Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/40—Two or more oxygen atoms
• • 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
• • 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
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
  • Y10T442/277—Coated or impregnated cellulosic fiber fabric

Definitions

• This invention relates to the appliction of 4,5-bis(all oxy)-2-imidazolidinones and their methylol derivatives, to a textile fabric.
• the new 4,5-bis(alkoxy)-2-imidazolidinones which are of great use as the raw materials of various synthetic resins such as resins for finishing a textile fabric, resins for treating paper, and fixing agents for pigment resin colour printing paste and as intermediates for the synthesis of various organic compounds, obtained by reacting 4,5-dihydroxy-2-imidazolidinone with aliphatic lower alcohol containing from 1 to 5 carbon atoms, in an acidic medium, are disclosed and claimed in copending application, Serial No. 13,451, filed by some of the present coapplicants.
• the new and valuable condensation products are obtained by reacting 4,5-bis(alkoxy)-2-imidazolidinone with formaldehyde or substances which split olf formaldehyde, in an acidic or neutral region, as disclosed and claimed in copending application, Serial No. 101,678, of some of the present co-applicants.
• the methylol derivatives of 4,5-bis(alkoxy)-2-imidazolidinone obtained by the said method show superior usefulness in treating textile fabric, paper and the like or in fixing of pigment resin colour printing paste.
• the textile fabrics treated with the latter resinous products have, on the one hand, indeed more superior characteristics in the respects of crease proof and resistance to shrinkage than is the case with the conventional resins such as dimethylol ethylene urea, but on the other hand, the treated goods have such defects that their tensile strengths are considerably lower than is the case with the conventional resins. Because of this fact, the practical usages of the methylol compounds of 4,5-dihydroxy-2-irnidazolidinone have been limited.
• the textiles treated with the compounds according to this invention not only have such characteristics that the crease proof and resistance to shrinkage thereof are of almost the same degree with that of the case With the methylol derivatives of 4,5-dihydroxy-2-imidazolidinone, but also have such characteristics that negligible .loss in tensile strength of the treated fabrics is observed. Consequently, the new condensation products of this invention are very valuable in an industrial application.
• the 4,5-bis(alkoxy)-2-imidazolidinones are obtained by reacting 4,5-dihydroxy-2- imidazolidinone with an aliphatic alcohol containing from 1 to 5 carbon atoms, in acidic media, and the methylol derivatives of said 4,5-bis(alkoxy)-2-imidazolidinones are obtained by reacting the latter with formaldehyde or substances which split off formaldehyde, in an acidic or neutral region.
• the reactions may be represented by the following scheme.
• R is an alkyl radical containing 1-5 carbon atoms.
• the alkyl-etherification reaction of 4,5-dihydroxy-2- imidazolidinone with an aliphatic lower alcohol can be carried out smoothly in an acidic region to give 4,5-bis- (alkoxy)-2-imidazolidinonc in good yield.
• the aliphatic lower alcohol works as not only the reaction component, but also the reaction medium.
• the amounts of aliphatic lower alcohol in practicing the reaction are in excess of rather than the theoretical amounts. Practically, from 3 to 10 mols of aliphatic lower alcohol may be adequatcly employed per mol of 4,5-dihydroxy-2-imidazoli dinone. There is, however, absolutely no adverse effect when more increased amounts of the alcohol are employed than the above limitation.
• the method in which the aliphatic lower alcohol per se serves as the reaction medium has another advantage such that, when the reaction is over, the filtrate obtained by the separation of 4,5-bis(all oxy)-2-imidazolidinone can be recovered and re-used as the raw material of the next batch.
• other reaction media such as, for example, others, may be successfully employed.
• the dehydration condensation of 4,5-dihydroXy-2-imidazolidinone with aliphatic lower alcohol can be carried out smoothly in an acidic region and particularly the reaction can be carried out almost quantitatively in a pH of less than 3.
• the said pH value is. measured by glass electrode pH meter.
• the acidifying agent such inorganic acids as hydrochloric, sulfuric and phosphoric acid and such organic acids as formic and oxalic acid may be advantageously employed.
• reaction temperature of the said alkyls etherification it may be adequately chosen from the temperature range of 0 C. to the boiling point of the said reaction mixture, but in order that the said. reaction may proceed smoothly, a temperature range of from 60 to 65 C. is preferable.
• the reaction time is correlated with the reaction temperature. In case the reaction temperature is from 60 to 65 C., the reaction is completed in about 30 minutes to 1 hour.
