US2275685A

US2275685A - Mixed polyvinyl esters containing dicarboxylic acid groups

Info

Publication number: US2275685A
Application number: US325185A
Authority: US
Inventors: Salo Martti
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1939-04-06
Filing date: 1940-03-21
Publication date: 1942-03-10
Anticipated expiration: 1959-03-10
Also published as: GB529035A

Description

' Patented Mar. 10, 1942 MIXED POLYVINYL ESTERS CONTAINING DICARBOXYLIC ACID GROUPS Martti Salo, Rochester, N. Y., assignor to- Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 21, 1940, Serial No. 325,185. In Great Britain April 6, 1939 7 Claims.

This invention relates to mixed polyvinyl esters containing lower fatty acid groups and dicarboxylic acid groups, and their preparation.

In producing photographic materials it is often desirable to employ coatings which are readily soluble in alkalies so that these materials are present initially but are removed in the developing baths used in processing. Various materials which are alkali soluble and useful for coatings are known but due to the expense involved in their preparation they are used only sparingly. An object of my'invention is to provide alkalisoluble material which can be readily coated out as a layer onto photographic film but which may be dissolved oil by treating the film with alkali. Another object of my invention is to provide a method of making materials of this type which is inexpensive and easily carried out. A further object of my invention is to provide a method of making dicarboxylic acid esters of polyvinyl compounds in which the use of pyridine or other organic base is unnecessary.

My invention in its broadest aspects comprises the treatment of a lower fatty acid ester of polyvinyl alcohol with a dicarboxylic acid anhydride,

\ in an inert solvent containing a little water, at a moderately elevated temperature. I have found that the polyvinyl ester of a lower fatty acid can be readily esterifled, taking on dicarboxylic acid groups in this manner.

Any of the lower fatty acid esters of polyvinyl alcohol may be used as the starting material of my process. For instance, polyvinyl acetate has been found suitable but the propionate or butyrate may be employed, if desired, or the mixed esters, such as the acetate propionates and acetate butyrates, might be used. As the. higher viscosity polymers introduce difliculties in carrying out the reaction, the low and medium vis- --cosity polyvinyl esters are most useful as the starting material. For example, with the polyvinyl acetates, those having a viscosity within the range of 2-60 0. p. s. are the most useful. The polyvinyl esters, which areemployed as the start- .ing material. may be either fully esterifled or partially hydrolyzed materials. With the use of partially hydrolyzed polyvinyl esters or those containing hydroxyl groups, the amount of water employed need not be as great as with a corresponding process using fully esterifled polyvinyl acetate.

The anhydride employed in my process should be the anhydride of a dicarboxylic acid in which the carbons of the two carboxyls are Joined by one or more carbons or other atoms. Examples of acids of this type are phthalic, succinic, glutaric, diglycolic and maleic. In most cases the carboxyls are joined by intermediate carbon linkages.

The solvent, which is employed, may be any solvent which has the following characteristics: 1. At least moderately miscible with water.

2. Chemically stable.

3. A solvent for the starting materials and for the final product.

I have found that the mostl suitable solvents of this nature are the lower aliphatic ketones, such as acetone, and -methyl ethyl ketone. Although the amount of solvent which is employed is not critical, I prefer to employ at least one part of solvent to one part of polyvinyl ester. Ordinarily, an amount of solvent within the range of 1 to 2 parts per part of polyvinyl ester is suflicient. The practical limits of temperature range for this reaction are between about 250-350 F. A reaction temperature within this range is ordinarily suitable. The practical limits of the range of time within which this reaction should be carried out is 5-20 hours. Increasing the time beyond this range serves no useful purpose. Under good working conditions, a time within the range of 5-8 hours is usually suflicient to obtain the desired reaction product.

