Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
  • C08G12/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with carboxylic acid amides
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins

Definitions

• This invention relates to a novel class of aminoplasts, to their process of preparation and to their use as creaseproofiing agents on cellulosic textile materials. More particularly, it relates to poly(methylolamido) compounds containing at least one carboxy group, to their process of preparation, to their use on cellulosic textile materials and to the cellulosic textile materials so treated.
• A is the residue of a carboxylated organic amide
• X is selected from the group consisting of hydrogen, alkyl and a monovalent salt-forming atom or group
• R is selected from the group consisting of hydrogen, alkyl or -CH OR R is selected from the group consisting of hydrogen and lower alkyl
• m is a positive value of about 0.2 and larger, though preferably at least 1
• n is normally at least 2 but may be 1 when R is --CH OR N is nitrogen of the amide type
• m +n is equal to the valence of A.
• In is a positive value of about 0.2 and larger, though preferably a value of at least 1. It will be appreciated that the minimum value for m being about 0.2 and above is an average value, which may be obtained, for example, by mixing a compound where m is l with four parts of such a compound where m is zero. Obviously, the value of 0.2 might also refer to the average analytical value for (XOOC+ groups for any given given production batch of product.
• the invention further relates to the process of applying compounds of the formula above to cellulosic textile materials and to the textile materials so treated.
• the radial A may be varied widely.
• it may be a polycarbonyl radical having as a nucleus a group of atoms, either straight chain or cyclic, either homogeneous or heterogeneous, and either aliphatic or aromatic.
• groups of atoms are the trivalent radicals derived from alkanes, such as ethane, propane, butane and the like; cyclic alkanes such as cyclohexanes; aromatic hydrocarbons, such as benzene, toluene and the like.
• the radical A may be the nucleus of a triazine or pyrimidine.
• the nitrogen atoms in the compounds of Formula I are the amide type, i.e., in what will be referred to as type A compounds, they are part of a carboxamide (carbamoyl) group.
• -CO-N or they may be of the kind referred to as type B, where the nitrogen atom is part of groupings such as
• the carboxamide types are amides of carboxylic acids and include not only amides of the acetamide type, but also urea, cyclic ureas, urons, triazones, and the like.
• the second type, or type B are represented by aminotriazines and aminopyrimidines.
• Preferred type A compounds may be represented by the formula (HOOC D (CH CH CONHCH OH) where D, as in the case above, is a nucleus having avalence of at least 3, such as a nitrogen or a short-chain hydrocarbon residue, and m and n are as identified hereinabove.
• the preferred compounds may be represented by the formula 1. 2 /C ⁇ N N N wherein R is selected from the group consisting of hydrogen, alkyl, carboxyalkyl and --CH OR R is selected from the group consisting of hydrogen and alkyl; and R is selected from the group consisting of hydrogen, alkyl,
• carboxyalkyl and providing the molecule contains at least one carboXy group.
• Compounds of the general formula covering both type A and type B compounds of this invention and wherein R is hydrogen may be prepared by reacting an amide of the formula l a (X 0 O)mA(NH)n where R is selected from the group consisting of hydrogen and alkyl, with formaldehyde under acid, neutral or alkaline conditions, preferably under alkaline conditions.
• methylol compounds of Formula I or the formaldehyde condensates of the amides set forth in Formula II above may be alkylated by reacting with an alcohol and preferably lower aliphatic alcohols such as methanol, ethanol, propanol, butanol and the like in the presence of an acid. In this manner, compounds of Formula I wherein R is alkyl may be prepared.
• Compounds of Formula II which will produce products of type A include monocarboxy-dicarboxamides, dicarboxy-dicarboxamides, monocarboxy-tricarboxamides, and the like.
• Representative aliphatic, non-cyclic monocarboXy-dicarboxamides include 2,3-dicarbamoylpropionic acid (by carbamoyl is meant -CONH 2,4-dicarbamoyl-2- methylbutyric acid, 2,3-dicarbamoyl-3-methyl-4-phenylbutyric acid, 4,4-dicarbamoylbutyric acid, 2,4-dicarbamoyl-2-methylvaleric acid, 2,4-dicarbamoyl-2-ethy1hexanoic acid, 2,3-dicarbamoyl-3-phenyloctanoic acid, diamide of citric acid, diamide of tricarballylic acid, and the like.
