US2923645A - Novel formyloxetanes and process of preparing same - Google Patents

Novel formyloxetanes and process of preparing same Download PDF

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US2923645A
US2923645A US787346A US78734659A US2923645A US 2923645 A US2923645 A US 2923645A US 787346 A US787346 A US 787346A US 78734659 A US78734659 A US 78734659A US 2923645 A US2923645 A US 2923645A
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formyloxetanes
alcohol
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fabric
textile
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Robert K Miller
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring 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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • 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
    • Y10S8/08—Oxirane

Definitions

  • Nurnerous agents are known in the art for treating of cellulose fibers to'impart dimensional stabilization.
  • nitrogenous resins of which dimethylolethylene urea 'is a good example.
  • nitrogenous resins .have the general disadvantage of retaining chlorine on bleaching thetreated fabric. This results in the cellulose fibers being damaged by a reduction of tensile strength after bleaching and ironing operations.
  • Another class of agents known in the art to impart dimensional stabilization to cellulose are aliphatic alde- ,hydes.
  • jIt is an object of the present invention to provide novel formyloxetanes which may be applied to cellulosic .fabrics to give a significant dimensional stability thereto.
  • the present invention is directed to compounds of the structure wherein R is a lower alkyl group and n is 0 or 1.
  • This invention also includes a process for preparing the novel formyloxetanes described, saidprocess comprising reacting a gaseous mixture of oxygen and an alcohol of thestruct'ure wh ereinR is a lower alkyl group and 'n is taken from the group consisting of zero and 1 at a temperature within the range of 200 to 600 C. in the presence of a de- I'hydrogenation' catalyst.
  • q ffIn addition it is part of the present invention to provide a process for imparting dimensional stability to cellulosic textiles by depositing on said textile, from an 2,923,645 Patented Feb. 2, 1960 'RCQ aqueous pad bath, between and 15% (on the weight of the textile) of a compound having the structure R-(OCHzh CHO Cg: CH:
  • R is a lower alkyl group and n is taken from the group consisting of zero and 1, and 0.1% to 2% (by weight of the textile) of zinc fluoroborate, drying the textile and curing it at to C. for 0.5 to 5 minutes.
  • novel compounds of the present invention include 3-formyl-3-methyloxetane which has the structure ous systems.
  • the formyloxetanes of the present invention are prepared by feeding oxygen and the alcohol oxetane utilized into a heated chamber (alcohol boiler) which serves to vaporize the alcohol.
  • a heated chamber alcohol boiler
  • the mixed vapors of alcohol and oxygen are then fed into a reaction chamber which contains the catalyst and which is held at a temperature between about 200 and 600 C.
  • the gaseous reaction products pass into a condenser and the liquid formyloxetane is fed into the product receiver.
  • the alcohol oxetanes are known and may be derived from pentaerythritol or 1,1,1-trihydroxymethylalkanes. These compounds are disclosed and their preparation given in French Patent 1,122,903.
  • the source of oxygen may be air or pure oxygen.
  • the catalyst may be selected from any of the wide variety of known. catalysts for vapor phase dehydrogenation of alcohols to aldehydes. These catalysts .include many metals and their compoundssuch as those of platinum, palladium, nickel, cobalt, copper, silver, gold,
  • the temperature of the reaction will in general vary between about 200 and 600 C. depending upon the particular catalyst employed. The relationship of temperature to catalyst is well known in the art as taught by the monograph referred to above. When the preferred catalysts of silver or copper chromite are used, the temperature of the reaction will be between about 300 and 400 C.
  • the amount of oxygen used in the process may vary widely, some oxidation (i.e. dehydrogenation) of alcohol to aldehyde occurring even without it. However, it is preferred to use oxygen in order to obtain improved yields and conversions and these are best obtained when the amount of oxygen employed is less than the theoreti- 3 calamount required for the oxidation to occur. Pref erably the amount used will be 10% to 40% of the theoretical amountrequired based on the alcohol oxetane taken according to the following equation:
  • aldehyde-oxetanes of this invention are readily applied to cellulosic textiles, e.g., cotton. Because of their water solubility or miscibility the agents are applied from aqueous pad baths and an amount'of agent between about 1% and about 15% on the weight of the fabric will be applied. Usually, a wet pick-up between about 75% and 100% will be used and the pad bath concentration wil be adjusted accordingly.