• the mixture thus obtained shows the heterogeneous state. But when the mixture is further admixed with an acidifying agent and the combined mixture is heated to a temperature of 60 to 65 C. with stirring for a while, the homogeneous state is gradually observed and finally a perfect transparent solution can be obtained. In this step of the reaction, the 4,5-bis(alkoxy)-2-imidazolidinone is being formed as the alcoholic solution thereof.
• reaction conditions do not particularly vary depending upon the employed aliphatic lower alcohol, but the lower the number of carbon atoms of the aliphatic alcohol, the more rapidly the reaction is carried out to give the homogeneous and transparent reaction mixture.
• the reaction mixture When the reaction is over, the reaction mixture is cooled and allowed to stand to precipitate the white crystals of 4,5-bis(alkoxy)-2-imidazolidinone.
• the filtrate may be used repeatedly as the raw material of the next batch reaction. But if the filtrate is subjected to further concentration, the second crystals of the product can be obtained.
• the combined amounts of the first and the second crystals are normally equivalent to the yield of 90% based on the theoretical amounts.
• the 4,5-dihydroxy-2-imidazolidinone and the aliphatic lower alcohol are introduced continuously into the same reaction vessel at the supplying ratio of 1 mol to from 3 to mols, the contents of the said reaction vessel are heated with sufiicient stirring and controlled to be held at the definite acidity by using pH meter, after a certain period of time the reaction mixture i taken out continuously through such means as over-flowing system and the mixture thus discharged is cooled to obtain the object crystals of 4,5-bis(alkoxy)-2-imidazolidinone.
• the filtrate thus obtained may be continuously sent with the fresh raw material into the said reaction Vessel and may be used again. According to the continuou manufacturing method, it is quite possible to obtain the object product more efficiently than with the batch system.
• reaction time in the continuous process is determined in I correlation with the employed reaction temperature, but as an adequate condition in practice, for example, it is preferable to determine the holding time as from 20 to minutes in case the reaction temperature is from 60 to 65 C.
• the 4,5-bis(alkoxy)-2-imidazolidinones used in the method of this invention are all new compounds, which have not yet been described in the literature, and their water solubilities depend upon the number of carbon atoms in the alkoxy radicals. That is, as the number of the carbon atoms of the alkoxy radical increase, the water solubilities decrease gradually.
• 4,5- bis(methoxy)-2-imidazolidinone is easily soluble in water
• 4,5- bis(butoxy)-2-imidazolidinone is hardly soluble in water.
• EXAMPLE 1 118.1 grams (1.0 mol) of 4,S-dihydroxy-Z-imidazolidinone were added to 160.2 grams (5.0 mols) of methanol, and to the mixture was added 0.4 gram of concentrated hydrochloric acid to adjust the pH to such point that glass electrode pH meter indicated about 0.2.
• the reaction mixture was charged into a 300 milliliters capacity four necked flask connecting with a reflux conwas allowed to cool, neutralized with a 40% aqeous sodium hydroxide solution, and the excess amounts of methanol distilled off at an inner temperature of about 30 C. under reduced pressure. Thus, the reaction solution was concentrated to about /3 of the original eight. During the course of the said concentration, the products were gradually precipitated as needle crystals.
• EXAMPLE 2 118.1 grams (1.0 mol) of 4,5-dihydroxy-2-imidazolidinone were added to 230.4 grams (5.0 mols) of ethanol, and to this mixture 0.5 gram of concentrated hydrochloric acid was added in order to adjust the pH of the mixture to such point that glass electrode pH meter indicated about 1.0.
• the reaction mixture was charged into a 500 milliliters capacity four necked flask connecting with a reflux condenser, and heated in a water bath. When the inner temperature of the reaction mixture was held at the range of from 60 to 65 C. with stirring, the heterogeneous reaction mixture gradually turned to a homogeneous state within 5 minutes and finally a slightly yellow, clear solution was obtained.
• EXAMPLE 3 59.0 grams (0.5 mol) of 4,S-dihydroxy-Z-imidazolidinone were added to 185.3 grams (2.5 mols) of nbutanol and to this 0.5 gram of concentrated hydrochloric acid was added in order to adjust the pH of the mixture to such point that glass electrode pH meter indicated about 2.0.
• the mixed raw materials were charged into a 300 milliliters capacity four necked flask connecting with a reflux condenser, and heated in a water bath. When the inner temperature of the said reactor was held at the range of from 60 to 65 C. with stirring, the heterogeneous reaction mixture gradually turned to a homogeneous state within 5 minutes and finally a red-orange, clear solution was obtained.
