US2362768A - Moth repelling product - Google Patents

Description

Patented Nov. 14, 1944 MOTH REPELLING PRODUCT Willard L. Morgan, Columbus, Ohio, and Earle Davis McLeod, Rumford, B. L, assignors to Arnold, Hoflman & 00., Incorporated, a corporation of Rhode Island N Drawing.

Original application August 3, 1940, Serial No. 351,200.

Divided and this application November 26, 1942, Serial No. 467,062

13 Claims. (01. 8-1365) This application is a division of application Serial No. 351,200, Patent No. 2,304,369.

This invention relates to a textile material which has been treated with a new condensation product to make the material resistant to attack by moths.

One of the objects of this invention is to provide a protein textile material which has been treated with a new condensation product of such a character as to cause the material to resist attack by moths and which at the same time will give to the protein material such as wool, casein or soya bean fiber an improved softer quality.

As further objects of our invention, we describe condensation products which may be easily applied from aqueous solutions to give finishes on cloth of a maximum softness, which effects are resistant to washing and to dry cleaning.

A still further object 0! our invention is to describe condensation products which may be used to lubricate either yarns or fabric so as to make the mechanical flow of these in weaving or sewing proceed smoothly.

The condensation products proposed for use in this invention will contain sulphur and we have found that the higher the percentage of sulphur content in the molecule the better will the condensation products repel the attack by moths on the fabric.

These products are substituted ureas, thioureas, guanidines, .biurets, guanyl ureas, or diguanidines of high molecular weight in which each of the terminal carbamyl nitrogens has been substituted through linkage with a polyamino acid amide.

These compounds are readily prepared by reacting the carbamyl derivatives, such as urea, thiourea, guanidine salts, biuret, diguanidine, or guanyl urea with the condensation products secured from aliphatic polyamines and acids or acid esters or acid chlorides.

As suitable acids for condensing with the polyamines, we prefer those containing six or more carbons and preferably saturated aliphatic acids, such as, lauric, stearic, palm oil acids, although we may use the unsaturated or substituted fatty acids, such as rincinoleic, oleic, sebacic or chlorostearic, or the cycloaliphatic, aromatic, or resin acids may also be used such as naphthenic, benzoic, creositinic, and abietic or the resin acid secured from rosin and maleic anhydride. These acids may be condensed with any of the aliphatic chlorine.

polyamines or substituted polyamines, such as,

ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexamethylene diamine, hydroxy ethyl ethylene diamine, ethyl ethylene diamine, 2,2,dimethyl-1,3,di-

amino propane, 1,3,diamino iso propanol, beta NE W i= R|CN[(OH1)r-A](CH:)IN B/ \X 1 \B4 In this formula R1 corresponds preferably to a saturated aliphatic chain containing 6 or more carbons such as would result from the use of a saturated fatty acid or any of the other various types of acids already enumerated; thus, R1 may also represent other hydrocarbon radicals of 6 or more carbons such as a cyclic alkyl, an unsaturated hydrocarbon, an aryl radical, or a residue from a terpene acid, or R1 may carry other substituting groups such as hydroxyl, carboxyl or In each case the corresponding acid, acid chloride, or ester may be used as a source to introduce this radical into our condensation products as will be shown later. R6 is used to indicate hydrocarbon groups of similar type to R1 and in a given compound may be identical with R1 or be secured from a different acid.

In the formula R2, R3, R4, and Rs may represent either hydrogen, a simple alkyl of less than five carbons, or a similar hydroxy alkyl radical such as a beta ethanol group. R3 and R4 may also represent alternatively a second acid amide chain derived from an acid and a polyamine.

The chemical groups indicated by Di and D: may be oxygen (=0) in the caseof the ureas, sulphur (=8) with the thioureas, or imido (=N'H) with the guanidines. The letter 9 represents a small whole number ranging from 0 to 3 and while D1 and D2 may be the same as in the biurets they may be difierent as in the guanyl ureas,

Depending upon the nature of the aliphatic polyamine used in the condensation with the acids, the letter A is used to represent either an amino -(NH)- group, a simple alkyl or alkylol substituted amino of less than five carbons, such as, -(NC'.5H5) or (NC:H4OH), or oxygen, or sulphur. The letters I, y, e, l, m, and t represent small whole integers, f and :i varying from 1 to 6, e 'and I from to 6, and m and t from 1 to 6, and any of the hydrogens in the CH2 groups may be substituted by a simple alkyl or a hydroxy roup.

x We have indicated in the above two paragraphs that D1 and D2 may be sulphur and when either of these are sulphur the letter A may represent any of the groups specified in the paragraph relating to letter A. When the letter A represents sulphur the letters D1 and D2 may represent any of the indicated examples as specified in the paragraph relating to D1 and D2. In other words, some sulphur will be present in the formula at either the position indicated by the letter A or the position indicated by the letters D1 and D2.

