, oleyl amine.
Fatty amides which may be used to prepare the ethylie oxide adducts include fatty amides having at least 1e fatty group containing from 12 to 28 carbon atoms. preferred group of fatty amides may be represented the formula RNR'H wherein R is an acyl group con- .ining from l2 to 28 carbon atoms and R is hydrogen an alkyl or alkenyl group containing from 1 to 28 ll'bOI'l atoms. Illustrative examples of such fatty ames include dodecanamide, hexadecanamide, oc- .decanamide, octadecenamide, eicosanamide, pen- .cosanamide, N-methyl-octadecanamide, n-stearyldroxystearamide, dodecenamide, N-oleyl- :tadecanamide, N-oleyl-pentadecenamide, and N uryl-stearamide.
Polyols which may be used to prepare the ethylene tide adducts include polyols having from 3 to 6 caran atoms and from 2 to 6 hydroxyl groups. A prerred group of polyols may be represented by the forula R(OH),,, wherein R is an aliphatic group having om 3 to 6 carbon atoms and m is from 2 to 6. Illustrave examples of these polyols include propylene glycol, :xamethylene glycol, butanediol, isosorbide, isoman- .de, glycerine, hexanetriol, pentaerythritol, erythritol, )lbilfil'l, mannitan, sorbitol, mannitol, dulcitol, guertol, inositol, and arabitol.
The novel carbamates of this invention may be char- :terized by a formula selected from the group consistg of the following generalized formulae wherein idencal symbols have identical signification:
B 3) R -N \B and (3) 01.0),0 wherein R is an alkyl group containing from 12 to 28 carbon atoms, an alkenyl group containing from l2 to 28 carbon atoms, an acyl group containing from 12 to 28 carbon atoms, or the group resulting from removing a hydroxyl group from lanolin,
R, is hydrogen or CH,OH,
R is hydrogen or -CH OH,
n is an integer from 1 to 150,
R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
x is an integer from 2 to 6,
each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from l2 to 28 carbon atoms, acyl groups containing from l2 to 28 carbon atoms,
and 4cH, cH, o R,
wherein R is hydrogen, an acyl group containing from 12 to 28 carbon atoms, or
with the proviso that at least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms, at least one A contains a -(-CH,C- H 0) R group, and at least one A contains R is an alkyl group containing from 12 to 28 carbon atoms, an alkenyl group containing from 12 to 28 carbon atoms, or an acyl group containing from l2 to 28 carbon atoms,
each B is independently selected from the group consisting of alkyl groups containing from 1 to 28 carbon atoms, alkenyl groups containing from 1 to 28 caratoms, and -(-CH -CH,-O},, R wherein R is hydrogen or with the proviso that at least one B contains a 11 R 5 C N: I group,
R 1s H or E N \R2 with the proviso that at least one R is In order that those skilled in the art may better understand the nature and preparation of the carbamates of the present invention, the following examples are given. These examples are set forth solely for the purpose of illustration and any specific enumeration of details contained therein should not be interpreted as expressing limitations of this invention. All parts and percentages are by weight, unless otherwise stated.
The following procedure is employed in Example 1 to 25. The indicated amounts of urea and ethylene oxide adduct are charged to a three-necked flask and the contents of the flask heated to the indicated temperature for the indicated length of time. The reaction product is filtered to remove any unreacted urea. The filtrate is the carbamate of the starting ethylene oxide adduct. The recovered carbamate is then mixed with a 37% aqueous solution of formaldehyde and heated to about 50C. for 10 to 12 hours to form the methylolated carbamate.