• the product had a melting point of from 103 to 104 C.
• reaction of 4,5-bis(alkoxy)-2-imidazolidinone with formaldehyde or substances which split ofi formaldehyde can be carried out usually by employing water as a reaction medium, but use can also be made of alcohols including methanol and ethanol, as Well as conventional organic solvents for the purpose of the present reaction medium.
• water is the most preferable reaction medium, and in usual case, the reaction of 4,5-bis(alkoxy)-2-imidazolidinone with formalin is considered to be the most practicable one.
• the hydroxymethylation'of 4,5-bis(all oxy)-2-imidazolidinone with formaldehyde can be carried out smoothly in the neutral or alkaline condition and particularly the reaction can be carried out extremely rapidly in a pH of more than 8.
• the reaction mixture turns gradually into a transparent solution as the hydroxymethylation proceeds, and finally waterwhite, clear solution is obtained.
• the alkalizing agent may be properly selected from the group consisting of alkali-metal hydroxides such as sodium and potassium hydroxide, alkaline-earth-metal hydroxides such as calcium and barium hydroxide and organic amines such as lower alkyl amines and lower alkylol amines.
• alkali-metal hydroxides such as sodium and potassium hydroxide
• alkaline-earth-metal hydroxides such as calcium and barium hydroxide
• organic amines such as lower alkyl amines and lower alkylol amines.
• the standard reaction condition is such that the time period of from about 30 minutes to 1 hour is adequate for the pH of 10 and reaction temperature of 35 C.
• the free formaldehyde content in the reaction mixture is measured by the conventional analytical method in the field of aminoplast chemistry. Furthermore, as the combined formaldehyde exists in the form of methylol group, it is possible to find out the end point of the reaction by measuring the amounts of methylol group by iodometric titration. As the result of these analytical methods, the products obtained by the described method have been ascertained to be the methylol derivatives of 4,5-bis(alkoxy)-2-imidazolidinone.
• these groups of resins have one or more undesirable tendencies in the properties; thus when fabrics are treated with these resins, bleached with a chlorine-containing bleaching agent and ironed, the treated fabrics have a tendency of yellowing or to be impaired in their tear strength, and when dyed fabrics are treated with these resins the treated dyeings have a tendency to be impaired seriously in their fastness to light.
• the treated fabrics When textile fabrics are treated with the methylol derivatives of 4,5-dihydroxy-2-imidazolidinone, the treated fabrics have, on the one hand, indeed, superior characteristics in the respect of crease-proof, resistance to shrinkage, the said chlorine resistance and fastness to light, but on the other hand, they have such defects, too, as the hard hand and extremely decreased tear strength. For that reason, the practical usages of the methylol derivatives of 4,5-dihydroxy-Z-imidazolidinone have been limited.
• the textile fabrics treated with the methylol derivatives of 4,5-bis(alkoxy)-2-imidazolidinone obtained by the method of this invention not only have such characteristics that the crease-proof, resistance to shrinkage and fastness to light thereof are of almost the same degree with that obtained with the methylol derivatives of 4,5-dihydroxy-2-imidazolidinone hereinabove described, but also have such superior characteristics that the treated fabrics have almost the same degree of soft hand as that of the original textile fabrics and no decrease in the tear strength is observed therein.
• the abilities of the treated fabrics can be acaatea freely changed in various ways by selecting the chain length of the two alkyl groups in the methylol derivatives of 4,5-bis(alkoxy)-2-imidazolidinone to be employed.
• the methylol derivatives of 4,5-bis(methoxy) -2-imidazolidinone give high wrinkle-resistant properties to the treated fabrics with but little loss of mechanical strength
• the methylol derivatives of 4,5-bis(nbutoxy)-2-irnidazolidinone renders the fabrics crease-resistant with full hand.
• combined effects of respective components are realized in case of mixed formulation.
• the methylol derivatives employed according to this invention are generally very stable in the lapse of time and even in the resin bath containing a curing catalyst the stabilities of the compounds are not influenced.
• the curing catalysts utilized in the present invention may be selected from the conventional groups of acidic catalysts, for example, either inorganic salts such as zinc nitrate, magnesium chloride, ammonium phosphate and ammonium sulfate, or organic salts such as the mineral acid salts of 2-amino-2-rnethylpropanol-1 and ethanol amine.