  • the padded fabric be cured after application to the textile.
  • the padded fabric will be air dried prior to the curing step in order to get crease resistance. In the absence of the air drying step, excessive loss of the agent from the textile seems to occur and no significant dimensional stabilization is obtained.
  • the air drying step will be carried out at room temperature or at elevated temperatures up to about 100 C. for a few minutes, the length of time 1 varying inversely with the temperature used. The cure eifects reaction of the aldehyde oxetane with the fabric and is accomplished simply by heating in the presence of a catalyst.
  • zinc fiuoborate is a suitable catalyst and yields a cured fabric having excellent durable crease resistant effects.
  • Other strongly acidic agents such as zinc perchlorate; zinc chloride, and citric acid catalyze the cure, but are much less eflicient than zinc fluoborate.
  • the amount of catalyst used will vary between 0.1% and 2% on the weight of the fabric, less giving poor crease resistance and more adversely affecting the tensile strength of the treated fabric.
  • the curing procedure is carried out over a period of about 0.5 to 5 minutes at temperatures between about 130 and 160 C., it being understood that at the higher temperatures, shorter times will be used.
  • the alcohol feed was dropped into a curved glasstube connected directly to a horizontal reaction tube.
  • This curved tube served as the alcohol boiler and was wrapped with an insulated electrical heating element.
  • a thermocouple placed next to the glass (under the heating element) was used to determine the boiler temperature
  • the reaction tube was a straight piece of copper tubing, 1.9 cm. OD. and approximately 100 cm. long.
  • Stainless steel, 28/ 15, male ball joints were silver soldered .at each end for interconnection with the other equipment.
  • the tube was heated with an insulated electrical heating element and surrounded with magnesia for thermal insulation.
  • the temperature of the reaction tube was measured by three thermocouples placed along the le gth of the tube, beneath the insulation and in contact with the outer wall of the tube.
  • the catalyst used was silver deposited on pumice and was prepared by the procedure described by R.R. Davies and H. H. Hodgson, J. Chem. Soc., 1943, p. 282. Its volume was approximately 200 ml.
  • 3-hydroxymethyl 3 methyloxetane (88.8 g., 0.870 mole) was fed to the boiler at the rate of 1.25 g./rnin. Dry air was introduced atthe rate of 120 mL/min. This air-alcohol ratio is such that the amount of oxygen used is 17.5% of that required by theory.
  • Theboiler temperature was maintained at 300 to 330 C and the center of the reaction tube at 330 to 340 C. Including volatile liquid condensed in the cold traps, 87.7 g. of crude product was obtained. By vapor phase chromatographic analysis, the crude product contained 34.9% 3-formyl-3-methyloxetane and 57.3% 3-hydroxymethyl- 3-inethyloxetane, the remainder being low boiling decomposition products.
  • the catalyst used was copper chromite supportedon pumice stones.
  • the copper chromite was prepared according to W. A. Lazier and H. R. Arnold (Organic Syntheses, coll. vol. II, John Wiley and Sons, Inc., New York (1943), p. 142), and deposited on the pumice as a paste with water. The lumps were loaded into the tube while damp, and dried by heating in a stream of nitrogen.
  • the catalyst zone was about 60 cm. in length, and was about 120 ml. in volume.
  • 3-ethoxymethyl-3-hydroxymethyloxetane (206 g., 1.41 moles) was fed to the boiler at the rate of 1.17 g./min. Dry air was introduced at the rate of 100 ml./ min. representing 22% of the theoretical amount of oxygen required.
  • the boiler temperature was maintained at 230- 240 C., and the center of the reaction tube at 310340 C. Including volatile liquid condensed in the cold traps, 192.2 g. of crude product'was obtained. Bytopping the crude product under vacuum in a simple-still, 49.6 g. of aldehyde rich fraction was obtained. This portion of the product was then distilled in an efiicient column at 5.0 mm. Hg to give a 7.2 g.