The condensation products of this invention are in many cases directly water soluble or water ispersible. In all cases the condensations are eadily dissolved after treatment with acids, such as, acetic, lactic, boric, oxalic, benzoic, salicylic,

furoic, citric, tartaric, formic, .phthalic, succinic, or alkyl naphthalene sulphonic acids or after reaction with an alkylating agent, such as, ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorhydrin, or dimethyl sulphate. The salts or 'alkylated products of our substituted urea condensates are indicated in the general formula givenwliere B represents the acid hydrogen or alkyl groups and X the acid radical or halogen group, while for our primary urea, etc., condensations B and X disappear from the formula.

The condensation products of this invention are readily prepared by heating equimolal quantities of the acid and polyamine at temperatures from 130 C. to 200 C. until the reaction is complete as shown by the loss of one molecule of water. The mix is then cooled back to 180 C. and one half mol or more of the urea or other carbamyl derivative added. Ammonia is rapidly ""liberated as the urea becomes substituted, the

temperature being held between 170 C. and 200 C. The product may be cooled and used directly or at temperatures of 80 C. to 140, the various solubilizing acid or alkylating agents may be added in quantities of .2 to .5 mol'or more.

The linking by urea or other carbamyl compounds of two or more acid polyamine, amide groups results in products of very large molecular weight which are found to show high substantivity to the various textile fibers, such as cotton, viscose, cellulose acetate, linen, jute, etc., and to give textile treatments which are permanent to washing and dry cleaning. This marked substantivity is found to arise from the presence of the urea or other similar carbamyl groups in such high molecular Weight products. The urea groups also increase the solubility in water which is very important since such large molecules which are desirable for substantivity are poorly soluble. Thus, our substituted ureas, although of double the molecular weight, are more soluble than the acid polyamine amide condensations from which they are produced.

We have found that the sensitiveness to oxidation and to heat or light of the acid polyamine amide condensations and other proposed nitrogen containing textile assistants which results in yellowing either in processing, drying, storage, or use of the treated fabrics is mainly caused by the presence of primary amino or NH: groups in the compounds and to a much lesser extent by secondary amino -(NH)-- groups. It is the primary amino group left in the acid polyamine amide condensations which is reacted upon by the urea or other carbamyl compound and removed during the formation of our substituted ureas, and we are thus able to secure compounds free of these difilculties which had checked technical use. Likewise, the urea and other carbamyl compounds will react with and eliminate secondary amino groups and the yellowing arising from such groups and it is an alternative under this invention to use sufficient urea or other carbamyl compound to combine with all the primary and the secondary amino groups in the acid polyamine amide, as well as merely the terminal groups as shown in the general formula already given. The resistance to scorching under heat is also found to be lowered to some degree by the use of unsaturatedacids as the source of R1 and R6 and while we may use them in many types of application, for products of maximumresistance we prefer the use of the saturated fatty acids.

Inasmuch as urea, thiourea, and guanidine are each decomposed readily at temperatures below C. or the reaction temperatures employed, it was impossible to foresee that the large molecule substituted urea. condensates would be stable at these temperatures or could be formed. Thus, the heating of urea and fatty acids at 160 C. does not lead to substituted ureas, but decompositions occur yielding only fatty amides as shown in U. S. 1,989,968 and U. S. 2,109,941. In a similar way we have been unable to react urea with simple fatty amides or fatty ethanol amides and we find that it is only when we use the amide of an acid and a polyamine containing either or both a primary or secondary amino group that reaction to our substituted ureas can be secured. The condensations go readily and are free of side reactions, thus, leading to full yields of products which do not need to be purified.

We find that a fatty acid radical not too high in number of carbons by which we mean below 17 carbons provides a better compound for resisting moths than fatty acid radicals with higher carbon contents. It also appears advisable that a reduction or absence of the amino group provides a better moth-proofing compound than where this group is present.

