US2524399A - Cellulose treated with di-vinyl sulfone to shrinkproof - Google Patents
Cellulose treated with di-vinyl sulfone to shrinkproof Download PDFInfo
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- US2524399A US2524399A US37507A US3750748A US2524399A US 2524399 A US2524399 A US 2524399A US 37507 A US37507 A US 37507A US 3750748 A US3750748 A US 3750748A US 2524399 A US2524399 A US 2524399A
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- fabric
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- vinyl sulfone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
-
- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/272—Unsaturated compounds containing sulfur atoms
- D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds
-
- 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
- Y10S8/02—Vinyl sulfones and precursors thereof
Definitions
- Patented 3,, 1950 CELLULOSE TREATED WITH III-VINYL SULFONE T SHRINKPROOF Dwight L.
- This invention relates to modified cellulosic products.
- An object of the invention is to provide products derived from cellulose, regenerated cellulose, such as viscose and rayon, and the like, which products .are dimensionally stable to water.
- a particular and outstanding object is to provide a method of reducing the shrinkage of cotton and regenerated cellulose textile materials and fabrics which are subject to washing.
- Another object is to provide fabrics havingcdmproved creaseresistance. Further'objects will be apparent from the hereinafter description.
- the treatment on both cotton and rayon is substantially the alkaline catalyst.
- the reaction may be carried out from 0 .C. to 100 reaction is complete and temperatures of 0-50 C. are preferred.
- the fabric or yarn is washed substantially free ofcatalyst and limeacted vinyl sulfone, and then dried.
- the catalyst may be removed as such, byneutralization by dilute acid which eflectively stops the reaction. 7
- the treated cellulose and rayon no longer dis solve in the usual solvents for these materials, such as cupra ammonia, and the quaternary in water or alkali solutions.
- reaction may be carried out under anhydrous conditions
- the catalyst solutions may be pro-mixed and used for, the treatment. Advisedly, this latter procedure is used when the pre-mixing and treatment are accomplished in a period of a few minutes. Also, since in the presence of aqueous alkali, the vinyl sulfone will react very slowly with water at room temperatures, e. g., 20-25 0., such temperatures are preferred.
- catalyst we may employ any base or alkali which is unreactive with vinyl sulfone.
- Ammonia any base or alkali which is unreactive with vinyl sulfone.
- Any salt such as sodium chloride, sodium sulfate, sodium acetate.
- sodium phosphate may be used, the purpose being that this reduces the leaching of the sulfone from the fabric into the catalyst solution.
- the concentration of catalyst solution used depends upon the speed required in the reaction and upon the desire to avoid treatment by more concentrated alkali, which would tend to degrade the fabric.
- concentrations of alkali such as sodium hydroxide of 20 to 30%, may be employed satisfactorily with a reaction time of 15 seconds or less. A- concentration of 0.5% will effect essentially the same reaction in a period of about 30 minutes. Concentrations ranging from 0.1% may be employed with somewhat longer reaction times. With fabrics con-- taining regenerated cellulose, high concentrations of alkali are to be avoided, because of their tendering effect. With such materials, sodium hydroxide concentrations ranging from 0.1% to about 8% may be employed satisfactorily. Similar considerations hold for the other catalysts.
- the concentration of the vinyl sulfone employed will depend upon the textile material, yarn, or filament used, and also from the desired use for the treated fabric.
- the fabric To obtain, for example, a 5% concentration of the sulfone on the fabric, it is convenient to dip the fabric into a 5% solution of the vinyl sulfone in water, and then pass it through rolls set at a tension to provide a wet pick-up of about 100%. The wet fabric is then passed through a solution of the basic catalyst in a concentrated aqueous salt solution and then through another set of rolls set to give a wet pick-up or about 120-200%. The fabric is allowed to stand until the reaction is substantially complete, and is then washed, dried, and finished according to normal textile finishing operations.
- the fabrics are impregnated or sized with textile sizing materials, such as starch, dextrin, methyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, and various alkali soluble vegetable gums, such as gum arabic, and the like, that fabrics are obtained having permanent stiffness, improved hand, and in some cases improved crease-resistance, in addition to improved shrink resistance.
- textile sizing materials such as starch, dextrin, methyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, and various alkali soluble vegetable gums, such as gum arabic, and the like.
- This treatment is accomplished readily by simple procedures.
- the fabric may be immersed in a solution or suspension of the sizing material and dried, leaving the fabric impregnated with the sizing. It is then treated with the vinyl sulfone according to the usual procedure. Part of the sulfone reacts with the cellulosic fabric and part often convenient to treat a. sized fabric with vinyl sul
- EXAMPLEI 'A plain weave viscose spun rayon fabric having a count of 54 x 53, a weight of 5.3 oz. per yard, and made of 16.3/1 warp and 16.4/1 filling of spun viscose staple fibre is passed through an aqueous impregnating solution containing 20 grams of vinyl sulfone in 1000 ml. of solution.