  • EXAMPLE 3 7 Application of 3-f0rmyl-3-methyloxetane tov cotton An aqueous pad bath was prepared to contain on the weight of the 'bath 16.2% of 3-formyl-3-methyloxetane and .675 of zinc fiuoborate. A piece of cotton fabric was padded at pickup on the weight of the fiber and the padded fabric air dried at 21 C. and 65% relative humidity. The treated fabric thus contained 13% of its weight of the aldehyde oxetane and 0.5% catalyst. Then the fabricwas cured at 137 C. for 84 seconds, after which it was evaluated for crease resistance, whiteness (i.e., reflectanceat 400 m and discoloration after chlorine bleaching. The results obtained showed a crease; recovery angle of,24-6, a high reflectance value of 85 and no discoloration after bleaching and exposure to a Fade- 1 Test method As'rM D-l295-53T.
  • any of the formyloxetanes of the present invention may be substituted in any of the preceding examples to give substantially the same results.
  • the various described catalysts may be substituted throughout the examples to give acceptable and significant results.
  • R is a lower alkyl group of from 1 to 4 carbon atoms and n is taken from the group consisting of 0 and 1.
  • a process for preparing formyloxetanes which comprises reacting a gaseous mixture of oxygen and an alcohol of the structure R- oom). 011,011
  • R is a lower alkyl group of from 1 to 4 carbon atoms and n is taken from the group consisting of 0 and l, at a temperature Within the range of 200-600 C. in the presence of a dehydrogenation catalyst.
  • a process for imparting dimensional stability to cellulosic textiles by depositing on said textile from an aqueous pad bath between 1 and 15% by weight of said textile of a compound having the structure R(OCH2)n CHO CH CH2 wherein R is a lower alkyl group and n is taken from the group consisting of 0 and 1, from 0.1 to 2% by weight of said textile of zinc fluoborate, followed by drying the treated textile and curing said textile at a temperature within the range of to C. from 0.5 to 5.0 minutes.

Description

United States Patent- NoVEL FoRMYLoXETANEs i RocEss OF PREPARING SAME.
Robert K. Miller, New Castle, DL, assignor to E. I. do Pout de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application January 19,1959 I Serial No. 787,346
6 Claims. (Cl. In -139.4)
... Nurnerous agents are known in the art for treating of cellulose fibers to'impart dimensional stabilization.
The most common of these agents are nitrogenous resins of which dimethylolethylene urea 'is a good example. However, nitrogenous resins .have the general disadvantage of retaining chlorine on bleaching thetreated fabric. This results in the cellulose fibers being damaged by a reduction of tensile strength after bleaching and ironing operations.
Another class of agents known in the art to impart dimensional stabilization to cellulose are aliphatic alde- ,hydes.
Since these agents contain no nitrogen atoms there is no problem with chlorine retention; however, these aldehydes do cause cellulose fibers and fabrics reated with them to discolor either on curing or after exposure to light for a short time.
- A novel class of certain formyloxetanes has been discovered which impart unexpected dimensional stability to cellulosic fabrics without the attendant difficulties of chlorine retention and discoloration.
jIt is an object of the present invention to provide novel formyloxetanes which may be applied to cellulosic .fabrics to give a significant dimensional stability thereto.
It is a further object of the present invention to provide a novel class of said oxetanes which avoid the prior art attendant difficulties of chlorine-retention and discoloration.-, It is still a further object of the present invention to provide a novel process for preparing the formyl- .oxetane s to cellulosic textiles to impart a significant di- 'mensional stability thereto without attendant difiiculties ,of chlorine retention and discoloration. These and other objects will become apparent in the following description and claims. V
More specifica ly, the present invention is directed to compounds of the structure wherein R is a lower alkyl group and n is 0 or 1.
This invention also includes a process for preparing the novel formyloxetanes described, saidprocess comprising reacting a gaseous mixture of oxygen and an alcohol of thestruct'ure wh ereinR is a lower alkyl group and 'n is taken from the group consisting of zero and 1 at a temperature within the range of 200 to 600 C. in the presence of a de- I'hydrogenation' catalyst. q ffIn addition, it is part of the present invention to provide a process for imparting dimensional stability to cellulosic textiles by depositing on said textile, from an 2,923,645 Patented Feb. 2, 1960 'RCQ aqueous pad bath, between and 15% (on the weight of the textile) of a compound having the structure R-(OCHzh CHO Cg: CH:
wherein R is a lower alkyl group and n is taken from the group consisting of zero and 1, and 0.1% to 2% (by weight of the textile) of zinc fluoroborate, drying the textile and curing it at to C. for 0.5 to 5 minutes.
