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Publication numberUS2415040 A
Publication typeGrant
Publication dateJan 28, 1947
Filing dateMar 23, 1944
Priority dateMar 23, 1944
Publication numberUS 2415040 A, US 2415040A, US-A-2415040, US2415040 A, US2415040A
InventorsRust John B
Original AssigneeMontclair Res Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Ketone-cellulose products and the process of making same
US 2415040 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Jan. 2 8,

KE'L'ONE-CELLULOSE raonuc'rs AND PROCESSOF MAKING SAME THE John B. Rust, West Orange, N. IL, assignor to Montclair Research Corporation, a corporation of New Jersey No Drawing. Application March 23, 1944, Serial No. szasss 11 Claims. (c1. 106197) 1 The present invention relates to cellulose derivatives and to the process of making same. It is an. object of this invention to provide derivatives of cellulose which are soluble in dilute a1- kalies.

It is a further object of this invention to make available cellulose derivatives which are useful as textile sizing compositions.

It is an object of this invention to provide washand laundering-fast cellulosic textile sizes.

It is a further objectto provide cellulose derivatives which may be, dissolved in alkali solutions and spun into fibers in a suitable precipitating bath for the production of artificial silk or precipitated in the form of film and foil. It

'is also an object of this invention to provide paper sizing and modifying agents.

Other objects and advantages will become apparent from the more detailed description of the invention given hereinaftein' Such detailed description should not be construed as limiting, but only by way of explanation and illustration, since numerous variations may be made by those skilled in the art without departing from the scope and spirit of the present invention.

The derivatives of the present invention may be formed by the reaction of an alkali cellulose derivative, as for instance, soda cellulose, potash cellulose, lithium cellulose, quaternaryammonium cellulose and the like, with an alpha-beta unsaturated ketone. The reaction may be effected in the cold, in some instances, and in others by the application of heat.

As instances of ketones which may be used in the process of the present invention are vinyl methyl ketone, isopropenyl methyl ketone, isopropenyl ethyl ketone, methylene-amyl methyl ketone, vinyl phenyl ketone, alpha-phenylvinyl methyl ketone, mesityl oxide, isophorone, divinyl ketone and the like. I first react cellulose with sodium hydroxide, for instance, to form soda cellulose. After aging the soda cellulose to a satisfactory degree, it is mixed with cooling with the unsaturated ketone. in the cold or the reaction mixture is allowed to warm up and further heating applied. I prefer.

suggested that the following reaction may oc- 'cur. Representing cellulose as Cell-OH:

Reaction is effected-either to employ, if possible, ketones which are substituted in the two alpha-positions, since they are then not capable of undergoing aldol condensation or resinification. However, I may use unsubstituted ketones and work with diluents or low temperature to obviate or reduce resinifying reactions. Thus, the "ketones of the present invention may be represented by:

aralkyl, olefinyl, alkynyl, and the like or R and R" may be hydrogen.

I R! R" R! Cell-OH R"oH=( :-coR cen-o-cH-cm-ooR The above is given by way of possible explanation only and should not be construed aslimiting since I do not wish to be limited by any theoretical explanation of the reaction of the present invention.

The cellulose derivatives are soluble in alkalies according to the number and kind of substituent groups. Thus, I may make a derivative which is insoluble in'alkali at ordinary temperatures but which is readily soluble by cooling the alkali suspension to about 0 C. Such solutions are valuable as textile sizing agents. tions, usually of about 1% to 10% strength, are applied to cotton, linen, or rayon goods on a padder, squeezed, dried, and coagulated by using a solution of an acid, acid salt, or a precipitating concentrated salt solution. The treated textile is washed thoroughly after coagulating and then dried. A firm hand is imparted to the fabric which is resistant to laundering and the ordinary cleansing agents. The finish-may be applied at practically any convenient stage of processing I such as before kier boiling, before dyeing and the like.

Since the derivatives of the present invention contain keto groups, they may be caused to undergo further reaction, as for instance, with aldehydes, acids, amines and ammonia, hydroxylamine, hydrazine, hydrogen cyanide and the like. Thus, if used as a sizing material, the derivatives of the present invention may be subjected to heat after coagulation which causes a further reaction ofthe keto groups with subsequent crosslinking and curing of the derivative on the tex-- tile. On the other hand, a textile sized with the derivatives of the present invention maybe treated with formaldehyde or other aldehyde in order to effect curing and fixation. Still further, the textiles sized with the derivatives of this invention may be treated with ammonia, amines, or

other nitrogenous derivatives reactive" with ketones. Such treated sized textiles are then much more receptive to dyeing by dyestuffs used for coloring Wool, silk, hair, and the like.

Cellulose in its various forms may be used in the present invention. However, after forming the alkali, or quaternary ammonium cellulose, I prefer to age it to secure some controlled degradation until the desired viscosity is obtainable. Theviscosity of the solution may be varied both by using different forms and sources of cellulose, by introducing more or less reactant and by degrading the cellulose to a greater or lesser degree.