- the excess solution is removed by passing the rayon fabric through rolls set at such a pressure that the weight of the wet fabric is about twice the weight of the dry fabric, 1. e., a 100% wet pick-up.
- the wet fabric is then immersed in an aqueous solution containing about 10 grams of sodium hydroxide and 200 grams of sodium sulfate in 1000 ml. of solution.
- the fabric is again passed through squeeze rolls, the pressure of which is less than that of the rolls mentioned above.
- the fabric is then allowed to stand for at least 30 minutes at or near room temperature (ca. 25 C.). At the end of this time it is immersed in an aqueous solution containing pproximately 1% acetic acid to neutralize the alkali.
- the fabric is then washed in water and dried. Best results are obtained if the tension applied to the fabric during drying is sufllcient only to hold it in the dimensions maintained during treatment.
- the following table gives the results of laundering tests run with /z% of mild soap at F. for 15 minutes.
- the samples described as dried stretched are dried to their original dimensions after treatment, those described as dried relaxed, are dried hung on a line.
- the table below presents the results of laundering tests:
- EXAMPLE 5 A /1 all viscose spun rayon yarn wound on perforated tubes is impregnated with a 3% aqueous solution of vinyl sulfone in a, package dyeing machine. The excess solution is allowed to drain oil, and a. 2% aqueous sodium hydroxide solution containing sodium sulfate, is circuthe yarn. The yarn is allowed to stand for minutes, and the alkali is neutralized with dilute acetic acid. The dried, and woven into a fabric. This fabric has much less shrinkage than a fabric woven from an untreated yarn.
- EXAMPLE6 A specially woven all cotton fabric with warp threads twisted into a coiled form. so that the material is highly elastic, is thoroughly wet with a freshly prepared aqueous solution containing 10 grams of vinyl sulfone and 0.5 gram of sodium hydroxide per 100 ml. of solution. The excess solution is allowed to drain of! and the material kept 50 C. for about one-half an hour in a closed container. The reaction is stopped by neutralizing the alkali with an excess of dilute acetic acid and the fabric is then washed with water and dried.
- a strip 3 inches wide in the fill direction is wet with water and loaded with the weights indicated in the table below.
- the percent elongation in the warp direction resulting from this load and the percent increase in length remaining removed is given for each loadmg. It .can be seen from these figures that the treated fabric resists stretching to a much greater degree. It also returns to more nearly its original length after the load is removed than does the previous samples andthe yarn is washed.
- Example 1 except that a 4% aqueous solution of vinyl sulfone is used in place of the 2% solution specified there.
- the neutralization with acid, washing, and drying are the same as described in lilrsample 1.
- the table below presents the resu w 1 Percent warp shrinkage with water. It is then spread out and pressed with a hot iron until it is only slightly moist. When the iron is lifted, the fabric snaps back into the original folds, i. e., approximately recovery. When pressing is continued to dryness, the fabric lies flat but the position of the original creases is still visible.
- the fabric is allowed to stand in contact with asses EXAMPLE
- a viscose rayon fabric, as described in Example 8 is treated in the same way as described in that example, except that a 2% aqueous solution of benzyltrimethyl ammonium hydroxide, containing about sodium sulfate, is used in place of the 5% aqueous sodium carbonate solution.
- the following table gives the results of laundering tests.
- EXAMPLE 11 fabric and then washed in water. It is stretched to its original dimensions and dried in this stretched condition. The finished fabric is subjected to a laundering test as in previous examples and the following table gives the results.
- a 4 oz. spun viscose rayon fabric is treated in the greige, without removing warp size, with a solution containing 3% vinyl sulfone and alkali catalyst, according to the procedure of Example 1.
- the treated fabric and a control are then laundered at 180 F. for 30 minutes, dried, and examined.
- the treated fabric shows only slight shrinkage and remains nearly as stiff as the original unwashed fabric, 1. e., the size is not removed.
- the washed control shows much more shrinkage and is less stiff due to removal of the size.
- a method which comprises subjecting cellulose to chemical reaction with divinyl sulfone.
- a method which comprises contacting and chemically combining cellulose and derivatives of cellulose containing cellulosic hydroxyl groups with divinyl sulfone in the presence of a basic compound unreactive to divinyl sulfone as a catalyst therefor, which basic compound is from the class consisting of alkali-metal, alkali-earth metal, quaternary ammonium hydroxides, and alkali-metal carbonates.