EX. Grams of Grams of Temp. Time- Carbamate Methylol Number Ethylene Oxide Adduct Adduct Urea C. Hours Hydroxy Carbamate l Polyoxyethylene (4) lauryl alcohol 200 35.6 155 13 0.67 1.2 2 Dioleate of polyoxyethylene sorbitol 60 5.8 150 9 0.62 1.2 3 Polyoxyethylene (l5) castor oil 500 5.8 160 6 0.66 1.2 4 Polyoxyethylene (20) tall oil 200 13.4 160 9 0.6 1.2 5 Dioleate of Polyoxyethylene (20) glycerol 106 5.3 150-160 5 0.69 1.2 6 Polyoxyethylene (20) ether of lanolin 200 7.8 160 7 0.27 1.2 7 Monopalmitate of Polyoxyethylene (20) glycerol 200 21 2 1 15-160 7% 0.83 1.2 8 Polyoxyethylene ()-N-stearyl-12 hydroxystearamide 200 5.4 160 6% 0.42 1.2 9 Polyoxyethylene (20) ether of sorbitol monooleate 200 17 155-160 6% 0.64 1.2 10 Polyoxyethylene (30) stearic acid 200 10.4 160 4 0.51 1.2 1 l Polyoxyethylene (5) ARMEEN SD 100 26 155-165 6% 0.83 1.2 12 Polyoxyethylene (l4) cocoamine I00 16.6 150 5% 1 1.2 13 Polyoxyethylene (20) sorbitan monolaurate 100 33 150 7 l 1.2 14 Polyoxyethylene (20) sorbitan monostearate 100 27.6 150 5 0.95 1.2 is Dioleate of polyoxyethylene (20) sorbitol I00 15 150 7 0.8 12 I6 Polyoxyethylene (5) octadecylamine 100 24 150-160 12 0.6 [.2 l7 Polyoxyethylene (20) ARMEEN TD 100 19.8 155 6 0.6 1.2 18 Polyoxyethylene (25) hydrogenated castor oil 100 8.4 155 6 0.5 1.2 19 Polyoxyethylene (54) castor oil 100 6.6 I 7% 0.88 1.2 20 Polyoxyethylene (8|) castor oil 100 4.5 150-165 10 0.6 1.2 2! Polyoxyethylene (150) hydrogenated castor oil 100 3.2 155 6% 0.75 1.2 22 Polyoxyethylene (50) octadecylamine 100 6 150 12 0.77 1.2 23 100 24 170-175 6% 0.8 1.2 24 Polyoxyethylene (25) hydrogenated castor oil 100 5.6 155 7 0.53 1.7 25 Polyoxyethylene (25) hydrogenated castor oil 100 10.1 155 7 l 1.5
(I) Number of carbamate groups introduced (2) Number of N-methylol groups per carbamate group.
per hydroxy group in ethylene oxide adduct charged (by analysis for non-urea nitrogen).
(3) Prepared by reacting ethylene oxide with an aqueous sorbitol solution, and esterifying the reaction product with 2 mols of oleic acid per six equivalent of hydroxyl.
y is a number from 1 to 5, and D is the group remaining after removing all the hy- The procedure of Examples 1 to 25 is followed in Examples 26 to 29 except that the indicated amount of ethyl carbamate is used instead of urea and a toluene azetrope is used to remove the liberated ethanol. grams of the indicated ethylene oxide adduct are employed in each example.
Grams of Example Ethyl- Tem zerature Tirne- Carbamate' Methylol' Number Ethylene Oxide Adduct Carbamate C. Hours Hydroxy carbamate 26 Polyoxyethylene (5) octadecylamine 44.5 140 9.75 0.8 1.2 27 Polyoxyethylene (25) hydrogenated castor oil 1 3.3 6 0.9 1.2 28 Polyoxyethylene (20) sorbitan monlaurate 48.5 130 10% l 1.2 29 Polyoxyethylene (5) octadecylamine 44.5 12% 0.8 1.2
(1) Number of carbamate groups introduced per hydroxy group in ethylene oxide adduct.
(2) Number of N-methylol groups per carbamate group.
droxyl groups from an adduct of ethylene oxide and a partial fatty acid ester of a polyol having from 65 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from 12 to 28 carbon atoms.