• Representative aliphatic, non-cyclic dicarboxy-dicarboxamides include 2,3-dicarbamoylsuccinic acid, 2,3- dicarbamoyl 2 methylsuccinic acid, 2,4-dicarbamoyl-3- methylglutaric acid, 2,3-dicarbamoyl-3,4-dimethylglutaric acid, 2,4-dicarbamoyl-3-pentylglutaric acid, 4,4-dicarbamoylpimelic acid, 2,3-dicarbamoylmaleic acid, bis(carbamoylmethyl)malonic acid, bisQ-carbamoylethyl)malonic acid, bis(4-carbamoylbutyl)malonic acid, and the like.
• Representative aliphatic, non-cyclic monocarboxytricarboxamides include 2,4,4-tricarbamoylbutenoic acid, 2,5,5-tricarbamoyl-Z-pentenoic acid, 2,2-bis(2-carbamoylethyl)malona-mic acid, and the like.
• Representative aliphatic, non-cyclic carboxamides containing nitrogen in the nucleus include N-carbamoylmethyl-N-(2-carbamoyethyl)-3-aminopropionic acid, 3- bis[(2 carbamoylethyl)amino]propionic acid, 2 [bis(2- carbamoylethyl)aminoJpropionic acid, 2 [bis(2 carbamoylethyl)amino]succinic acid, 2,2-diureidoacetic acid, 2 [bis(2 carbamoylethyl)amino]butyric acid, 2-[bis(2- carbamoylethyl)amino]-3-methylbutyric acid, N,N-bis(2- carbamoylethyl)fumaramic acid, N,N-bis(2-carbamoylethyl)glutamic acid, N,N bis(carbamoylethyl) glycine, N,
• Representative aliphatic, cyclic carboxamides include 4- carboxymethyl-5-methyl-2-imidazolidinone, 4-(3-carboxypropyl)-5-methyl-2-imidazolidinone, 4 carboxy-Z-imidazolidinone, 4,S-dicarboxy-Z-imidazolidinone, 4-(6-carboxyhexyl)-2-imidazolidinone, 4-(17 carboxyheptadecyl)-5- methyl-Z-imidazolidinone, 4-carboxytrimethyleneurea, 4,5- dicarboxytrimethyleneurea, and the like.
• aromatic carboxamides include 1,2-dicarbamoyl 4,5 benzenedicarboxylic acid, tricarbamoylbenzenetricarboxylic acid, 2,5-dicarbamoylterephthalic acid, and the like.
• Compounds of Formula II which give products of type B include triazines and pyrimidines; all of the following compounds of type B, or their esters, are known.
• triazines include 2-carboxymethylthio- 4,6-diamino-s-triazine, 2-( l-carboxyethylamino) 4,6 diamino-s-triazine, 2-(3-carboxypropylamino)-4,6-diaminos-triazine, 2-(2-carboxyphenylamino) -4,6-diamino s triazine, 2-(2-carboxyphenyl)-4,6-diamino-s-triazine, 2 (1- carboxypropylthio -4,6-diamino-s-triazine, 2-( l-carboxyethylthio) 4,6-diamino-s-triazine, 2-carboxymethyl-4,6- diamino s triazine, 2 carboXym-ethyl 4,6 -diaminocarboxyoctyl)-4,6--
• Representative pyrimidines include 4-(carboxymethylthio)-2,6-diaminopyrimidine, 5-(p-carboxyphenyloxy)-2,6- diaminopyrimidine, 4-(2-carboxyethylthio) 2,6-diaminopyrimidine, S-carboxymethyl-6-methyl-2,4-diaminopyrimidine, 4-carboxy-2,6-diaminopyrimidine, and the like.
• a particularly preferred class of compounds coming within the scope of Formula I are those containing N-methylolated propionamide groups, i.e., CH CH CO-NHCH OH and, of course, one or more carboxy groups.
• Typical of such compounds are HOHO HOOC-OI-I2N(CH CH2CONHZ); (1)
• the compounds of Formula 4 set forth hereinabove may be prepared in a manner similar to that used for preparing those of 2, the starting material having the general formula (alky C)z(
• the amides may be methylolated in accordance with standard procedures and in aqueous solutions employing formaldehyde and preferably an alkaline reagent, as for example sodium or potassium hydroxide.