Description
Patented 3,, 1950 CELLULOSE TREATED WITH III-VINYL SULFONE T SHRINKPROOF Dwight L.
Naugatuck, Conn, Rubber tion or New Jersey Schoene and Victor assignors to United States Company, New York, N. Y.,
8. Chambers,
8 corpora- No Drawing. Application July 7, 1948,
Serial No. 87,507
4 Claims. (0]. 8116) 1 i This invention relates to modified cellulosic products.
An object of the invention is to provide products derived from cellulose, regenerated cellulose, such as viscose and rayon, and the like, which products .are dimensionally stable to water. A particular and outstanding object is to provide a method of reducing the shrinkage of cotton and regenerated cellulose textile materials and fabrics which are subject to washing. Another object is to provide fabrics havingcdmproved creaseresistance. Further'objects will be apparent from the hereinafter description.
found that the treatment with vinyl sulfone in. the presence of a basic catalyst substantially reduces the shrinkage of the rayon.
Although shrinkage is not so pronounced with cotton fabrics as with rayon, our process has definite application'to cotton also. When a cotton fabric is creased and then treated, it takes on the surprising property of returning ,to the same creased condition when wet. Similarly,
when a cotton or rayon fabric is pressed smooth Such effects can be applied in the manufacture of pleated or shaped fabrics, or in setting the twist in yarns. The treatment on both cotton and rayon is substantially the alkaline catalyst. The in a period ranging from a few seconds to about two hours, depending primarily upon the strength and concentration of the basic catalyst used. The reaction may be carried out from 0 .C. to 100 reaction is complete and temperatures of 0-50 C. are preferred. At the end of the reaction period, the fabric or yarn is washed substantially free ofcatalyst and limeacted vinyl sulfone, and then dried. Alternatively, the catalyst may be removed as such, byneutralization by dilute acid which eflectively stops the reaction. 7
We postulate the following reactionin the formation of vinyl sulfone-cellulose, although it is C. tion, we find it convenient not desired to be restricted to this mechanism: cellulose-0H cHl=cHs0,cH=-.cm HO-cliulose I catalyst cellulOSe-O-CHaOHrSOaCHgOHz-O-CelllllOSe where cellulose 0H represents part of the cellulose or regenerated cellulose chain.
The treated cellulose and rayon no longer dis solve in the usual solvents for these materials, such as cupra ammonia, and the quaternary in water or alkali solutions.
A number of variations in the treatment are possible without departing from the spirit and scope of the invention. The reaction may be carried out under anhydrous conditions;
Alternatively, the catalyst solutions may be pro-mixed and used for, the treatment. Advisedly, this latter procedure is used when the pre-mixing and treatment are accomplished in a period of a few minutes. Also, since in the presence of aqueous alkali, the vinyl sulfone will react very slowly with water at room temperatures, e. g., 20-25 0., such temperatures are preferred.
As catalyst, we may employ any base or alkali which is unreactive with vinyl sulfone. Ammonia,
sulfone and catalysts.
When a two-bath system ple, when the fabric is first sulfone bath. and
Q in a concentrated salt solution. Any salt such as sodium chloride, sodium sulfate, sodium acetate. sodium phosphate may be used, the purpose being that this reduces the leaching of the sulfone from the fabric into the catalyst solution.
The concentration of catalyst solution used depends upon the speed required in the reaction and upon the desire to avoid treatment by more concentrated alkali, which would tend to degrade the fabric. With cotton'fabrics, concentrations of alkali, such as sodium hydroxide of 20 to 30%, may be employed satisfactorily with a reaction time of 15 seconds or less. A- concentration of 0.5% will effect essentially the same reaction in a period of about 30 minutes. Concentrations ranging from 0.1% may be employed with somewhat longer reaction times. With fabrics con-- taining regenerated cellulose, high concentrations of alkali are to be avoided, because of their tendering effect. With such materials, sodium hydroxide concentrations ranging from 0.1% to about 8% may be employed satisfactorily. Similar considerations hold for the other catalysts.
Compounds capable of forming vinyl sulfone in situ under the conditions of the reaction also are to be considered as operative.
The concentration of the vinyl sulfone employed will depend upon the textile material, yarn, or filament used, and also from the desired use for the treated fabric.
An observable effect is obtained with as little as 0.1% based on the weight of the cellulose, and preferred concentrations lie between about 1 and 10%, although concentrations up to 1 part of vinyl sulfone per part of cellulose, by weight, may be used.
.As applied to fabrics, increasing concentrations of vinyl sulfone cause a progressive decrease in the tensile strength so it is desirable to keep the concentration as low as possible consistent with obtaining the desired effect. With regenerated cellulose, concentrations of vinyl sulfone between approximately 1 part and approximately 5 parts per 100 of the cellulose give satisfactory results with negligible tensile deterioration.