In accordance with the present invention, the carbamates containing at least one methylol group may be used to treat textile material to impart thereto improved physical characteristics such as softness. It has been found that if the methylolated carbamates of the resent invention are applied to textile material along ith a textile resin catalyst for the methylolated carbaate and the textile material heated to an elevated mperature, the methylolated carbamate will be atmay be dipped into the liquid and the excess liquid extracted by centrifugation. In the spraying method of application, the fabrics are simply sprayed with an aqueous solution or dispersion of the carbamate and then .ched to the fiber so that the softening properties imdried by any suitable means. arted to the fabric will not be removed by subsequent The amount of methylolated carbamate applied to ashing or drycleaning. The methylolated carbamates the textile material may vary over a wide range and will the present invention have been found to work well depend, mainly, on the degree of softness desired. Prefi cellulosic fibers. Although this invention is in no erably, the methylolated carbamates are applied to tex- :nse limited by theoretical considerations, the methyltile fabrics in amounts within the range of about 0.1% ated carbamates of the present invention are believed to about 5% by weight based on the dry weight of the I react with the treated cellulosic fibers during the fabric. iring operation by means of a condensation reaction The heat cure of the textile fabric treated with the :tween the methylol groups of the carbamate and the methylolated carbamates may be effective at tempera ydroxyl groups of the cellulose. Similarly, the methyll5 tures from about 300F. to 350F. and in periods of ated carbamates are believed to react with the amino time ranging from about 10 to about minutes at the pups or the carboxyl groups present in wool, with the lower temperature to about 2 to 3 minutes at the higher rminal amino or carboxyl groups in nylon or the temperature. The reaction may take place at lower nide groups therein having active hydrogen atoms, or temperatures if the curing time is extended. Higher ith the end hydroxyl or carboxyl groups in polyester temperatures may also be employed. berS- The following examples are illustrative of the appli- The textile resin catalysts for the methylolated carbacation of two preferred methylolated carbamates of the ate may be any of the catalysts known in the art for present invention to fabric materials. It is understood, italyzing the reaction of methylol groups with active of course, that other methylolated carbamates may be ydrogen atoms of textile materials. A preferred class readily substituted for those employed in the following :catalyst is the acid or latent acid catalysts. By latent examples. :id catalysts is meant substances which develop acid- The following procedure is employed in Examples yduring the curing step. Particularly suitable catalysts and 31. Swatches of cotton poplin fabric are treated clude metal salts of strong acids such as magnesium with the indicated treating solution at 80% pickup on iloride, magnesium sulfate, zinc nitrate, and alumi- 30 the Butterworth Pad.The treated swatches contains 1% JlTl sulfate; ammonium salts such as ammonium chloof the indicated methylolated carbamate and 0.1% of de, ammonium dihydrogen phosphate, and ammothe zinc catalyst. The swatches are air dried at 200F. 1um thiocyanate; amine salts such as triethylamine hyfor 5 minutes and then cured at 325F. for 5 minutes. rochloride, and triethanolamine hydrochloride. The One half of the swatches are washed ten times in an aunount of curing catalyst for the methylolated carbatomatic washing machine using 0.2% detergent (TIDE) am will depend on the nature of the carbamate, texsolution at 60C. The swatches are dried in a clothes le material, and catalyst and on the curing temperadryer after each wash. The subjective hand rating and 1re and curing time. In general, satisfactory results tear strength values are then determined using standard .ay be obtained by using from about 0.05% to about textile laboratory testing procedures.
Subjective Hand Rating Warpwise Elmendort" Tear Strength (1b.) Example Treating Number Solution 0 Wash 10 Washes 0 Wash 10 Washes Control Water 3 .3 3.0 1.56 l .51
(l) The lower the numerical rating, the softer the fabric (2) ASTM D1424-59 (3) 96.13% of water plus 0.12% of Zn(NO,],.6H,O plus 3.75% ofthc methylolated carbamate of Example 2 (4) 97.98% of water plus 0.12% ofZn(NO,),.6H,O plus 2.9% ofthe methylolated carbamate ot'Exam' ple 21.
3%, preferably from about 3% to about 10%, by eight of catalyst based on the weight of methylolated irbamate.
Preferably, although not necessarily, the methylol- ;ed carbamates are applied to textile materials in the irm of aqueous dispersions thereof by conventional ethods. The curing catalyst may be applied to the texle material along with the carbamate or from a sepaite bath. The textile material may be treated with an queous dispersion of the carbamate by immersion ierein or by spraying. In the immersion method of aplication, the textile material may either be run through padding machine wherein the textile material is first ipped into the aqueous dispersion or solution of the arbamate and then squeezed, or the textile materials Although this invention has been described with reference to specific reactant materials, including specific ethylene oxide adducts, carbamate agents, and methylolating agents, it will be apparent that still other different and equivalent materials may be substituted for those described. Moreover, application processes and reaction steps thereof may be modified within the spirit and scope of this invention.