• the compounds of this invention may be applied to cellulosic textile material and, preferably, cotton fabric by any of the well known techniques, as for example spraying, dipping, immersing, padding and the like in such amounts as to apply from between 1 and about 25% and, in some instances, higher amounts of the composition of this invention, based on the dry weight of the fabric.
• the amount of reactant applied depends on the particular type of fabric being treated.
• the concentration of from 1 to about 25% and, preferably, from between 3 and 10% resin solids based on the dry weight of the fabric are utilized.
• the resinous composition is applied with a curing catalyst or accelerator.
• the catalyst utilized may be free acid, acid salts, alkanolamine salts, metal salts and the like.
• concentration of catalyst employed may range from about 0.1 to about 25 or higher, based on the weight of the reactant, depending upon the particular catalyst type employed.
• a free acid such as phosphoric, tartaric, oxalic or the like, may be employed, while in the case of ammonium chloride amounts of from between 0.5 and about 10% are used.
• amine salts including alkanolamine salts, such as diethanolamine hydrochloride
• alkanolamine salts such as diethanolamine hydrochloride
• salts such as magnesium chloride, zinc chloride, zinc nitrate, and aluminum chloride
• concentration of the catalyst is based on the weight of the resin solids employed.
• the material is subject to drying and curing operations to effect the properties of shrinkage control and wrinkle resistance.
• the drying and curing operation may be carried out in a single step or in separate steps.
• the temperatures at which the drying and curing operations are effective vary widely and are influenced to some extent by the type of catalyst employed. Normally, the range of temperature extends from about 180 F. to about 450 F. or even higher.
• the time of the drying and/or curing operation is inversely proportional to the temperature employed, and of course is influenced by whether or not separate or combined drying and curing steps are employed.
• a time of from about 1 minute to about minutes may be employed at temperatures from about 450 to 250 F., respectively.
• curing times of the order of 5 minutes to about A minute at a temperature of from between 250 and 450 F., respectively, have been successfully employed.
• EXAMPLE 2 Tetrakis [2- (N-methylolcarbamoyl) ethoxymethyl] methane C(CH OCH CH CONHCH OH) 4
• the pH of a reaction mixture comprising 119 parts of 44% Formalin (1.74 moles of formaldehyde), 120 parts of water and 150 parts (0.36 mole) of tetrakis(2- carbamoylethoxy)methane [product of Example 1(A)] at 50 C. is adjusted to 10.0 by adding about 4.5 parts of 50% aqueous sodium hydroxide. After 45 minutes, analysis for unreacted formaldehyde indicates that 3.92 moles of formaldehyde per mole of amide have reacted. The pH is then adjusted with nitric acid to about 7.5.
• Example 3 The product solution of Example 2 is applied to x 80 cotton percale at a 5% solids level (O.W.F.). The application is made by standard padding procedure from an aqueous pad bath of pH 4.0 containing 12% of magnesium chloride based on the resin solids. The treated fabric is dried at 225 F. for 1 minute and then heated at 350 F. for 1.5 minutes. The fabric is then process washed using warm water containing 1% sodium carbonate and 0.5% non-ionic surface active agent (condensation product of nonylphenol and about 9.5 moles of ethylene oxide) and dried at 225 C.
• non-ionic surface active agent condensation product of nonylphenol and about 9.5 moles of ethylene oxide
• the wrinkle recovery (total warp plus fill) of the treated and untreated fabrics is measured in degrees by Tentative Test Method 66-l959T of the American As sociation of Textile Chemists and Colorists.
• the tensile strength loss due to chlorine retention followed by scorching is measured by Standard Test Method 92-1962 of the American Association of Textile Chemists and Colorists.
• the strength loss due to chlorine retention is repeated after the fabrics are subjected to an acid stripping operation to simulate repeated commercial launderings wherein acid sours are employed.
• the fabric is immersed for 20 minutes in water at F. containing 5% of urea and 0.5% of phosphoric acid.
• the fabrics are then rinsed in water at 80 F., in 0.1% aqueous sodium carbonate at 80 F., in water again and finally press dried.
• EXAMPLE 5 (2-carboxyethoxymethyl -tris [2- (N-methylolcarb'amoyl)ethoxymethyl] methane HOOC-CH2CH2OCH2 C(CH2OCH2CH2CONHCH2OH)3
• the product solution of Example 5 is applied to 80 x 80 cotton percale at a 5% solids level (O.W.F.) by the procedure of Example 3, except for the curing of the finish which in this example is done at 350 F. for 1 minute.