The solu- In the reaction of the present invention, I

may use inert diluents if desired, such as ethylene dichloride; carbon tetrachloride, benzene, ethyl ether, heptane, and the like. When making the alkali cellulose, concentrations of from 15% to 50% of alkali may be used although greater or lesser concentrations can be employed. I usually prefer to employ concentrations of about 30% to 40%. This is also true of the quaternary ammonium hydroxides. When using these latter materials, solution of the cellulose sometimes 7 occurs. In such cases, the solutions may be diluted with alkali metal hydroxide solutions before reaction. Such quaternary ammonium hydroxides may be trimethylbenzyl ammonium hydroxide, tetraethylammonium hydroxide, diethyl dipropyl ammonium hydroxide, diethyl piperidinium hydroxide, methyl pyridinium hydroxide and the like.

The proportions of reactants may be varied within very large limits of, for instance, from to 100% or more of the cellulose. For several reasons it may be desirable to use an excess of unsaturated ketone. For instance, in some cases resinification reaction occurs with subsequent impoverishment of the mixture of the ketone. On the other hand, a greater proportion of unsaturated ketone may be used to accelerate the reaction, which may then be terminated before completion, if desired.

As well as utilizing the ketones given above, I may also use alpha-beta unsaturated ketones containing other negative substituents "as, for instance, alpha-cyano vinyl methyl ketone, alphacarbethoxyvinyl methyl ketone, beta-cyanovinyl methyl ketone, alpha-acetylvinyl methyl ketone, =beta-acetyl-alpha-methylvinyl ethyl ketone, and the like. These may be represented by the general formula:

where, besides being alkyl, aryl, etc., R." and R may be cyano, carboxy, carbalkoxy, aldehyde, acyl andthe like.

Therefore, the process of the present invention consists in allowing cellulose to react with an excess of a 15% to 50% (preferably about 30% to 40%) aqueous solution of an alkali such as sodium hydroxide to form alkali cellulose, the amount of alkali amounting to from 3 to about 8 moles per CGH1005 group of cellulose. To this mixture is then added from 5% to about 100% (based on dry cellulose) of an alpha-beta unsaturated ketone as above defined and reacted for a period from 1 to about 5 hours. The reaction temperature is between ice temperature and boiling, higher temperatures being employed when a degraded product (that is, one producing a lower viscosity) is desired, but in any case it is desirable ,to start the reaction at ice temperature. Afterwards the reaction mixture is acidified, whereby the product is coagulated and can be filtered, washed and dried. The dried product is capable of dissolving in dilute aqueous alkalies to form a homogeneous solution useful particularly as a wash-fast size for fabrics.

The following examples are given to illustrate the products and processes of the present invention. All proportions are in parts by weight.

Example 1.-64.1 parts oi soda cellulose, containing 10 parts of cellulose and 54.1 parts of 30% sodium hydroxide solution, were mixed with 20 parts of crushed ice and 10 parts of isopropenyl methyl ketone. The mixture was homogenized and heated at 50 C. for 2 hours. An orange colored reaction mixture resulted which on acidi'- 'fication, washing with water and acetone, and

drying gave a pale'yellow powder. This powder was soluble in 10% sodium hydroxide solution ,when cooled to 0 C. to give a viscous 5% solution having a yellow color.

Example 2.A solution of isopropenyl methyl ketone cellulose-of Example 1 was made by stirring 5 parts of the cellulose derivative with 30 parts of 33%% sodium hydroxide solution and 40 parts of water. 30 parts of crushed ice were added to eiTect solution. The solution was applied .to cotton broadcloth by a back-fllling tech? nique. The treated cloth was dried and finally treated with a 10% sulfuric acid bath. The cloth was washed thoroughly and dried. A firm somewhat stifi hand was imparted to the broadcloth which resisted laundering.

Example 32-651 parts of soda cellulose, containing 10 parts of cellulose and 54 parts of 30% sodium hydroxide solution, were mixed with parts of ice and 10 parts of mesityl oxide. The mixture was homogenized and allowed to stand at room temperature for 3 hours. The material was neutralized, washed with water and acetone, and dried. It was soluble in 10% sodium hydroxide solution with cooling to give a very viscous 5% solution.

Ezample 4.35 parts of soda cellulose, containing 10 parts of cellulose and parts of 33 sodium hydroxide solution, were mixed with 5 parts of methyl vinyl ketone in 5 parts of dioxan, The mixture was homogenized and allowed to react at room temperature for 1 hour. The mixture was then heated to 40-60 C. on a water bath for 1 hour, A dark brown reaction product was obtained. This was neutralized with acetic acid, washed with water and acetone and dried. A brown powder was secured which was soluble in 10% sodium hydroxide solution at room temperature to give a clear, brown solution.