To obtain, for example, a 5% concentration of the sulfone on the fabric, it is convenient to dip the fabric into a 5% solution of the vinyl sulfone in water, and then pass it through rolls set at a tension to provide a wet pick-up of about 100%. The wet fabric is then passed through a solution of the basic catalyst in a concentrated aqueous salt solution and then through another set of rolls set to give a wet pick-up or about 120-200%. The fabric is allowed to stand until the reaction is substantially complete, and is then washed, dried, and finished according to normal textile finishing operations.
It has also been found that if the fabrics are impregnated or sized with textile sizing materials, such as starch, dextrin, methyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, and various alkali soluble vegetable gums, such as gum arabic, and the like, that fabrics are obtained having permanent stiffness, improved hand, and in some cases improved crease-resistance, in addition to improved shrink resistance. This treatment is accomplished readily by simple procedures. For example, the fabric may be immersed in a solution or suspension of the sizing material and dried, leaving the fabric impregnated with the sizing. It is then treated with the vinyl sulfone according to the usual procedure. Part of the sulfone reacts with the cellulosic fabric and part often convenient to treat a. sized fabric with vinyl sulfone, thus achieving stiflness and dimensional stability at the same time.
The following examples are given to illustrate our invention, but are not to be construed as limiting thereto.
EXAMPLEI 'A plain weave viscose spun rayon fabric having a count of 54 x 53, a weight of 5.3 oz. per yard, and made of 16.3/1 warp and 16.4/1 filling of spun viscose staple fibre is passed through an aqueous impregnating solution containing 20 grams of vinyl sulfone in 1000 ml. of solution. The excess solution is removed by passing the rayon fabric through rolls set at such a pressure that the weight of the wet fabric is about twice the weight of the dry fabric, 1. e., a 100% wet pick-up. The wet fabric is then immersed in an aqueous solution containing about 10 grams of sodium hydroxide and 200 grams of sodium sulfate in 1000 ml. of solution. The fabric is again passed through squeeze rolls, the pressure of which is less than that of the rolls mentioned above. The fabric is then allowed to stand for at least 30 minutes at or near room temperature (ca. 25 C.). At the end of this time it is immersed in an aqueous solution containing pproximately 1% acetic acid to neutralize the alkali. The fabric is then washed in water and dried. Best results are obtained if the tension applied to the fabric during drying is sufllcient only to hold it in the dimensions maintained during treatment. The following table gives the results of laundering tests run with /z% of mild soap at F. for 15 minutes. The samples described as dried stretched are dried to their original dimensions after treatment, those described as dried relaxed, are dried hung on a line.
Percent warp shrinkage Washes 1 2 x 3 i 5 7 Untreated 8.4 7.7 10.8 9.7 14.6 Treated:
Dried Stretched. .1. 0 0.7 2. 8 2.1 4. 2 Dried Relaxed +0.3 +0.7 +0.7 0.3 2.1
Norm-The values for the "dried stretched" shrinkage mean that the sample after the treatment was dried in a stretched condition. ifter gzgshlng the drying was done relaxed. The values denote s re c g.
' EXAMPLE2 Percent warp shrinkage Washes 1 2 a a 1 Unttgidted 5.9 0.7 14.9 as; .9 Dried Stretched. as 4.9 4.5 as 6.2 Dried Relaxed o 1.1 0.3 +1.4 as
The value denotes stretching.
, least 30 minutes.
ple 1.
- lated through mums Percent warp shrinkage Washes 1 2 3 5 7 Untreated 6.0 0.7 14.0 26.4 31.0 Treated:
DriedStretched 2.1 2.1 2.8 1.4 218 Dried Relaxed +1.4 +1.7 +1.7 +2.4 1.1
A viscose rayon fabric, as described in Example l, is treated with vinyl sulfone and alkali, as described in Example 3. The table below presents the results of laundering tests:
Percent warp shrinkage Washes l 2 3 5 I 7 Untreated. 8.3 15.3 16.0
. Treated:
Dried Stretched. 1. l 1.4 0.3 0. 7 0. 3 Dried Relaxed.-- +1.4 +1.4 +0.3 +0.3 +0.8
EXAMPLE 5 A /1 all viscose spun rayon yarn wound on perforated tubes is impregnated with a 3% aqueous solution of vinyl sulfone in a, package dyeing machine. The excess solution is allowed to drain oil, and a. 2% aqueous sodium hydroxide solution containing sodium sulfate, is circuthe yarn. The yarn is allowed to stand for minutes, and the alkali is neutralized with dilute acetic acid. The dried, and woven into a fabric. This fabric has much less shrinkage than a fabric woven from an untreated yarn.