The alkali solubility of the product obtained depends upon the amount of dicarboxylic acid ester groups introduced into the resin. This is governed by two factors, the proportion of phthalic anhydride and the proportion of water. In order to obtain alkali solubility, the proportion of phthalic anhydride used should be at least .75 part per part of polyvinyl ester. An amount of phthalic anhydride within the range of .75 to 1.25 parts per part of the polyvinyl ester has been found to be most satisfactory in my process. The proportion of water should be at least 0.05 part per part of polyvinyl ester to obtain alkali solubility. With an increase of the amount of phthalic anhydride and the amount of water, the amount of phthalyl introduced into the resin will be increased. However, if only one of these ingredients is increased in proportion without the other, the proportion of phthalyl introduced is not affected. If only the amount of water is increased, hydrolysis off of some of the acyl content in preparing my product will result without any added taking on of dicarboxylic acid groups. I have found that the best range for content of water in processes in accordance with my invention are 0.05 to 0.2 part for every one part of polyvinyl ester. By the means described,

' equipped with a stirring device.

- perature.

an alkali-soluble product is obtained; In order to be alkali soluble the phthalates must have a content of at least 15-20% combined phthalyl.

A formula, which I have found works very sat- With the lower boiling solvents an autoclave or refiuxingshould be used to avoid loss of solvent. The following examples illustrate my invention:

Example I 400 parts of fully esterified polyvinyl acetate, having a viscosity of 7 c; p. s., was dispersed in 400 parts of methyl ethyl ketone in arr-autoclave There was then added with stirring, 400 parts of phthalic anhydride and 43 parts of water. The autoclave was closed, the stirrer was set in motion andthe temperature of the reaction mixture was raised to 280-290" F. After stirring for five hours at this temperature, the mass was cooled to room temperature, diluted with approximately ten volumes of 70:30 acetone-water mixture. The product was precipitated into water at room temperature, washed, centrifuged and dried, at a low tem- The product, which was soluble in a number of organic solvents and in dilute alkalies, had an acetyl content of 29.6% and a phthalyl content'of 26.7%. It was found also to have a viscosity of 5 c. p. s. at 25 C. in a solution of 55:45 by weight ethyl alcohol-acetone mixture.

4 Example 11- The procedure of the above example was re-- peated except that80 parts of water was used and the reaction was run for 6 hours in an autoclave at a temperature of approximately 300 F. The

resulting product was found to be soluble in a number of organic solvents and. also in dilute aqueous alkali.

Example III a 75 pounds of, fully esterifled polyvinyl acetate, having a viscosity of 25 c. p. s., was dissolved in 75 pounds of methyl ethyl ketone in a 75 gallon steam-heated reaction vessel. 75 pounds of phthalic anhydride and 7.5 pounds of distilled rapidly as possible. The mixture was agitated for 7 hours with the temperature of the mixture kept between290 and 302 F. Tests made on smallsamples showed that the product reached solubility in 3% aqueous sodium hydroxide inabout 6% hours. Thevessel was cooled to room temperature and emptied. The product was precipitated in water with violent agitation and washed thoroughly with cold water and then with hot water. The product was dried at room. temperature and was found to have a phthalyl content of 19.2% and an acetyl content of 32.5%.

Example IV then cooled to room temperature, diluted with approximately 10 volumes of a 70:30 acetonewater mixture and precipitated in water at room temperature. ing, an enclosed reaction vessel such as an autoclave or refluxing vessel was not necessary as the temperature employed did not drive off any appreciable amount of the acetonyl acetone.

The dicarboxylic acid esters of polyvinyl alcohol of my invention may be combined with bases, either organic or inorganic, to form salts. For

' instance, a polyvinyl acetate phthalate or polysalts may be prepared by a double-decomposition water was added thereto. The reaction vessel was closed and the temperature was raised as vinyl acetate succinate of my invention may be mixed with an aqueous solution of an alkali metal carbonate, such as sodium bicarbonate, to form awater-soluble alkali metal salt. Heavy metal reaction of the alkali metal salt with a watersoluble salt of the heavy metal. For instance, the sodium salt of polyvinyl acetate phthalate may be combined with copper sulfate in aqueous solution to form the copper salt of the polyvinyl acetate phthalate. The polyvinyl ester in accordance with my invention may also be combined with ammonia or a. substituted ammonia such as ethyl amine or an ethanolamine to form the corresponding water-soluble salt.