Example 5-35 parts of soda cellulose, containing 10 parts of cellulose and 25 parts of 33 /3 sodium hydroxide solution, were mixed with 5 parts of dioxan containing 5 parts of alphamethylene-n-amyl methyl ketone. The mixture was homogenized and allowed to react at 70 C. for 3 hours. The material was acidified with acetic acid, washed with water and acetone and dried. A white fibrous powder was obtained which gave a clear white solution in 10% sodium hydroxide at roomtemperature. Cooling speeded the solution of the ketone cellulose derivative.

I claim:

1. The process of making a ketone-cellulose product which is soluble in dilute aqueous alkali solutions, which consists in reacting an alphabeta unsaturated ketone with alkali cellulose, coagulating the reaction mixture by acidifying it and recovering the reaction product by filtering, washing and drying the same; said ketone having the formula 35 R"cn=d-co-a where R is selected from the class consisting of alkyl, aryl, alkaryl, aralkyl, olefinyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo andacyl groups, and R and R" are selected from the class consisting of hydrogen and the groups corresponding to R.

2. The process of making a ketone-cellulose product which is soluble in dilute aqueous alkali solutions, which consists in allowing cellulose to 5 react with a 30% to 40% aqueous solution of sodium hydroxide until soda cellulose is formed, adding thereto an alpha-beta unsaturated ketone in amount from about 5% to 100% of the cellulose and permitting same to react at between ice temperature and below boiling temperature until a ketone-cellulose compound is formed, acidifying the reaction mixture and recovering the reaction product by filtering, washing and drying same; said ketone having the formula RI R"CH=(7COR where R is selected from the class consisting of alkyl, aryl, alkaryl, aralkyl, olefinyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo and acyl roups, and R and R" are selected from the class consisting of hydrogen and the groups corresponding to R;

3. Process of making a ketone-cellulose product which is soluble in dilute aqueous alkali solutions, which consists in reacting isopropenyl methyl ketone and alkali cellulose, acidifying the reaction mixture and recovering the reaction product by filtering, washing and drying the same. a

4. Process of making a ketone-cellulose product which is soluble in dilute aqueous alkali solutions,-which consists in reacting vinyl methyl ketone and, alkali cellulose, acidifying thereaction mixture and recovering the reaction product by filtering, washing and drying the same.

5. Process of making a ketone-cellulose prodnot which is soluble in dilute aqueous alkali solutions, which conslstsin reacting alpha-methylene-n-amyl methyl ketone and alkali cellulose, acidifying the reaction mixture and recovering the reaction product by filtering, washing and drying the same. A

6. A ketone-cellulose product soluble in dilute aqueous alkali solutions, consisting of the acidcoagulated, washed and dried reaction product or an alpha-beta unsaturated ketone and alkali- I cellulose; said ketone having the formula BI arenas-c o-a where R is selected from the class consisting of .alkyl, aryl, alkaryl, aralkyl, oleflnyl, alkynyl, cy-

ano, carboxy, carbalkoxy, aldehydo and acyl of the cellulose; said ketone having the formula R"OH=( JC0-R where R. isselected from the class consisting of alkyl, aryl, alkaryl, aralkyl, olefinyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo and 'acyl groups, and R" and R" are selected from the class consisting ofhydrogen and the groups corresponding to R.

8. A ketone-cellulose product soluble in dilute aqueous alkali solutions, consisting of the acidcoagulated, washed and dried reaction product of isopropenyl methyl ketone and alkali cellulose. I

9. A ketone-cellulose product soluble in dilute aqueous alkali solutions, consisting of the acid- 'coagulated, washed and dried reaction product of vinyl methyl ketone and alkali cellulose.

10. A ketone-cellulose product soluble in dilute aqueous alkali solutions, consisting of the acid-coagulated, washed and dried reaction product of alpha-'methylene-n-amyl methyl ketone and alkali cellulose.

11. A solution of the ketone-cellulose product of claim 6 in dilute aqueous sodium hydroxide solution.

JOHN B. RUST.

and the groups cor-

Non-Patent Citations
Reference
1 *None
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5876706 *Aug 18, 1997Mar 2, 1999S. C. Johnson & Son, Inc.Air freshener dispenser device with taper candle feature
US5919423 *Aug 20, 1997Jul 6, 1999S. C. Johnson & Son, Inc.Polymeric wick composition for air freshener candle product
US5955034 *Aug 20, 1997Sep 21, 1999S. C. Johnson & Son, Inc.Wickless; candlewax, thermoplastic polymer, polysaccharide filler
US6013231 *Dec 17, 1997Jan 11, 2000S. C. Johnson & Son, Inc.For candles having wicks which releases air-freshener in controlled manner
US6036925 *Dec 17, 1997Mar 14, 2000S. C. Johnson & Son, Inc.For dispensing of an air freshener from wickless candle product
Classifications
U.S. Classification106/198.1, 8/116.4, 536/84
International ClassificationC08B11/00, C08B11/04
Cooperative ClassificationC08B11/04
European ClassificationC08B11/04