EXAMPLE6 A specially woven all cotton fabric with warp threads twisted into a coiled form. so that the material is highly elastic, is thoroughly wet with a freshly prepared aqueous solution containing 10 grams of vinyl sulfone and 0.5 gram of sodium hydroxide per 100 ml. of solution. The excess solution is allowed to drain of! and the material kept 50 C. for about one-half an hour in a closed container. The reaction is stopped by neutralizing the alkali with an excess of dilute acetic acid and the fabric is then washed with water and dried.
A strip 3 inches wide in the fill direction is wet with water and loaded with the weights indicated in the table below. The percent elongation in the warp direction resulting from this load and the percent increase in length remaining removed is given for each loadmg. It .can be seen from these figures that the treated fabric resists stretching to a much greater degree. It also returns to more nearly its original length after the load is removed than does the previous samples andthe yarn is washed.
Per Cent Elongation, treated- 9 Per Cent Elongation, control- Per Cent Bet, treated 5 5 Per Cent Set, oontroL. mm
Example 1, except that a 4% aqueous solution of vinyl sulfone is used in place of the 2% solution specified there. The neutralization with acid, washing, and drying are the same as described in lilrsample 1. The table below presents the resu w 1 Percent warp shrinkage with water. It is then spread out and pressed with a hot iron until it is only slightly moist. When the iron is lifted, the fabric snaps back into the original folds, i. e., approximately recovery. When pressing is continued to dryness, the fabric lies flat but the position of the original creases is still visible.
condition. This demonstrates how our treatment tends to fix" the fabric in its original dimensions. A similar but less pronounced effect is observed with regenerated cellulose.
EXAMPLE 9 solution containing about 20% sodiumsulfate, is used in place of the sodium hydroxide solution. The fabric is allowed to stand in contact with asses EXAMPLE A viscose rayon fabric, as described in Example 8, is treated in the same way as described in that example, except that a 2% aqueous solution of benzyltrimethyl ammonium hydroxide, containing about sodium sulfate, is used in place of the 5% aqueous sodium carbonate solution. The following table gives the results of laundering tests.
Percent warp shrinkage Washes i- 1 2 3 5 7 Untreated 8.3 9.0 10.0 12.2 13.6
Treated 2.8 2.8 6.2 4.2 3.5
EXAMPLE 11 fabric and then washed in water. It is stretched to its original dimensions and dried in this stretched condition. The finished fabric is subjected to a laundering test as in previous examples and the following table gives the results.
Percent warp shrinkage Washes 1 2 3 5 7 ggdfIIIIIIiIIIIIIIIIIIIIIII 31 2i; 22 if? it EXAMPLE 12 A piece of viscose rayon fabric is treated with 5% vinyl sulfone under the conditions of Example 11. At the end of the reaction the rayon does not dissolve in a 38% solution of benzyl trimethyl ammonium hydroxide, while an untreated .control dissolves in a few minutes;
A 4 oz. spun viscose rayon fabric is treated in the greige, without removing warp size, with a solution containing 3% vinyl sulfone and alkali catalyst, according to the procedure of Example 1. The treated fabric and a control are then laundered at 180 F. for 30 minutes, dried, and examined. The treated fabric shows only slight shrinkage and remains nearly as stiff as the original unwashed fabric, 1. e., the size is not removed. The washed control shows much more shrinkage and is less stiff due to removal of the size.
Having thus described our invention, what we claim and desire to protect by Letters Patent is: l. A method which comprises contacting and chemically combining cellulose and derivatives of cellulose containing cellulosic hydroxyl groups with divinyl sulfone.
1. A method which comprises subjecting cellulose to chemical reaction with divinyl sulfone.
3. A method which comprises contacting and chemically combining cellulose and derivatives of cellulose containing cellulosic hydroxyl groups with divinyl sulfone in the presence of a basic compound unreactive to divinyl sulfone as a catalyst therefor, which basic compound is from the class consisting of alkali-metal, alkali-earth metal, quaternary ammonium hydroxides, and alkali-metal carbonates.
4. A product of reaction of divinyl sulfone and cellulose fibres in which the fibre form of the cellulose is retained in the modified cellulose, said modified cellulose fibres being more resistant to shrinking by water than the untreated cellulose fibres.
DWIGHT L. SCHOENE.
VICTOR S. CHAMBERS.