The esters which I have described herein, are desirable aslayers on photographic film; for instance, for anti-halation backings, or the like, when mixed with a small proportion of a dye, such as a blue or black dye, which will overcome halation. This backing, dueto its alkali solubility. will be dissolved by a conventional type of developing bath, thus leaving a transparent negative. They are also useful in any other cases where a temporary resin coating is desired,

The viscosity of polyvinyl acetate, referred to herein, is' the viscosity in centipoises at 20 C. of a solution containing 8.6 gmsof tate in 10000. of benzene.

' I claim:

1. The process of preparing a polyvinyl ester containing lower fatty acid and dicarboxylic acid,

groups which comprises reacting together approximately one'part of 'a polyvinyl ester of a fatty acid of 2-4 carbon atoms, approximately .75-1.25 parts of a dicarboxylic acid anhydride and approximately 0.05-0.2 part of water in approximately 1-2 parts of an inert, water-miscible solvent for the starting materials and the polyvinyl ester prepared, at a temperature within the range 01' 250-350 F.

2. The process of preparing a polyvinyl ester containing lower fatty acid and dicarboxylic acid groups which comprises reacting together approximately one part of a polyvinyl ester of a fatty acid of 2-4 carbon atoms, one part of a dicarboxyllc acid anhydride and 0.1 part of water in approximately 1-2 parts of an inert watermiscible solvent for the starting materials and the polyvinyl ester prepared, at a temperature within the range of 250-350" F.

- 3. The process of preparing a polyvinyl ester containing lower fatty acid and phthalyl groups which comprises reacting together approximately one part of a polyvinyl ester of a fatty acid of 2-4 carbon atoms, approximately .75-1.25 parts of phthalic anhydride and approximately 0.05-0.2 part of water in approximately 1-2 parts of an inert water-miscible solvent for the starting materials and the polyvinyl ester prepared,'at a temperature within the range of 250-350 F.

4. The process of preparing alpolyvinyl ester containing lower fatty acid and succinyl groups As the solvent used was high boilpolyvinyl I acewhich comprises reacting together approximately one part of a polyvinyl ester of a fatty acid 012-4 carbon atoms, approximately 175-125 parts of succinic anhydride and approximately 0.05-0.2 part of water in approximately 1-2 parts of an inert water-miscible solvent for the starting materials and the polyvinyl ester prepared, at a temperature within the range of250-350.

5. The process of preparing a polyvinyl ester containing acetyl and dicarboxylic acid groups which comprises reacting together approximately one part of polyvinyl acetate, approximately .75- 1.25 parts of a dicarboxylic acid anhydride and approximately 0.05-0.2 part of water in approxi- 1-2 parts of an inert water-miscible solvent for the starting materials and the polyvinyl ester prepared, at a temperature within the range of 250-350 F.

proximately one part of polyvinyl acetate,'approximately 315-125 parts of phthalic anhydride and approximately 0.05-0.2 part of water in approximately 1-2 parts of'methyl ethyl ketone, at a temperature within the range or 250-350 F. 7. The process of preparing a polyvinyl ester containing lower fatty acid and dicarboxylic acid groups which comprises reacting together approximately one part of a polyvinyl ester of a fatty acid of 2-4 carbon atoms, one part of a dicarboxylic acid anhydride and 0.1 part. of water in approximately 1-2 parts of methyl ethyl ketone, at a temperature within the range of 250 350 F. s p i t MAR'I'II SALO.

6. The process of preparing a'polyvinyl acetate phthalate which comprises reacting together ap-