Having described the invention, what is desired to be secured by Letters Patent is:
1. An ester of (l) carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and (2) an ethylene oxide adduct of castor oil.
2. An ester of (1) carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and (2) an ethylene oxide adduct of hydrogenated castor oil.
3. An ester of l) carbamic acid or N-methylol carbamic acid, and (2) polyoxyethylene(25)hydrogenated castor oil.
containg from l2 to 28 carbon atoms.
5. A carbamate characterized by the formula B (3) R -N: or
wherein R is an acyl group containing from 12 to 28 carbon atoms or the group resulting from removing a hydroxyl group from lanolin,
R is hydrogen or CH OH,
R is CH OH,
n is an integer from 1 to 150,
R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
x is an integer from 2 to 6,
each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from 12 to 28 carbon atoms, acyl groups containing from 12 to 28 carbon atoms,
wherein R is hydrogen, an acyl group containing from l2 to 28 carbon atoms, or
with the proviso that at least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms, at least one A contains a {CH CH 0-}, R, group, and at least one A contains a N group,
with the proviso that at least one B contains a group, R is H or with the proviso that at least one R is y is a number from I to 5, and D is the group remain ing after removing all the hydroxyl groups from an adduct of ethylene oxide and a partial fatty acid ester ofa polyol having from 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from l2 to 28 carbon atoms.
6. A carbamate of claim 5 having the formula wherein R is an acyl group containing from 12 to 28 carbon atoms, n is an integer from l to 150, R is hydrogen or methylol, and R is methylol.
7. A carbamate of claim 5 having the formula wherein R is an alkyl group containing from 12 to 28 carbon atoms or an alkenyl group containing from l2 to 28 carbon atoms,
each B is independently selected from the group consisting of alkyl groups containing from 1 to 28 carbon atoms, alkenyl groups containing from I to 28 carbon atoms, and {Cl-l Cl-l O-,, R wherein R is hydrogen or 0 I ate Z,
with the proviso that at least one B contains a wherein R, is hydrogen or methylol, and wherein R is methyloL 8. A carbamate of claim 5 having the formula (R ,D wherein R is H or with the proviso that at least one R is y is a number from 1 to 5,
D is the group remaining after removing all the hydroxyl groups from an adduct of ethylene oxide and a partial fatty acid ester of a polyol having from 2 to 6 hydroxyl groups and from 3 to 6 carbon atoms, said fatty acid containing from 12 to 28 carbon atoms, R is hydrogen or methylol, and R is methylol.
9. A carbamate of claim 5 having the formula R is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups,
x is an integer from 2 to 6,
each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from 12 to 28 carbon atoms, acyl groups containing from 12 to 28 carbon atoms,
from l2 to 28 carbon atoms, or
O 1:. N/ l 12 with the proviso that at least one A contains an alkyl, alkenyl, or acyl group containing from 12 to 28 carbon atoms, at least one A contains a CHgC' fi -0} R group, and at least one A contains a I -E-N group,
R is hydrogen or methylol, and R is methylol. 10. A carbamate of claim 9 having the formula R (OA) wherein R is the group remaining after removing all the hydroxyl groups from sorbitol, A is independently selected from the group consisting of hydrogen,
or 4CH CH O) R, wherein R is hydrogen, an acyl group containing from 12 to 28 carbon atoms, or
with the proviso that at least one A contains an acyl group containing from 12 to 28 carbon atoms, at least one A contains a {CH,CH,O)-,, R group, and at least one A contains a 11. A process of treating textile material containing cotton and nylon which comprises depositing a carbamate of claim 5 and an acidic textile resin catalyst on the surface of the textile material and thereafter curing by heating the textile material to an elevated temperature.
12. An article of manufacture comprising textile material treated in accordance with the process of claim 11.
group.
sitar-u UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,925, 09
DATED December 9, 1975 INV ENTOR(S) Thomas F. Rutledge and John D. Zech It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line 4, "R to R should read R and R Column 3, line 60, "guercitol" should read quercitol Column 6, lines 22 & 56,"Carbamate "should readCarbamate Hydroxy Hydroxy Column 6, lines 22 & 56,"Methylol "should read-Methylol Carbamate Carbamate 9 1 Column 10, line 65, "-(-CH -CH -O -)-CN: should read 1' P 4 2" 'fn C g Signed and Scaled this Twenty-seventh Day Of September 1977 [SEAL] Arrest:
RUTH C. MASON LUTRELLE F. PARKER Arresting Qflicer Acting Commissioner of Patents and Trademarks

Claims (12)

1. An ester of (1) carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and (2) an ethylene oxide adduct of castor oil.