REFERENCES CITED 'lhe following references are of record in the file of this patent:
' unrrnn s'rs'ms PATENTS- Number Name Date 2,969,774 Reid Feb. 9, 1937 2,103,879 Ufer Dec. 28, 1937 2,243,630 Honk et al. May 2'1, 1941 2,427,640 Whitehili et al. Sept. 16, 1947
Claims (1)
1. A METHOD WHICH COMPRISES CONTACTING AND CHEMICALLY COMBINING CELLULOSE AND DERIVATIVES OF CELLULOSE CONTAINING CELLULOSIC HYDROXYL GROUPS WITH DIVINYL SULFONE.
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US37507A US2524399A (en) | 1948-07-07 | 1948-07-07 | Cellulose treated with di-vinyl sulfone to shrinkproof |
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Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2623807A (en) * | 1950-08-02 | 1952-12-30 | American Viscose Corp | Cellulosic textiles reacted with urea-vinyl sulfone addition products |
US2753338A (en) * | 1953-01-21 | 1956-07-03 | American Viscose Corp | Process for preparing a viscose solution |
US2955016A (en) * | 1956-10-15 | 1960-10-04 | Joseph E Moore | Modification of keratins with sulphones and related compounds |
US2985501A (en) * | 1956-04-03 | 1961-05-23 | Deering Milliken Res Corp | Process of producing flat drying, wet crease resistant cellulosic fabrics by reaction with cross-linking agents and products produced thereby |
US3000762A (en) * | 1960-08-25 | 1961-09-19 | Stevens & Co Inc J P | Process for reacting polymeric materials with sulfones and products resulting therefrom |
DE1118743B (en) * | 1958-07-23 | 1961-12-07 | Rohm & Haas | Process for the treatment of cellulose-containing fabrics |
US3061399A (en) * | 1959-02-09 | 1962-10-30 | Stevens & Co Inc J P | Treating cotton to improve wet and dry crease recovery in one operation |
DE1139465B (en) * | 1960-04-29 | 1962-11-15 | Deering Milliken Res Corp | Process for the crosslinking of hydroxyl groups in cellulosic textiles |
US3068123A (en) * | 1960-09-27 | 1962-12-11 | Dan River Mills Inc | Divinyl sulfone derivatives useful for rendering cellulosic textile fabric crease-resstant |
US3106439A (en) * | 1959-01-17 | 1963-10-08 | Tootal Broadhurst Lee Co Ltd | Process of dry creaseproofing cellulosic fabrics with divinyl shlphone |
DE1166145B (en) * | 1960-12-28 | 1964-03-26 | Hoechst Ag | Process for dyeing and finishing textile material containing cellulose |
US3175874A (en) * | 1959-01-29 | 1965-03-30 | Deering Milliken Res Corp | Method of creaseproofing cellulosic fabrics by wet creaseproofing followed by dry creaseproofing and the resulting product |
US3175875A (en) * | 1960-04-25 | 1965-03-30 | Deering Milliken Res Corp | Cellulosic fabrics and methods for making the same |
US3194627A (en) * | 1956-04-03 | 1965-07-13 | Deering Milliken Res Corp | Processes for producing modified cellulosic textile materials |
US3202474A (en) * | 1962-01-23 | 1965-08-24 | Clark M Welch | Process for crosslinking cellulose with formaldehyde adducts of divinyl sulfone |
US3214235A (en) * | 1961-03-17 | 1965-10-26 | Monsanto Co | Crosslinked derivatives of polyhydroxy compounds and an ester of propiolic acid |
US3222119A (en) * | 1959-03-10 | 1965-12-07 | Monsanto Co | Process for treating cellulosic textile materials with bis(beta-methoxyethyl) sulfone |
US3227511A (en) * | 1961-08-02 | 1966-01-04 | Kendall & Co | Methods of forming woven stretchable fabrics |
US3230031A (en) * | 1962-02-06 | 1966-01-18 | Clark M Welch | Process for making aryloxyethylsul-fonylethyl ethers of cellulose |
US3240797A (en) * | 1959-12-31 | 1966-03-15 | Deering Milliken Res Corp | Bis (sulfatoethyl) sulfoxide salts |
US3281204A (en) * | 1962-06-21 | 1966-10-25 | Clark M Welch | Polymeric adducts of divinyl sulfone with water as crosslinking agents for cellulose |
US3293340A (en) * | 1966-02-09 | 1966-12-20 | Union Carbide Corp | Method of producing colored structures |
US3294779A (en) * | 1964-01-17 | 1966-12-27 | Austin L Bullock | Process for making crosslinked cellulose derivatives utilizing acetylenic carboxylic acids |
US3294780A (en) * | 1964-01-17 | 1966-12-27 | Austin L Bullock | Process for making crosslinked cellulose derivatives utilizing halo-acrylic acids |