• the treated fabric is tested by the procedures of Example 3. The results are shown in Table II.
• Example 8 The product solution of Example 7 is applied to X 80 cotton percale at a 5% level (O.W.F.) by the procedure of Example 6. The treated fabric is tested by the procedure of Example 3. The results are shown in Table III.
• EXAMPLE 9 Diethyl bis (Z-methylolcarb amoylethyl malonate (C H OOC) C(CH CH CONHCH OH 2
• EXAMPLE 10 The product solution of Example 9 is applied to white cotton broadcloth at two levels of application. A commercial melamine-formaldehyde-ethyleneurea-formaldehyde aminoplast textile finish is also applied for comparison.
• the finishes are applied from aqueous baths of pH 4 containing 12% magnesium chloride, based on the resin solids, by standard padding procedures.
• the treated fabrics are dried at 225 F. for 1.5 minutes and then heated at 350 F. for 1.5 minutes.
• EXAMPLE l2 Tetraethyl 1,7-dicarbamoyl-3,3,5,5- heptanetetracarboxylate
• tetraethyl l,7-dicyano3,3,5,S-heptanetetracarboxylate product of Example 11
• the reaction mixture is poured into a mixture of ice and water, and about 380 parts of 50% aqueous sodium hydroxide is added to neutralize the acid.
• the product is separated by extracting with a mixture of acetone and chloroform, evaporating the resulting solution until crystals form, and filtering off the crystals.
• the product after recrystallization from methanol, melts at 129130 C.
• EXAMPLE 13 Tetraethyl 1,7-(N-methylolcarbamoyl)-3,3,5,5-heptanetetracarboxylate (0211 0 0 C)2CCH2CHzC ONHCHzOH (021150 0 C)2CCHzCHzC ONHCH2OH
• a mixture of 120 parts of water 142 parts (0.3 mole) of tetraethyl 1,7-dicarbamoyl-3,3,5,5-heptanedicarboxylate (product of Example 12) and 61.5 parts of 44% Formalin (0.9 mole of formaldehyde) there is added 9 parts of 50% aqueous sodium hydroxide over 1.5 hours while maintaining a temperature of 4550 C. Analysis for reacted formaldehyde indicates that 2 moles of formaldehyde per mole of amide have reacted.
• EXAMPLE 14 The product solution from Example 13 is applied to 80 x 80 cotton percale at a 7.4% solids (O.W.F.) level. The application is made by normal padding procedures from an aqueous pad bath containing 12% magnesium chloride based on the amount of resin, and having a pH of 4.0. The fabric is dried and heated at 350 F. for 1.5 minutes.
• EXAMPLE 17 The pad bath contained 12% magnesium chloride based on the amount of resin used and had a pH of 4.0.
• the fabrics are subjected to five washes of 5 minutes duration in 0.05% aqueous solutions of zinc silicofluoride with hot pressing of the fabric for 30 seconds after each wash, except the final wash, which is followed by a water rinse at 72 F. and a hot pressing.
• EXAMPLE 21 The product solution from Example 20 is applied to 80 x 80 cotton percale at a 5.0% solids (O.W.F.) level.
• the application is made by normal padding procedures from an aqueous pad bath containing 12% magnesium chloride on the amount of resin, and having a pH of 3.8.
• the padded fabric is dried for one minute at 225 F.
• the fabric is then process washed to remove soluble salts and dried.
• the fabrics are dried at 225 F. for 2 minutes and then heated at 350 F. for 1.5 minutes.
• Citramic acid To a solution of 114 parts (0.6 mole) of citramide in 400 parts of water is added a solution of 4.8 parts of It should be noted that the acid stripping operation causes no loss in wrinkle recovery of the fabric treated with the product of this example in contrast to the high loss suffered by the triazone finished fabric. Further- 50 more, the loss in strength due to bleaching and scorching is much greater for the triazone finish than for the methylolated citramic acid finish.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Cited By (5)

Citations (10)

• 1964
  • 1964-07-07 US US380915A patent/US3465036A/en not_active Expired - Lifetime
• 1965
  • 1965-03-25 NL NL6503793A patent/NL6503793A/xx unknown
  • 1965-05-07 BE BE663637D patent/BE663637A/xx not_active Expired
  • 1965-05-12 ES ES0312835A patent/ES312835A1/es not_active Expired

Patent Citations (10)

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