2. An ester of (1) carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and (2) an ethylene oxide adduct of hydrogenated castor oil.
3. An ester of (1) carbamic acid or N-methylol carbamic acid, and (2) polyoxyethylene(25)hydrogenated castor oil.
4. An ester of (1) carbamic acid, N-methylol carbamic acid, or N,N-dimethylol carbamic acid and (2) an ethylene oxide adduct of a secondary fatty amine containg from 12 to 28 carbon atoms.
5. A CARBAMATE CHARACTERIZED BY THE FORMULA
6. A carbamate of claim 5 having the formula
7. A carbamate of claim 5 having the formula
8. A carbamate of claim 5 having the formula (R5O)yD wherein R5 is H or
9. A carbamate of claim 5 having the formula R3(OA)x wherein R3 is the group remaining after removing all the hydroxyl groups from a saturated, aliphatic polyhydric alcohol having from 3 to 6 carbon atoms and from 2 to 6 hydroxyl groups, x is an integer from 2 to 6, each A is independently selected from the group consisting of hydrogen, alkyl groups containing from 12 to 28 carbon atoms, alkenyl groups containing from 12 to 28 carbon atoms, acyl groups containing from 12 to 28 carbon atoms,
10. A carbamate of claim 9 having the formula R3(OA)3 wherein R3 is the group remaining after removing all the hydroxyl groups from sorbitol, A is independently selected from the group consisting of hydrogen,
11. A PROCESS OF TREATING TEXTILE MATERIAL CONTAINING COTTON AND NYLON WHICH COMPRISES DEPOSITING A CARBAMATE OF CLAIM 5 AND AN ACIDIC TEXTILE RESIN CATALYST ON THE SURFACE OF THE RTEXTI MATERIAL AND THEREAFTER CURING BY HEATING THE TEXTILE MATERIAL TO AN ELEVATED TEMPERATURE.
12. AN ARTICLE OF MANUFACTURE COMPRISING TEXTILE MATERIAL TREATED IN ACCORDANCE WITH THE PROCESS OF CLAIM 11.
US831756A 1969-06-09 1969-06-09 Fatty group containing methylolated, polyoxyalkylene carbamates and textile materials softened by treatment therewith Expired - Lifetime US3925009A (en)

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GB2749770A GB1318564A (en) 1969-06-09 1970-06-08 Carbamates based on ethylene oxide adducts
DE19702028115 DE2028115A1 (en) 1969-06-09 1970-06-08 Textile treatment agents and methods for treating textiles
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US4197409A (en) * 1978-08-08 1980-04-08 Chevron Research Company Poly(oxyalkylene)aminocarbomates of alkylene polyamine
US4329240A (en) * 1979-07-02 1982-05-11 Chevron Research Company Lubricating oil compositions containing dispersant additives
US6113656A (en) * 1995-01-17 2000-09-05 Milliken & Company Method of dyeing low pill polyester
CN103214398A (en) * 2013-05-02 2013-07-24 浙江师范大学 Method for preparing carbamate

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DE2412217A1 (en) * 1974-03-14 1975-10-09 Bayer Ag URETHANE POLYOLS CONTAINING POLYALKYLENE OXIDE WITH SULPHONIC ACID GROUP (N)
US4353707A (en) * 1981-09-15 1982-10-12 The United States Of America As Represented By The Secretary Of Agriculture Textile finishing agents from reaction products of carbamates and glutaraldehyde
DE4006255A1 (en) * 1990-02-28 1991-08-29 Basf Ag CONDENSATION PRODUCTS SUITABLE AS EMULGATORS OF OIL-IN-WATER EMULSIONS
DE4101158C2 (en) * 1991-01-14 1994-06-23 Dainippon Ink & Chemicals Thermosetting reaction resin mixtures, use of the reaction resins according to the invention for the production of moldings and coatings
CN1375024A (en) * 1999-09-10 2002-10-16 内诺-特克斯有限责任公司 Durable finishing agent for textiles

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