The novel compounds of the present invention include 3-formyl-3-methyloxetane which has the structure ous systems.
The formyloxetanes of the present invention are prepared by feeding oxygen and the alcohol oxetane utilized into a heated chamber (alcohol boiler) which serves to vaporize the alcohol. The mixed vapors of alcohol and oxygen are then fed into a reaction chamber which contains the catalyst and which is held at a temperature between about 200 and 600 C. The gaseous reaction products pass into a condenser and the liquid formyloxetane is fed into the product receiver.
The alcohol oxetanes are known and may be derived from pentaerythritol or 1,1,1-trihydroxymethylalkanes. These compounds are disclosed and their preparation given in French Patent 1,122,903.
The source of oxygen may be air or pure oxygen.
The catalyst may be selected from any of the wide variety of known. catalysts for vapor phase dehydrogenation of alcohols to aldehydes. These catalysts .include many metals and their compoundssuch as those of platinum, palladium, nickel, cobalt, copper, silver, gold,
iron, chromium and aluminum. These dehydrogenation catalysts are disclosed and discussed by Marek and Hahn in their monograph Catalytic Oxidation of Organic Compounds in the Vapor Phase, published by the Chemical Catalogue Co., 1932; pages 67 to 88 deal particularly with the catalytic dehydrogenation of alcohols to alde- 'hydes. For the process of this case, the preferred catalysts are metallic silver or copper chromite deposited on a support such as pumice.
The temperature of the reaction will in general vary between about 200 and 600 C. depending upon the particular catalyst employed. The relationship of temperature to catalyst is well known in the art as taught by the monograph referred to above. When the preferred catalysts of silver or copper chromite are used, the temperature of the reaction will be between about 300 and 400 C.
The amount of oxygen used in the process may vary widely, some oxidation (i.e. dehydrogenation) of alcohol to aldehyde occurring even without it. However, it is preferred to use oxygen in order to obtain improved yields and conversions and these are best obtained when the amount of oxygen employed is less than the theoreti- 3 calamount required for the oxidation to occur. Pref erably the amount used will be 10% to 40% of the theoretical amountrequired based on the alcohol oxetane taken according to the following equation:
The aldehyde-oxetanes of this invention are readily applied to cellulosic textiles, e.g., cotton. Because of their water solubility or miscibility the agents are applied from aqueous pad baths and an amount'of agent between about 1% and about 15% on the weight of the fabric will be applied. Usually, a wet pick-up between about 75% and 100% will be used and the pad bath concentration wil be adjusted accordingly.
In order that these agents impart durable crease resistant effects to the fabric it is necessary that the padded fabric be cured after application to the textile. The padded fabric will be air dried prior to the curing step in order to get crease resistance. In the absence of the air drying step, excessive loss of the agent from the textile seems to occur and no significant dimensional stabilization is obtained. The air drying step will be carried out at room temperature or at elevated temperatures up to about 100 C. for a few minutes, the length of time 1 varying inversely with the temperature used. The cure eifects reaction of the aldehyde oxetane with the fabric and is accomplished simply by heating in the presence of a catalyst. It has been found that zinc fiuoborate is a suitable catalyst and yields a cured fabric having excellent durable crease resistant effects. Other strongly acidic agents such as zinc perchlorate; zinc chloride, and citric acid catalyze the cure, but are much less eflicient than zinc fluoborate. The amount of catalyst used will vary between 0.1% and 2% on the weight of the fabric, less giving poor crease resistance and more adversely affecting the tensile strength of the treated fabric.
The curing procedure is carried out over a period of about 0.5 to 5 minutes at temperatures between about 130 and 160 C., it being understood that at the higher temperatures, shorter times will be used.
The representative examples illustrating the present invention are as follows.
EXAMPLE 1 Oxidation of 3-hydr0xymethyl-3-methyloxetane vthe alcohol feed line between the needle valve and the alcohol boiler to maintain a fixed head above the needle valve. This assured a constant alcohol flow for a given setting of the needle valve.