US3314744A (en) * | 1961-07-03 | 1967-04-18 | Gen Aniline & Film Corp | Crosslinkage of cellulose fibers with phosphate esters of di-ethanol sulfones |
US3338883A (en) * | 1961-03-31 | 1967-08-29 | Stevens & Co Inc J P | Process for modifying polymeric materials, and modifier reactants for such use |
US3359061A (en) * | 1961-12-19 | 1967-12-19 | Clark M Welch | Process for making alkoxyethylsulfonylethyl ethers of cellulose |
US3407026A (en) * | 1961-02-24 | 1968-10-22 | Deering Milliken Res Corp | Soil retention of aminoplast resin-softener-epichlorohydrin modified cellulosic fabrics obviated by inclusion of carboxymethyl cellulose in reaction system |
US3477802A (en) * | 1963-03-19 | 1969-11-11 | Stevens & Co Inc J P | Modification of cellulose,polyvinyl alcohol and starch with compounds characterized by ethylene radicals having an electron attracting group which stabilizes carbanions on one carbon atom thereof and an alkoxy or hydroxy group on the other |
US3501260A (en) * | 1964-03-18 | 1970-03-17 | Stevens & Co Inc J P | Polyvinyl alcohol and starch bound to cellulosic textile substrate through reaction with beta-oxyethyl sulfones |
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US3619277A (en) * | 1969-11-26 | 1971-11-09 | Christina L Allen | Method of improving the crease resistance of a cellulosic fabric |
US8834679B2 (en) | 2012-12-26 | 2014-09-16 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
US8980054B2 (en) | 2012-12-26 | 2015-03-17 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
US9410292B2 (en) | 2012-12-26 | 2016-08-09 | Kimberly-Clark Worldwide, Inc. | Multilayered tissue having reduced hydrogen bonding |
US9416494B2 (en) | 2012-12-26 | 2016-08-16 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
US20180354853A1 (en) * | 2017-05-26 | 2018-12-13 | Clemson University Research Foundation | Covalently cross-linked lignocellulosic composites and applications thereof |
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Cited By (43)
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US2623807A (en) * | 1950-08-02 | 1952-12-30 | American Viscose Corp | Cellulosic textiles reacted with urea-vinyl sulfone addition products |
US2753338A (en) * | 1953-01-21 | 1956-07-03 | American Viscose Corp | Process for preparing a viscose solution |
US2985501A (en) * | 1956-04-03 | 1961-05-23 | Deering Milliken Res Corp | Process of producing flat drying, wet crease resistant cellulosic fabrics by reaction with cross-linking agents and products produced thereby |
US3194627A (en) * | 1956-04-03 | 1965-07-13 | Deering Milliken Res Corp | Processes for producing modified cellulosic textile materials |
US2955016A (en) * | 1956-10-15 | 1960-10-04 | Joseph E Moore | Modification of keratins with sulphones and related compounds |
US3218118A (en) * | 1958-07-23 | 1965-11-16 | Rohm & Haas | Crease-proofing cellulosic fabrics, the fabrics obtained and methods of making them |
DE1118743B (en) * | 1958-07-23 | 1961-12-07 | Rohm & Haas | Process for the treatment of cellulose-containing fabrics |
US3106439A (en) * | 1959-01-17 | 1963-10-08 | Tootal Broadhurst Lee Co Ltd | Process of dry creaseproofing cellulosic fabrics with divinyl shlphone |
DE1179536B (en) * | 1959-01-17 | 1964-10-15 | Brian Frederick Sagar | Process for the finishing of woven, knitted and non-woven cellulose textiles |
DE1212486C2 (en) * | 1959-01-29 | 1974-11-07 | Deering Milliken Res Corp | Process for wrinkle-proof finishing of textiles containing cellulose fibers |
US3175874A (en) * | 1959-01-29 | 1965-03-30 | Deering Milliken Res Corp | Method of creaseproofing cellulosic fabrics by wet creaseproofing followed by dry creaseproofing and the resulting product |
DE1212486B (en) * | 1959-01-29 | 1966-03-17 | Deering Milliken Res Corp | Process for the crease-resistant finishing of textiles containing cellulose fibers |
US3061399A (en) * | 1959-02-09 | 1962-10-30 | Stevens & Co Inc J P | Treating cotton to improve wet and dry crease recovery in one operation |
US3222119A (en) * | 1959-03-10 | 1965-12-07 | Monsanto Co | Process for treating cellulosic textile materials with bis(beta-methoxyethyl) sulfone |
US3240797A (en) * | 1959-12-31 | 1966-03-15 | Deering Milliken Res Corp | Bis (sulfatoethyl) sulfoxide salts |