• inorganic salts such as zinc nitrate, magnesium chloride, ammonium phosphate and ammonium sulfate
• organic salts such as the mineral acid salts of 2-amino-2-rnethylpropanol-1 and ethanol amine.
• the curing temperature and time which are commonly employed in the treatment of textile fabrics are successfully utilized. For instance, to 10 parts of the resin solution of this invention (concentration of 50%) are added 2 parts of a zinc nitrate aqueous solution (concentration of 30%) and to this, sufiicient quantities of water are added to make the total volume 100 parts.
• cotton broadcloth fabrics 40s are dipped and the fabrics are nipped to give a wet pick-up of from 65 to 68%.
• the impregnated fabrics are subjected to pro-drying at a temperature of 105 C. for 2 minutes, and then heated at a temperature of 140 C. for 5 minutes. Thereafter, the fabrics are subjected to soaping with 0.2% of soda ash and 0.2% of soap at a temperature of 45 C. Upon drying, the treated fabrics have permanent crease-resistance.
• EXAMPLE 5 To 162 grams (2.0 mole) of 37% formalin, about 1 gram of a 40% sodium hydroxide aqueous solution was added to adjust the pH of the solution to and the solution was poured into a 500 milliliters capacity three necked flask. To this, 146 grams (1.0 mol) of crystalline 4,5-bis(methoxy)-2-imidazolidinone were added and the mixture was stirred. The heating and stirring were continued for 1 hour at a temperature of 35 C., thereafter the solution was neutralized with concentrated hydrochloric acid and 94 grams of water added. Thus, 403 grams of a 50% 1,3.-dimethylol-4,5-bis(methoxy)-2- imidazolidinone aqueous solution was obtained.
• EXAMPLE 6 To 162 grams (2.0 mols) of 37% formalin, about 1 gram of a 40% sodium hydroxide aqueous solution was added to adjust the pH of the solution to 10 and the solution was poured into a 500 milliliters capacity three necked flask. To this, 174 grams (1.0 mol) of crystalline To 162 grams (2.0 mols) of 37% formalin, about 1 gram of a 40% sodium hydroxide aqueous solution was added to adjust the pH of the solution to 1,0, and the solution was poured into a liter capacity four necked flask.
• EXAMPLE 8 To a mixture of 64 grams (2.0 mols) of methanol and 100 grams of water, about 2 grams of concentrated hydrochloric acid were added to adjust the pH of the solution to 1.5 and the mixture was poured into a 500 milliliters capacity three necked flask. To this mixture, 118 grams (1.0 mol) of 4,5-dihydroxy 2 imidagolidinone in crystalline form were added and the mixture wasstirred. The heating and stirring were continued for 30 minutes at a temperature of 35 C., and thetranspare nt solution thus obtained was adjusted to a pH of 10 by adding about 4 grams of a 40% sodium hydroxide aqueous solution.
• EXAMPLE 9 The 50% resin solution obtained -by the method of Example 5 was divided into three portions of 7.5, 10 and 15 grams. To these liquids, 1.5, 2.0 and 3.0 grams of 30% zinc nitrate aqueous solutions were added respectively and each portion was diluted with water to a total volume of cc. Thus, three resin baths, A, B and C, were provided. Into the said resin baths, cotton broadcloth fabrics (40s) were dipped and the fabrics were nipped to give a wet pick up of 65%. Then the impregnated fabrics were subjected to the pre-drying ,at a temperature of C. for 2 minutes, then heated at a temperature of C. for 5 minutes. Thereafter, the fabrics were subjected to soaping with 0.2% of soap and 0.2% of soda ash. Such treated fabrics showed an increased chlorine resistance and superior crease resistant properties in each sample.
• a method for producing permanent crease-resistance in cellulosic textile fabric which comprises impregnating the fabric with an aqueous solution containing 1,3-dimethylol-4,5-bis(alkoxy)-2-irnidazolidinone of the general formula:
• 1,3-dimethylol-4,5-bis(alkoxy)-2-imidazolidinone is 1,3-dimethylol-4,5 -bis (methoxy) -2-imidazolidinone.

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

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• 1960
  • 1960-02-19 GB GB602060A patent/GB897757A/en not_active Expired
  • 1960-03-08 US US1342360 patent/US3029164A/en not_active Expired - Lifetime
  • 1960-03-12 DE DES72966A patent/DE1190425B/de active Pending
  • 1960-03-12 CH CH281660A patent/CH402875A/fr unknown

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