The alcohol feed was dropped into a curved glasstube connected directly to a horizontal reaction tube. This curved tube served as the alcohol boiler and was wrapped with an insulated electrical heating element. A thermocouple placed next to the glass (under the heating element) was used to determine the boiler temperature The reaction tube was a straight piece of copper tubing, 1.9 cm. OD. and approximately 100 cm. long. Stainless steel, 28/ 15, male ball joints were silver soldered .at each end for interconnection with the other equipment. The tube was heated with an insulated electrical heating element and surrounded with magnesia for thermal insulation. The temperature of the reaction tube was measured by three thermocouples placed along the le gth of the tube, beneath the insulation and in contact with the outer wall of the tube.
The catalyst used was silver deposited on pumice and was prepared by the procedure described by R.R. Davies and H. H. Hodgson, J. Chem. Soc., 1943, p. 282. Its volume was approximately 200 ml.
3-hydroxymethyl 3 methyloxetane (88.8 g., 0.870 mole) was fed to the boiler at the rate of 1.25 g./rnin. Dry air was introduced atthe rate of 120 mL/min. This air-alcohol ratio is such that the amount of oxygen used is 17.5% of that required by theory. Theboiler temperature was maintained at 300 to 330 C and the center of the reaction tube at 330 to 340 C. Including volatile liquid condensed in the cold traps, 87.7 g. of crude product was obtained. By vapor phase chromatographic analysis, the crude product contained 34.9% 3-formyl-3-methyloxetane and 57.3% 3-hydroxymethyl- 3-inethyloxetane, the remainder being low boiling decomposition products.
The crude product was distilled in an efficientcolumn at 30 mm. pressure to obtain pure 3-formyl-3-methyl1- oxetane (refractive index at =l'.4356) which boiled at 63 at mm. Hg pressure and which analyzed as follows: C H O -Theory: 60% C, 8.1% H. Found: 59.6% C, 7.9% H.
EXAMPLE 2 Oxidation of 3-ethoxymethyl-3-hydr0xymethyl0retane The equipment used was essentially the same as that used for the oxidation of 3-hydroxymethyl-3-methyloxetane, with the exception that a curved copper tube, silver soldered to the reaction tube, was used as the alcohol-boiler in place of the curved glass tube previously described.
The catalyst used was copper chromite supportedon pumice stones. The copper chromite was prepared according to W. A. Lazier and H. R. Arnold (Organic Syntheses, coll. vol. II, John Wiley and Sons, Inc., New York (1943), p. 142), and deposited on the pumice as a paste with water. The lumps were loaded into the tube while damp, and dried by heating in a stream of nitrogen. The catalyst zone was about 60 cm. in length, and was about 120 ml. in volume.
3-ethoxymethyl-3-hydroxymethyloxetane (206 g., 1.41 moles) was fed to the boiler at the rate of 1.17 g./min. Dry air was introduced at the rate of 100 ml./ min. representing 22% of the theoretical amount of oxygen required. The boiler temperature was maintained at 230- 240 C., and the center of the reaction tube at 310340 C. Including volatile liquid condensed in the cold traps, 192.2 g. of crude product'was obtained. Bytopping the crude product under vacuum in a simple-still, 49.6 g. of aldehyde rich fraction was obtained. This portion of the product was then distilled in an efiicient column at 5.0 mm. Hg to give a 7.2 g. cut of pure 3-ethoxymethyl- 3-formyloxetane boiling at 71 to 73 C. at 5.0 mm. Hg pressure. The colorless liquid product had a refractive index at 25 C. of 1.4415. Analysis for 071 11203: Calc.: 58.3% C, 8.4% H. Found: 58.6% C, 8.4% H.
EXAMPLE 3 7 Application of 3-f0rmyl-3-methyloxetane tov cotton An aqueous pad bath was prepared to contain on the weight of the 'bath 16.2% of 3-formyl-3-methyloxetane and .675 of zinc fiuoborate. A piece of cotton fabric was padded at pickup on the weight of the fiber and the padded fabric air dried at 21 C. and 65% relative humidity. The treated fabric thus contained 13% of its weight of the aldehyde oxetane and 0.5% catalyst. Then the fabricwas cured at 137 C. for 84 seconds, after which it was evaluated for crease resistance, whiteness (i.e., reflectanceat 400 m and discoloration after chlorine bleaching. The results obtained showed a crease; recovery angle of,24-6, a high reflectance value of 85 and no discoloration after bleaching and exposure to a Fade- 1 Test method As'rM D-l295-53T.