US3175875A (en) * | 1960-04-25 | 1965-03-30 | Deering Milliken Res Corp | Cellulosic fabrics and methods for making the same |
DE1139465B (en) * | 1960-04-29 | 1962-11-15 | Deering Milliken Res Corp | Process for the crosslinking of hydroxyl groups in cellulosic textiles |
US3000762A (en) * | 1960-08-25 | 1961-09-19 | Stevens & Co Inc J P | Process for reacting polymeric materials with sulfones and products resulting therefrom |
US3068123A (en) * | 1960-09-27 | 1962-12-11 | Dan River Mills Inc | Divinyl sulfone derivatives useful for rendering cellulosic textile fabric crease-resstant |
DE1166145B (en) * | 1960-12-28 | 1964-03-26 | Hoechst Ag | Process for dyeing and finishing textile material containing cellulose |
US3407026A (en) * | 1961-02-24 | 1968-10-22 | Deering Milliken Res Corp | Soil retention of aminoplast resin-softener-epichlorohydrin modified cellulosic fabrics obviated by inclusion of carboxymethyl cellulose in reaction system |
US3214235A (en) * | 1961-03-17 | 1965-10-26 | Monsanto Co | Crosslinked derivatives of polyhydroxy compounds and an ester of propiolic acid |
US3338883A (en) * | 1961-03-31 | 1967-08-29 | Stevens & Co Inc J P | Process for modifying polymeric materials, and modifier reactants for such use |
US3314744A (en) * | 1961-07-03 | 1967-04-18 | Gen Aniline & Film Corp | Crosslinkage of cellulose fibers with phosphate esters of di-ethanol sulfones |
US3227511A (en) * | 1961-08-02 | 1966-01-04 | Kendall & Co | Methods of forming woven stretchable fabrics |
US3512916A (en) * | 1961-10-06 | 1970-05-19 | Gaf Corp | Two step reaction of textile fibers with 2-vinylsulfonylethanol |
US3359061A (en) * | 1961-12-19 | 1967-12-19 | Clark M Welch | Process for making alkoxyethylsulfonylethyl ethers of cellulose |
US3202474A (en) * | 1962-01-23 | 1965-08-24 | Clark M Welch | Process for crosslinking cellulose with formaldehyde adducts of divinyl sulfone |
US3230031A (en) * | 1962-02-06 | 1966-01-18 | Clark M Welch | Process for making aryloxyethylsul-fonylethyl ethers of cellulose |
US3281204A (en) * | 1962-06-21 | 1966-10-25 | Clark M Welch | Polymeric adducts of divinyl sulfone with water as crosslinking agents for cellulose |
US3477802A (en) * | 1963-03-19 | 1969-11-11 | Stevens & Co Inc J P | Modification of cellulose,polyvinyl alcohol and starch with compounds characterized by ethylene radicals having an electron attracting group which stabilizes carbanions on one carbon atom thereof and an alkoxy or hydroxy group on the other |
US3528964A (en) * | 1963-08-13 | 1970-09-15 | Stevens & Co Inc J P | Process for the chemical modification of cellulosic polymers and products produced thereby |
US3294780A (en) * | 1964-01-17 | 1966-12-27 | Austin L Bullock | Process for making crosslinked cellulose derivatives utilizing halo-acrylic acids |
US3294779A (en) * | 1964-01-17 | 1966-12-27 | Austin L Bullock | Process for making crosslinked cellulose derivatives utilizing acetylenic carboxylic acids |
US3501260A (en) * | 1964-03-18 | 1970-03-17 | Stevens & Co Inc J P | Polyvinyl alcohol and starch bound to cellulosic textile substrate through reaction with beta-oxyethyl sulfones |
US3293340A (en) * | 1966-02-09 | 1966-12-20 | Union Carbide Corp | Method of producing colored structures |
US3619277A (en) * | 1969-11-26 | 1971-11-09 | Christina L Allen | Method of improving the crease resistance of a cellulosic fabric |
US8834679B2 (en) | 2012-12-26 | 2014-09-16 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
US8980054B2 (en) | 2012-12-26 | 2015-03-17 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
US9410292B2 (en) | 2012-12-26 | 2016-08-09 | Kimberly-Clark Worldwide, Inc. | Multilayered tissue having reduced hydrogen bonding |
US9416494B2 (en) | 2012-12-26 | 2016-08-16 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
US20180354853A1 (en) * | 2017-05-26 | 2018-12-13 | Clemson University Research Foundation | Covalently cross-linked lignocellulosic composites and applications thereof |
US10899667B2 (en) * | 2017-05-26 | 2021-01-26 | Clemson University | Covalently cross-linked lignocellulosic composites and applications thereof |
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