The invention will be further illustrated, but is not limited by the following examples in which the quantities are stated in parts by weight:

Example 1 143 parts (1 mol) of the condensate of lauric acid and hydroxyethyl ethylene diamine were further condensed with 19 parts /2 mol) of thiourea by addition of the thiourea at C. and raising the temperature to C. The product was a heavy viscous brown liquid which was water soluble directly or after adding acids and had the following formula:

If 38 parts (1 mol) of thiourea is added in the above example, a thiobiuret linkage is formed, which product is a viscous amber colored liquid, water and acid soluble and has the following formula: 5

or as their salts such as the acetate, fluoride, fluoborate, furoate or fluosilicate.

Example 2 200 parts (1 mol) of lauric acid were heated with 120 parts (1 mol) of diamine ethyl thio ether and the temperature gradually raised to 160 C., during which 18 parts or 1 mol of water were evolved yielding a product of the following formula:

ll CpHaa-C-NHCHzCHz-SCH:CH:NH: 3

two mols of the compound were further condensed with one mol of thiourea at 180 C., during which time ammonia was evolved and a 0 8 linkage introduced. The product obtained was water soluble after treatment with acids, such as, furoic, hydrofluoroboric, hydrofluoric. Applied to wool or casein fibers, it possessed good mothprooflng qualities and was resistant to washing and dry cleaning.

The fluosilicate salt had the following formula: 40

0 CnHza--NH-CHzCHz-S-CHzCH -NH H sm :3 onmrtt-Nn-omorrrs-cmcrn-Nn H SiFt We claim:

1. A textile moth proofed by impregnation with a substituted carbamyl compound of the following formula:

wherein R1 and Re represent a hydrocarbon radical of at least six carbons and selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cycloalkyl group, an aryl group, and a terpene acid residue, and in which R2, R2, R4 and R5 represent a material selected from the group consisting of hydrogen, a simple alkyl of less than five carbons, and an alkylol of less than five carbons, and in which R: and R4 may further represent a second acid polyamide chain, and in which general formula the carbamyl groups D1 and D2 represent a material 78 selected from the group consistingof oxygen, sulfur, and imido groups, the number of such groups being as a ranges from 0 to 3; while in the side chains the letter A represents a material selected from the group consisting of amino (NH)--, a simple alkyl substituted amino of less than five carbons, an alkylol substituted amino of less than five carbons, oxygen, and sulfur; and the integers I and i vary from 1 to 6, while e and l vary from0to6,andmandtvaryfrom1to6,andin which general formula sulfur (S) is present in at least one of the groups represented by the letters D1, D2, and A.

2. A textfle material moth proofed by impregnation with a substituted thiourea compound of the following formula:

0 CuHr- NHCHsCH:N-CHsCH:OH

CuHr-l J-NHCHsCH:-IIGH:GH:OH

3. A textile material moth proofed by impregnation with a substituted thiobiuret compound of the following formula:

4. A textile material moth proofed by impregnation with a substituted thiourea compound of the following formula:

5.. A textile material moth proofed by impregnation with a substituted carbamyl compound of' the following formula:

6. A textile material of a protein fiber which has been moth proofed by treatment in a solution of a polyalkyl amino acid amide substituted thiocarbamyl compound as set forth in claim 1.

7. A textile material of wool which has been moth proofed by treatment in a solution of a polyalkyl amino acid amide substituted thiocarbamyl compound as set forth in claim 1.

8. A textile material of casein which has been moth proofed by treatment in a solution of a polyalkyl amino acid amide substituted thiocarbamyl compound as set forth in claim 1.

9. A textile material of soya bean protein filament which has been moth proofed by treatment in a solution of a polyalkyl amino acid amide substituted thiocarbamyl compound as set forth in claim 1.

10. A textile material of a protein fiber which has been moth proofed by treatment in a solution of a polyalkyl amino acid amide substituted thiobiuret compound as set forth in claim 1.

11. A textile material of wool which has been moth prooted by treatment in a solution or a polyalkyl amino acid amide substituted thiobiuret compound as set forth in claim 1.

12. A textile material of casein which has been moth prooied by treatment in a solution or a polyalkyl amino acid amide substituted thiobiuret as set forth in claim 1.

in a solution ot'a polyalkyl amino acid amide substituted thiobiuret as set forth in claim 1.

WILLARD L. MORGAN. EARLE DAVIS MCLEOD.