Ometer for 20 hours. (Fabric treated with prior art aldehydes; e.g. succinaldehyde, discolor badly in this test.)
EXAMPLE 4 Following the details of Example 3 other samples of cotton fabric were treated with the aldehyde oxetanes of this invention. The following table illustrates the conditions used and the results obtained:
Wash-fastness and freedom from chlorine retention were demonstrated by the following experiment: A cotton fabric treated with 3-formyl-3-rnethyloxetane had an original crease recovery angle of 223. After five Sanforize washes, the crease recovery angle was 223. This sample was then subjected to the standard AATCC chlorine retention test (tentative test method 69-1952). After bleaching, its tensile strength was 38 lb./in.; after scorching, the tensile strength was 41 lb./in., showing complete freedom from chlorine retention. There was also no discoloration of the treated fabric.
Any of the formyloxetanes of the present invention may be substituted in any of the preceding examples to give substantially the same results. In addition, the various described catalysts may be substituted throughout the examples to give acceptable and significant results.
As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments there of except as defined in the appended claims.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. Compounds having the structure R-(OCHzh CHO Cg: CH2
wherein R is a lower alkyl group of from 1 to 4 carbon atoms and n is taken from the group consisting of 0 and 1.
2. 3-formyl-3-methyloxetane.
3. 3-formyl-3-ethyloxetane.
4. 3-ethoxymethyl-3-formyloxetane.
5. A process for preparing formyloxetanes which comprises reacting a gaseous mixture of oxygen and an alcohol of the structure R- oom). 011,011
wherein R is a lower alkyl group of from 1 to 4 carbon atoms and n is taken from the group consisting of 0 and l, at a temperature Within the range of 200-600 C. in the presence of a dehydrogenation catalyst.
6. A process for imparting dimensional stability to cellulosic textiles by depositing on said textile from an aqueous pad bath between 1 and 15% by weight of said textile of a compound having the structure R(OCH2)n CHO CH CH2 wherein R is a lower alkyl group and n is taken from the group consisting of 0 and 1, from 0.1 to 2% by weight of said textile of zinc fluoborate, followed by drying the treated textile and curing said textile at a temperature within the range of to C. from 0.5 to 5.0 minutes.
No references cited.

Claims (1)

  1. 6. A PROCESS FOR IMPARTING DIMENSIONAL STABILITY TO CELLULOSIC TEXTILES BY DEPOSITING ON SAID TEXTILE FROM AN AQUEOUS PAD BATH BETWEEN 1 AND 15% BY WEIGHT OF SAID TEXTILE OF A COMPOUND HAVING THE STRUCTURE
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074898A (en) * 1959-02-13 1963-01-22 Rohm & Haas Composition comprising aqueous dispersion of aminoplast condensate and an oxetane
US3097050A (en) * 1959-12-28 1963-07-09 Rohm & Haas Process of creaseproofing cellulose fabrics with 2, 6-dioxaspiro (3, 3) heaptane and ormaldehyde and fabrics produced thereby
US5578091A (en) * 1990-04-19 1996-11-26 Exxon Chemical Patents Inc. Chemical compositions and their use as fuel additives

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* Cited by examiner, † Cited by third party
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074898A (en) * 1959-02-13 1963-01-22 Rohm & Haas Composition comprising aqueous dispersion of aminoplast condensate and an oxetane
US3239303A (en) * 1959-02-13 1966-03-08 Rohm & Haas Process for the treatment of textiles and the textiles obtained
US3097050A (en) * 1959-12-28 1963-07-09 Rohm & Haas Process of creaseproofing cellulose fabrics with 2, 6-dioxaspiro (3, 3) heaptane and ormaldehyde and fabrics produced thereby
US5578091A (en) * 1990-04-19 1996-11-26 Exxon Chemical Patents Inc. Chemical compositions and their use as fuel additives

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